Bismuth-Catalyzed Growth of SnS2 Nanotubes and Their Stability

"Ab initio" structure solution from electron diffraction data obtained by a combination of automated diffraction tomography and precession technique

Using a combination of our recently developed automated diffraction tomography (ADT) module with precession electron technique (PED), quasi-kinematical 3D diffraction data sets of an inorganic salt (BaSO(4)) were collected. The lattice cell parameters and their orientation within the data sets were found automatically. The extracted intensities were used for "ab initio" structure analysis by direct methods. The data set covered almost the complete set of possible symmetrically equivalent reflections for an orthorhombic structure. The structure solution in one step delivered all heavy (Ba, S) as well as light atoms (O). Results of the structure solution using direct methods, charge flipping …

Structural characterization of iron oxide/hydroxide nanoparticles in nine different parenteral drugs for the treatment of iron deficiency anaemia by electron diffraction (ED) and X-ray powder diffraction (XRPD)

Drug products containing iron oxide and hydroxide nanoparticles (INPs) are important for the treatment of iron deficiency anaemia. Pharmaceuticals prepared by the complexation of different kinds of INPs and carbohydrates have different physicochemical and biopharmaceutic characteristics. The increasing number of parenteral non-biological complex drugs (NBCD) containing iron requires physicochemical methods for characterization and enabling of cross comparisons. In this context the structure and the level of crystallinity of the iron phases may be connected to the in vitro and in vivo dissolution rates, which etiologically determine the therapeutic and toxic effects. X-ray powder diffraction…

Synthesis of MoO3 Nanostructures and Their Facile Conversion to MoS2 Fullerenes and Nanotubes.

The fast thermolysis of ammonium molybdate leads to a mixture of MoO3 and Mo5.3O14.5(OH)2.8(H2O)1.36 with spherical and rod-like morphologies. The oxide mixture can be converted in quantitative yield to inorganic fullerene-type (IF) MoS2 and MoS2 nanotubes (NT) by H2S reduction using a facile and quick procedure. The products were studied by X-Ray Diffraction (XRD) and by Transmission Electron Microscopy (TEM). TEM analysis reveals that the spherical and rod-like morphology of the oxide precursor is preserved during the H2S treatment.

A new hydrous Al-bearing pyroxene as a water carrier in subduction zones

Abstract A new Hydrous Al-bearing PYroxene (HAPY) phase has been synthesized at 5.4 GPa, 720 °C in the MgO–Al2O3–SiO2–H2O model system. It has the composition Mg2.1Al0.9(OH)2Al0.9Si1.1O6, a C-centered monoclinic cell with a = 9.8827(2), b = 11.6254(2) c = 5.0828(1) A and β = 111.07(1)°. The calculated density is 3.175 g/cm3 and the water content is 6.9% H2O by weight. Its structure has been solved in space group C2/c by the recently developed automated electron diffraction tomography method and refined by synchrotron X-ray powder diffraction. HAPY is a single chain inosilicate very similar to pyroxenes but with three instead of two cations in the octahedral layer, bonded to four oxygens and…

Strong enhancement of the Breit-Wigner-Fano Raman line in carbon nanotube bundles caused by plasmon band formation

We investigate the origin of the Breit-Wigner-Fano line in the Raman spectra of individual single-walled carbon nanotubes and their bundles. Using confocal Raman microscopy and atomic-force microscopy we found that the Breit-Wigner-Fano line intensity increases strongly with the bundle thickness. We confirmed this result by Raman investigations of partially decomposed bundles, which were additionally investigated by transmission electron microscopy. Our random-phase approximation based theory, which identifies the Breit-Wigner-Fano line as an excited band of plasmon-phonon modes, is fully consistent with the experimental results.

Automated Diffraction Tomography: A New Era for Electron Crystallography

Extended abstract of a paper presented at Microscopy and Microanalysis 2011 in Nashville, Tennessee, USA, August 7–August 11, 2011.

Ab Initio Structure Determination of Vaterite by Automated Electron Diffraction

tion that is fundamental for understanding material properties. Still, a number of compounds have eluded such kinds of analysis because they are nanocrystalline, highly disordered, with strong pseudosymmetries or available only in small amounts in polyphasic or polymorphic systems. These materials are crystallographically intractable with conventional Xray or synchrotron radiation diffraction techniques. Single nanoparticles can be visualized by high-resolution transmission electron microscopy (HR-TEM) up to sub�ngstrom resolution, [2] but obtaining 3D information is still a difficult task, especially for highly beam-sensitive materials and crystal structures with long cell parameters. Elec…

IVIVC for fenofibrate immediate release tablets using solubility and permeability as in vitro predictors for pharmacokinetics.

The goal of this study was to investigate the in vitro-in vivo correlation (IVIVC) for fenofibrate immediate release (IR) tablet formulations based on MeltDose-technique. The in vitro determined drug solubility and permeability data were related to the C(max) values observed from two in vivo human studies. Solubility and permeation studies of fenofibrate were conducted in medium simulating the fasted state conditions in the upper jejunum, containing the surfactant compositions of the six formulations at different concentrations. The behavior of all surfactant compositions was characterized by surface tension, dynamic light scattering, and cryo-TEM. The obtained solubility and permeation dat…

Crystalline nanorods as possible templates for the synthesis of amorphous biosilica during spicule formation in Demospongiae.

In tandem: High-resolution TEM shows that during the initial stages of demosponge spicule formation, a primordial crystalline structure is formed within the axial filament. The recently developed electron diffraction tomography technique (ADT) reveals that the nanorods have a layered structure that matches smectitic phyllosilicates. These intracellular nanorods have been considered as precursors of mature spicules. High-resolution microscopy shows that, during the initial stages of demosponge spicule formation, a primordial crystalline structure is formed within the axial filament. The recently developed electron diffraction tomography technique reveals that the nanorods have a layered stru…

A Novel Approach Towards Carbon–Ru Electrodes with Mesoporosity for Supercapacitors

Biosilicification of loricate choanoflagellate: organic composition of the nanotubular siliceous costal strips of Stephanoeca diplocostata.

SUMMARY Loricate choanoflagellates (unicellular, eukaryotic flagellates; phylum Choanozoa) synthesize a basket-like siliceous lorica reinforced by costal strips (diameter of approximately 100 nm and length of 3 μm). In the present study, the composition of these siliceous costal strips is described, using Stephanoeca diplocostata as a model. Analyses by energy-dispersive X-ray spectroscopy (EDX), coupled with transmission electron microscopy (TEM), indicate that the costal strips comprise inorganic and organic components. The organic, proteinaceous scaffold contained one major polypeptide of mass 14 kDa that reacted with wheat germ agglutinin. Polyclonal antibodies were raised that allowed …

From Layered Molybdic Acid to Lower-Dimensional Nanostructures by Intercalation of Amines under Ambient Conditions

Nanostructures of varied dimensionality such as rods, scrolls, and disks of molybdenum oxide have been synthesized in gram quantities under ambient conditions using exfoliation of the layers as a synthetic tool. Intercalation of alkylamines (CnH2n+2NH2, where n = 3, 4, 8, 12, and 16) into yellow molybdic acid (MoO3·2H2O) and subsequent treatment with nitric acid resulted in molybdenum oxide nanorods, nanodisks, or oxide−amine composite nanorods. The sizes of the nanoparticles range from a few nanometers to micrometers in length and 10 to 200 nm in diameter. Detailed X-ray, scanning electron microscopy, and transmission electron microscopy analyses reveal an inverse relation between the size…

Facile hydrothermal synthesis of crystalline Ta2O5 nanorods, MTaO3 (M = H, Na, K, Rb) nanoparticles, and their photocatalytic behaviour

Alkali metal tantalates are of interest for applications in photocatalysis as well as in high temperature resistance or capacitor dielectric materials. We have synthesized nanosized Ta2O5 rods and MTaO3 cubes (M = Na, K, Rb) hydrothermally and demonstrate the pH dependence of the synthesis of tantalum oxide and tantalate nanoparticles. The morphologies of the nanoparticles range from particle agglomerates in acidic reaction media over rods at neutral pH to tantalate cubes in basic reaction media. Whereas there is no apparent influence of the base cation on the particle morphology, there is a pronounced effect on the particle composition. At high base concentrations cubic tantalate particles…

Nanoparticle Vesicles Through Self Assembly of Cyclodextrin- and Adamantyl-Modified Silica

Stable nanoparticle vesicles were for the first time prepared from adamantyl- and cyclodextrin (CD)-modified silica nanoparticles forming host-guest interactions in aqueous solution. Adamantyl-functionalized nanoparticles were obtained from thiol-isocyanate reaction of thiol-modified nanoparticles with 1-adamantyl isocyanate. The CD modified silica particles were isolated from a reaction of mono-6-para-toluenesulfonyl-β-cyclodextrin with the thiol functionalized silica under microwave conditions in basic media. The obtained particles were characterized in respect of agglomeration and self-assembly behavior in aqueous solution by dynamic light scattering and transmission electron microscopy.…

Low temperature synthesis of monodisperse nanoscaled ZrO2with a large specific surface area

Thermal decomposition of Zr(C(2)O(4))(2)·4H(2)O within an autoclave or in a conventional tube furnace at temperatures below 380 °C resulted in nano- and micron-sized ZrO(2), respectively. Reactions under autogenic pressure yielded monodisperse monoclinic (m) and tetragonal (t) ZrO(2) nanoparticles with an average diameter of ~8 nm and interconnected t-ZrO(2) nanoparticles with diameters of ~4 nm, depending on the synthesis temperature. Samples were characterised by X-ray diffraction (XRD), small angle X-ray scattering (SAXS), scanning electron microscopy (SEM), transmission electron microscopy (TEM) associated with energy dispersive X-ray spectroscopy (EDS), Raman microspectroscopy and phot…

Anhydrous Amorphous Calcium Oxalate Nanoparticles from Ionic Liquids: Stable Crystallization Intermediates in the Formation of Whewellite

The mechanisms by which amorphous intermediates transform into crystalline materials are not well understood. To test the viability and the limits of the classical crystallization, new model systems for crystallization are needed. With a view to elucidating the formation of an amorphous precursor and its subsequent crystallization, the crystallization of calcium oxalate, a biomineral widely occurring in plants, is investigated. Amorphous calcium oxalate (ACO) precipitated from an aqueous solution is described as a hydrated metastable phase, as often observed during low-temperature inorganic synthesis and biomineralization. In the presence of water, ACO rapidly transforms into hydrated whewe…

Synthesis of a quenchable high-pressure form of magnetite (h-Fe3O4) with composition Fe1(Fe2+0.75Mg0.26)Fe2(Fe3+0.70Cr0.15Al0.11Si0.04)2O4

We report the synthesis of h-magnetite, ideally h-Fe 3 O 4 with considerable amounts of substitutional cations (Cr, Mg, Al, Si) and quenchable to ambient conditions. Two types of experiments were performed at 18 GPa and 1800 °C in a multi-anvil press. In one, we used an oxide mixture with a majoritic stoichiometry Mg 1.8 Fe 1.2 (Al 1.4 Cr 0.2 Si 0.2 Mg 0.2 )Si 3 O 12 , with Si and Mg in excess as starting material (MA-367, MA-380). In the second type of experiment (MA-376), we started from an oxide mixture on the composition of the Fe-oxide phase obtained in MA-367. The Fe-oxide phases of both experiments were investigated by electron microprobe and transmission electron microscopy includin…

Microphase separation upon crystallization of small amphiphilic molecules: ‘low’ temperature form II of sodium benzoate (E 211)

A so far unknown low temperature polymorph (form II crystallized at 350 °C) of the common food preservative sodium benzoate (NaBz; E 211) could be crystallized by annealing (7 days) of the poorly crystalline technical material. Its crystal structure was solved by indexing a tiny single crystal by electron diffraction followed by structure solution and refinement applying powder X-ray diffraction (PXRD). The new polymorph shows many structural similarities to form I (crystallized at 420 °C). Both form I and II are the result of a microphase separation: the structures consist of pseudo-hexagonal packings of rod-shaped micelles where the core consists of sodium cations being coordinated by the…

Solution synthesis of nanoparticular binary transition metal antimonides

The preparation of nanoengineered materials with controlled nanostructures, for example, with an anisotropic phase segregated structure or a regular periodicity rather than with a broad range of interparticle distances, has remained a synthetic challenge for intermetallics. Artificially structured materials, including multilayers, amorphous alloys, quasicrystals, metastable crystalline alloys, or granular metals, are mostly prepared using physical gas phase procedures. We report a novel, powerful solution-mediated approach for the formation of nanoparticular binary antimonides based on presynthesized antimony nanoparticles. The transition metal antimonides M-Sb (M = Co, Ni, Cu(2), Zn) were …

Design and synthesis of colloidal nanocrystal heterostructures with tetrapod morphology.

Darstellung und struktur von (EtO)2P(O)CH2Si(Me)2CH2SnMe2Cl—ein sechsringchelat mit sesselkonformation und PO ⋯ Sn(Cl)Me2CH2-trigonaler bipyramide am Lewis-aciden Zinn

Abstract The title compound (EtO)2P(O)CH2Si(Me)2CH2SnMe2Cl (2) has been synthesized by reaction of the new functional Grignard reagent (EtO)2P(O)CH2CH2SiMe2CH2MgCl with Me3SnCl and subsequent treatment with Me2SnCl2. 2 crystallizes in the non-centrosymmetric orthorhombic space group P212121. The structure was refined to a final R-value of 0.0476. The tin atom is pentacoordinated and exhibits a nearly ideal trigonal-bipyramidal coordination (SnCl 2.518(3), Sn ⋯ O 2.371(5) A). This coordination results from a 6-membered chelate involving a chair conformation. The structure of 2 is compared with analogous compounds containing a PO ⋯ Sn- or CO ⋯ Sn-coordination in the first place and a noncy…

Crystal structure determination of a new LaPO4 phase in a multicomponent glass ceramic via 3D electron diffraction

Abstract A glass ceramic from the MgO–Al2O3–SiO2 system containing additives of ZrO2, TiO2, La2O3 and P2O5 was investigated. Via x-ray powder diffraction (XRPD) and Transmission electron microscopy(TEM) the crystalline phases present could be identified as MgAl2O4 (Spinel), orthorhombic ZrTiO4 and a polymorph of LaPO4 with a previously unknown crystal structure. The crystal structure of this LaPO4 phase was solved ab initio via 3D ED Data. The polymorph occurs in a distorted barite structure type in the same space group (P21/n) as the stable monazite type polymorph, however the density is higher and the La has a higher coordination number. Furthermore the LaPO4 is present in a spinodal reli…

Controlled synthesis of linear and branched Au@ZnO hybrid nanocrystals and their photocatalytic properties.

Colloidal Au@ZnO hybrid nanocrystals with linear and branched shape were synthesized. The number of ZnO domains on the Au seeds can be controlled by the solvent mixture. Imidazole-functionalized Au@ZnO hybrid nanocrystals were soluble in water and exhibited a greatly enhanced photocatalytic activity compared to ZnO nanocrystals. The pristine heterodimeric NPs were characterized using transmission electron microscopy (TEM), X-ray diffraction (XRD), and UV-Vis spectroscopy.

Magnetic transitions in double perovskiteSr2FeRe1−xSbxO6(0⩽x⩽0.9)

The double perovskites ${\mathrm{Sr}}_{2}\mathrm{Fe}M{\mathrm{O}}_{6}$ $(M=\mathrm{Re},\mathrm{Mo})$ belong to the important class of half-metallic magnetic materials. In this study we explore the effect of replacing the electronic $5d$ buffer element Re with variable valency by the main group element Sb with fixed valency. X-ray diffraction reveals ${\mathrm{Sr}}_{2}{\mathrm{FeRe}}_{1\ensuremath{-}x}{\mathrm{Sb}}_{x}{\mathrm{O}}_{6}$ $(0lxl0.9)$ to crystallize without antisite disorder in the tetragonally distorted perovskite structure (space group $I4∕mmm$). The ferrimagnetic behavior of the parent compound ${\mathrm{Sr}}_{2}{\mathrm{FeReO}}_{6}$ changes to antiferromagnetic upon Sb subst…

Smectic Liquid-Crystalline Colloids by Miniemulsion Techniques

Direct Synthesis of Aluminosilicate IWR Zeolite from a Strong Interaction between Zeolite Framework and Organic Template.

A large amount of zeolite structures are still not synthetically available or not available in the form of aluminosilicate currently. Despite significant progress in the development of predictive concepts for zeolite synthesis, accessing some of these new materials is still challenging. One example is the IWR structure as well. Despite successful synthesis of Ge-based IWR zeolites, direct synthesis of aluminosilicate IWR zeolite is still not successful. In this report we show how a suitable organic structure directing agent (OSDA), through modeling of an OSDA/zeolite cage interaction, could access directly the aluminum-containing IWR structure (denoted as COE-6), which might allow access to…

Elucidating Gating Effects for Hydrogen Sorption in MFU-4-Type Triazolate-Based Metal-Organic Frameworks Featuring Different Pore Sizes

A highly porous member of isoreticular MFU-4-type frameworks, [Zn(5)Cl(4)(BTDD)(3)] (MFU-4l(arge)) (H(2)-BTDD=bis(1H-1,2,3-triazolo[4,5-b],[4',5'-i])dibenzo[1,4]dioxin), has been synthesized using ZnCl(2) and H(2)-BTDD in N,N-dimethylformamide as a solvent. MFU-4l represents the first example of MFU-4-type frameworks featuring large pore apertures of 9.1 Å. Here, MFU-4l serves as a reference compound to evaluate the origin of unique and specific gas-sorption properties of MFU-4, reported previously. The latter framework features narrow-sized pores of 2.5 Å that allow passage of sufficiently small molecules only (such as hydrogen or water), whereas molecules with larger kinetic diameters (e.…

Ab initio structure determination and quantitative disorder analysis on nanoparticles by electron diffraction tomography.

Nanoscaled porous materials such as zeolites have attracted substantial attention in industry due to their catalytic activity, and their performance in sorption and separation processes. In order to understand the properties of such materials, current research focuses increasingly on the determination of structural features beyond the averaged crystal structure. Small particle sizes, various types of disorder and intergrown structures render the description of structures at atomic level by standard crystallographic methods difficult. This paper reports the characterization of a strongly disordered zeolite structure, using a combination of electron exit-wave reconstruction, automated diffrac…

Synthesis and immobilization of molecular switches onto titaniumdioxide nanowires

Abstract The precursor [Fe III (L)Cl (L =  N , N ′-bis(2′-hydroxy-3′-methyl-benzyliden)-1,7-diamino-4-azaheptane) is combined with [Mo(CN) 8 ] 4− yields a star shaped nona-nuclear cluster, [Mo IV {(CN)Fe III (L)} 8 ]Cl 4 . This Fe 8 Mo molecule is a high-spin system at room temperature. On cooling to 20 K some of the iron(III) centres in the molybdenum(IV)-star switch to the low-spin state as proven by Mossbauer spectroscopy. This molecule was deposited on TiO 2 nanowires by electrostatic interactions between the cluster cations and the surface functionalized titanium oxide nanowire. The synthesis and surface binding of the multistable molecular switch was demonstrated using IR and UV–Vis s…

Molecular Camouflage: Making Use of Protecting Groups To Control the Self-Assembly of Inorganic Janus Particles onto Metal-Chalcogenide Nanotubes by Pearson Hardness

Hard and soft: Binding of inorganic Pt@Fe3O4 Janus particles to WS2 nanotubes through their Pt or Fe3O4 domains is governed by the difference in Pearson hardness: the soft Pt block has a higher sulfur affinity than the harder magnetite face; thus the binding proceeds preferentially through the Pt face. This binding preference can be reversed by masking the Pt face with an organic protecting group.

Highly stable and porous porphyrin-based zirconium and hafnium phosphonates – electron crystallography as an important tool for structure elucidation† †Electronic supplementary information (ESI) available: Experimental procedures, analytical data including NMR spectroscopy, Pawley fits, TG, IR, microscopy and sorption measurements. CCDC 1831844. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c8sc01533c

A highly porous and stable Zr-MOF containing a planar porphyrin-based tetraphosphonic acid was synthesized and characterized regarding its sorption properties and chemical stability.

Multistep Crystallization Pathways in the Ambient‐Temperature Synthesis of a New Alkali‐Activated Binder

Structural insights into M2O-Al2O3-WO3 (M = Na, K) system by electron diffraction tomography.

TheM2O–Al2O3–WO3(M= alkaline metals) system has attracted the attention of the scientific community because some of its members showed potential applications as single crystalline media for tunable solid-state lasers. These materials behave as promising laser host materials due to their high and continuous transparency in the wide range of the near-IR region. A systematic investigation of these phases is nonetheless hampered because it is impossible to produce large crystals and only in a few cases a pure synthetic product can be achieved. Despite substantial advances in X-ray powder diffraction methods, structure investigation on nanoscale is still challenging, especially when the sample i…

Hydrothermal growth mechanism of SnO2 nanorods in aqueous HCl

Abstract Rutile-type nanorods of SnO2 were obtained in a one-pot hydrothermal synthesis starting from SnCl4·5H2O and HCl in a temperature range between 200 and 240°C. Although the nanorods are polydisperse, the average length of the nanorods could be adjusted from 13 to 65 nm by varying of the reaction temperature. The resulting anisotropic nanocrystals were characterized using powder X-ray diffraction (PXRD), (high resolution-) transmission electron microscopy (HR-TEM), and selected area electron diffraction (SAED). The particle growth proceeds via a dissolution-recrystallization process with soluble [SnCl5(H2O)]− intermediates, as confirmed by PXRD, Raman spectroscopy, and magic angle spi…

Crystalline Non‐Equilibrium Phase of a Cobalt(II) Complex with Tridentate Ligands

In six-coordinate complexes, flexible tridentate ligands enable mer, cis-fac, and trans-fac stereoisomers. With labile metal ions of the first transition metal series, typically only the final thermodynamic product is available because of the rapid isomerization processes. Here we report on the structural characterization of a so far elusive kinetic intermediate of [Co(ddpd)2](BF4)2 (1; ddpd = N,N′-dimethyl-N,N′-dipyridine-2-yl-pyridine-2,6-diamine). Microcrystals of the cis-fac isomer of 1 were obtained by rapid precipitation. The solid-state structure of cis-fac-1 was determined from electron diffraction data.

Diels-Alder Reactions of Tetraphenylcyclopentadienones in Nanochannels: Fabrication of Nanotubes from Hyperbranched Polyphenylenes

Cover Picture: Nanostructuring with a Crosslinkable Discotic Material (Small 8/2007)

Innentitelbild: Fluorescent Nanowires Self-Assembled through Host-Guest Interactions in Modified Calcein (Angew. Chem. 32/2011)

ChemInform Abstract: Preparation and Structure of (EtO)2P(O)CH2Si(Me)2CH2SnMe2Cl. A Six- Membered Chelate Ring with Chair Conformation and a P=O××. times.Sn(Cl)Me2CH2-Trigonal Bipyramid at the Lewis-Acidic Tin.

Synthetic Approaches to Functionalized Chalcogenide Nanotubes

Recent advances in the preparation of zeolites for the selective catalytic reduction of NOx in diesel engines

Metal-exchanged zeolites with small pore sizes have attracted much attention in recent years due to their application in the selective catalytic reduction (SCR) of NOx in diesel engines. Typically, copper-chabazite (e.g. Cu-SSZ-13) has been gradually used as an SCR catalyst in heavy-duty diesel vehicles over the last decade due to its relatively excellent catalytic performance and stability. However, most SSZ-13 zeolites are still prepared via the traditional hydrothermal process in the presence of organic templates, requiring consecutive solid separation and thermal treatment steps to achieve the final zeolite products. In recent years, several strategies for the environmentally friendly p…

Elucidating structural order and disorder phenomena in mullite-type Al4B2O9 by automated electron diffraction tomography

The crystal structure and disorder phenomena of Al4B2O9, an aluminum borate from the mullite-type family, were studied using automated diffraction tomography (ADT), a recently established method for collection and analysis of electron diffraction data. Al4B2O9, prepared by sol-gel approach, crystallizes in the monoclinic space group C2/m. The ab initio structure determination based on three-dimensional electron diffraction data from single ordered crystals reveals that edge-connected AlO6 octahedra expanding along the b axis constitute the backbone. The ordered structure (A) was confirmed by TEM and HAADF-STEM images. Furthermore, disordered crystals with diffuse scattering along the b axis…

Solid-State Synthesis of “Bamboo-Like” and Straight Carbon Nanotubes by Thermolysis of Hexa-peri-hexabenzocoronene–Cobalt Complexes

Supramolecular PEG-co-oligo(p-benzamide)s prepared on a peptide synthesizer.

An automated synthesis protocol has been developed for the preparation of oligo(p-benzamide)s on solid support using a commercial peptide synthesizer employing a variation of standard Fmoc chemistry. Bis(trichloromethyl carbonate) in NMP was used to activate the aromatic carboxylic acids for acylation of secondary aromatic amines on solid support. N-Protected hepta(p-benzamide) was automatically prepared on solid support and manually converted to a solid supported block co-oligomer by attaching a poly(ethylene glycol) chain. Cleavage from the support could be achieved with minimal loss of the p-methoxybenzyl N-protective group. While the N-protected block co-oligomer was molecularly dissolv…

Automated electron diffraction tomography - a new tool for nano crystal structure analysis

Automated electron Diffraction Tomography (ADT) comprises an upcoming method for “ab intio” structure analysis of nano crystals. ADT allows fine sampling of the reciprocal space by sequential collection of electron diffraction patterns while tilting a nano crystal in fixed tilt steps around an arbitrary axis. Electron diffraction is collected in nano diffraction mode (NED) with a semi-parallel beam with a diameter down to 50 nm. For crystal tracking micro-probe STEM imaging is used. Full automation of the acquisition procedure allowed optimisation of the electron dose distribution and therefore analysis of highly beam sensitive samples. Cell parameters, space group and reflection intensitie…

Reversible Selbstorganisation von Metallchalkogenid-Metalloxid- Nanostrukturen basierend auf dem Pearson-Konzept

&Titel gek rzt. OK?& Die Nanotechnologie hat ein Entwicklungsstadium erreicht, in dem nicht mehr einzelne Nanopartikel, sondern komplexere Systeme im Fokus des Interesses stehen. Solche Strukturen bestehen aus zwei oder mehr unterschiedlichen Materialien, wie Metall-HalbleiterHybride, die die Eigenschaften beider Materialien effektiv vereinen. Der Aufbau von Nanopartikeln aus mehreren Komponenten mit unterschiedlichen optischen, elektronischen, magnetischen oder chemischen Eigenschaften kann zu neuartigen Funktionalit ten f hren, die unabh ngig von den einzelnen Komponenten masgeschneidert werden k nnen, um spezifischen Anforderungen zu gen gen. M gliche Anwendungen liegen in Gebieten wie d…

Reversible self-assembly of metal chalcogenide/metal oxide nanostructures based on Pearson hardness.

Nanotechnology has reached a stage of development where not individual nanoparticles but rather systems of greater complexity are the focus of concern. These complex structures incorporate two or more types of materials, an example of which is the formation of metal–semiconductor hybrids, which effectively combine the properties of both materials. The assembly of multicomponent nanoparticles from constituents with different optical, electrical, magnetic, and chemical properties can lead to novel functionalities that are independent of the individual components and may be tailored to fit a specific application. These applications include such far-reaching challenges as solar energy conversio…

Hydrogen peroxide sensors for cellular imaging based on horse radish peroxidase reconstituted on polymer-functionalized TiO2 nanorods

We describe the reconstitution of apo-horse radish peroxidase (apo-HRP) onto TiO2 nanorods functionalized with a multifunctional polymer. After functionalization, the horse radish peroxidase (HRP) functionalized TiO2 nanorods were well dispersible in aqueous solution, catalytically active and biocompatible, and they could be used to quantify and image H2O2 which is a harmful secondary product of cellular metabolism. The shape, size and structure of TiO2 nanorods (anatase) were analyzed by transmission electron microscopy (TEM), high resolution TEM (HRTEM), electron diffraction (ED) and X-ray diffraction (XRD). The surface functionalization, HRP reconstitution and catalytic activity were con…

Atomic structure solution of the complex quasicrystal approximant Al77Rh15Ru8 from electron diffraction data

The crystal structure of the novel Al77Rh15Ru8phase (which is an approximant of decagonal quasicrystals) was determined using modern direct methods (MDM) applied to automated electron diffraction tomography (ADT) data. The Al77Rh15Ru8E-phase is orthorhombic [Pbma,a= 23.40 (5),b= 16.20 (4) andc= 20.00 (5) Å] and has one of the most complicated intermetallic structures solved solely by electron diffraction methods. Its structural model consists of 78 unique atomic positions in the unit cell (19 Rh/Ru and 59 Al). Precession electron diffraction (PED) patterns and high-resolution electron microscopy (HRTEM) images were used for the validation of the proposed atomic model. The structure of the E…

ChemInform Abstract: Facile Synthesis and Characterization of Monocrystalline Cubic ZrO2Nanoparticles.

Abstract Crystalline ZrO2 nanoparticles were prepared from zirconium isopropoxide by slow hydrolysis and subsequent hydrothermal treatment of solutions containing various amounts of sodium hydroxide at 180 °C. Whereas moderately basic solutions lead to the formation of nanoparticles of monoclinic ZrO2 with plate-like morphology, and nanoparticles of the cubic ZrO2 high-temperature polymorph with diameters of approx. 5 nm were obtained from strongly basic solutions. The morphology, structure and properties of as-synthesized nanoparticles were characterized using HRTEM, XRD, Raman spectroscopy, UV–vis, PL spectroscopy and BET measurements. The formation of both, the monoclinic and the cubic p…

Electron Crystallography on Polymorphs

Structure analysis via electron diffraction in combination with x-ray powder diffraction and simulation methods has been performed on single crystals of small organic molecules which form polymorphs. For two different examples of pigments and non-linear optical active material data collection, cell parameter and space group determination, structure analysis and refinement are discussed.

Uniaxial Alignment of Polycyclic Aromatic Hydrocarbons by Solution Processing

The self-organization of two polycyclic aromatic hydrocarbons with different aromatic core sizes, dodecylphenyl-substituted hexa-peri- hexabenzocoronene and an extended disk consisting of 96 carbon atoms 6-fold-alkyl-substituted, on the surface from solution has been investigated. Highly ordered surface layers of both materials could be obtained by the zone-casting technique, despite an apparently low self-organization in drop-cast films. The zone-cast films revealed high macroscopic uniaxial orientation of the columns with a molecular edge-on arrangement on the glass support as confirmed by polarized optical microscopy, UV-vis measurements in polarized light, high-resolution transmission e…

Titelbild: Reversible Selbstorganisation von Metallchalkogenid-Metalloxid- Nanostrukturen basierend auf dem Pearson-Konzept (Angew. Chem. 41/2010)

Structure Determination by Electron Crystallography Using a Simulation Approach Combined with Maximum Entropy with the Aim of Improving Material Properties

Solving a crystal structure is only one of the many problems involved in the process of improving material properties. Because it is difficult to obtain large single crystals from most polymeric and many monomeric organic materials, it is essential to develop electron crystallography to make reliable crystal structure analysis possible.

Tailoring of the electrical and thermal properties using ultra-short period non-symmetric superlattices

Thermoelectric modules based on half-Heusler compounds offer a cheap and clean way to create eco-friendly electrical energy from waste heat. Here we study the impact of the period composition on the electrical and thermal properties in non-symmetric superlattices, where the ratio of components varies according to (TiNiSn)���:(HfNiSn)���������, and 0 ��� n ��� 6 unit cells. The thermal conductivity (��) showed a strong dependence on the material content achieving a minimum value for n = 3, whereas the highest value of the figure of merit ZT was achieved for n = 4. The measured �� can be well modeled using non-symmetric strain relaxation applied to the model of the series of thermal resistanc…

Facile Large Scale Synthesis of WS2 Nanotubes from WO3 Nanorods Prepared by a Hydrothermal Route.

Abstract Hexagonal WO 3 nanorods of 5–50 nm in diameter and 150–250 nm in length have been synthesised in gram quantities by a low temperature hydrothermal route using citric acid as a structural modifier and hexadecylamine as a templating agent. The ratio of [A]/[W] play an important role on WO 3 nanorods formation. These WO 3 nanorods were found highly suitable as a precursor for the synthesis of a good yield of multiwalled WS 2 nanotubes by reducing them with H 2 S at 840 °C for 30 min. The length and the wall thickness of the WS 2 nanotubes could be altered by controlled reduction of the oxide precursor. The morphology, structure and the composition of the WO 3 nanorods and WS 2 nanotub…

Synthesis of a New Copper-Azobenzene Dicarboxylate Framework in the Form of Hierarchical Bulk Solids and Thin Films without and with Patterning

Reaction of copper(II) acetate with azobenzene-4,4′-dicarboxylic acid results in the formation of a metal–organic framework with the unexpected stoichiometry of Cu(II):ligand of 2:1. The bulk synthesis results in microspheres assembled from either nanobricks or nanoflakes, depending on the ratio of the reactants in solution. While the former behaves like a bulk solid with clear reflections in the X-ray and electron diffraction experiments, the latter obviously is dominated by surface effects, with a significant fraction of slightly expanded elemental cells and a significantly increased outer surface area. The material could also be deposited on a variety of surfaces using a stepwise layer-b…

Detecting Crystalline Nonequilibrium Phases on the Nanometer Scale

The use of Automated electron Diffraction Tomography (ADT) is presented as a novel approach for crystallization studies at the nanometer scale for nonequilibrium phases. Here, ADT was applied to elucidate the structural identity of the recently reported hexagonal morphology of caffeine crystals, which grow only on specific surfaces. Caffeine was crystallized from solution on a specially treated TEM carbon grid. The analysis of ADT data revealed that the lattice parameters of these hexagons match those of the high temperature α- form of caffeine. Furthermore, it was observed that in this hexagonal morphology, the α-form remained stable for a prolonged period of time. The stabilization of hex…

Morphology of Sponge Spicules: Silicatein a Structural Protein for Bio-Silica Formation

Most forms of multicellular life have developed a calcium-based skeleton, while only a few specialized organisms complement their body plan with silica, such as sponges (phylum Porifera). However, the way in which sponges synthesize their silica is exceptional. They use an enzyme, silicatein, for the polymerization/polycondensation of silica, and thereby form their highly resistant and stabile massive siliceous skeletal elements (spicules). During this biomineralization process (i.e., biosilicification), hydrated amorphous silica is deposited within highly specialized sponge cells, ultimately resulting in structures that range in size from micrometers to meters. This peculiar phenomenon has…

Solution Synthesis of a New Thermoelectric Zn1-xSb Nanophase and Its Structure Determination Using Automated Electron Diffraction Tomography

Engineering materials with specific physical properties have recently focused on the effect of nanoscopic inhomogeneities at the 10 nm scale. Such features are expected to scatter medium- and long-wavelength phonons thereby lowering the thermal conductivity of the system. Low thermal conductivity is a prerequisite for effective thermoelectric materials, and the challenge is to limit the transport of heat by phonons, without simultaneously decreasing charge transport. A solution-phase technique was devised for synthesis of thermoelectric "Zn(4)Sb(3)" nanocrystals as a precursor for phase segregation into ZnSb and a new Zn-Sb intermetallic phase, Zn(1+delta)Sb, in a peritectoid reaction. Our …

The role of biosilica in the osteoprotegerin/RANKL ratio in human osteoblast-like cells

Abstract Earlier studies have demonstrated that biosilica, synthesized by the enzyme silicatein, induces hydroxyapatite formation in osteoblast-like SaOS-2 cells. Here we study the effect of biosilica on the expressions of osteoprotegerin [OPG] and the receptor activator for NF-κB ligand [RANKL] in the SaOS-2 cell model. We show that during growth of SaOS-2 cells on biosiliceous matrices hydroxyapatite formation is induced, while syntheses of cartilaginous proteoglycans and sulfated glycosaminoglycans are down-regulated. Furthermore, quantitative real-time RT-PCR analysis revealed a strong time-depended increase in expression of OPG in biosilica exposed SaOS-2 cells while the steady-state e…

Amphiphile Blockcopolymere mit einem flexiblen Block und einem kettensteifen Segment aus“zylindrischen Bürstenpolymeren”: metallocenkatalysierte Synthese und Bildung von Riesenmicellen

Fe-doped Beta zeolite from organotemplate-free synthesis for NH3-SCR of NOx

Two types of Beta zeolites, one from organotemplate-free synthesis with a Si/Al ratio of 9 and the other from a commercial one with a Si/Al ratio of 19, were employed here to dope Fe for NH3-SCR of NOx. Fe-Beta (Si/Al = 9) exhibits much higher activity than Fe-Beta (Si/Al = 19), especially at low-temperature regions (<250 °C). In addition, it also exhibits better hydrothermal stability as compared with Fe-Beta (Si/Al = 19), which demonstrates that it is a promising SCR catalyst with good activity as well as hydrothermal stability. The correlation between the quantitative calculation of the content of isolated Fe3+ in Beta zeolites and the NO conversion rate at 150 °C shows a linear relation…

The role of electron diffraction in zeolite structure determination

Because electron diffraction can sample individual microcrystals, it is clear that this single crystal method can facilitate, in at least two ways, structure determination for inorganic materials, such as zeolites, that are preferentially microcrystalline. First, in a qualitative application, three-dimensional tilts of individual small crystals, to map the reciprocal lattice, greatly facilitates unit cell and space group determination when powder diffraction indexing programs fail. If incoherent multiple scattering leads to violation of systematic absences, these absences can be restored by collection of precession diffraction patterns based on the Vincent-Midgley method [1], as demonstrate…

Switchable Supramolecular Crosslinking of Cyclodextrin-Modified Hyperbranched Polyethylenimine via Anthraquinone Dyes

Two anthraquinone dyes, 5,8-di-N-adamantylamino-1,4-dihydroxyanthraquinone (AQ-OH) and 1,4-di-N-adamantylaminoanthraquinone (AQ-H), are synthesized. The combination of AQ-OH and AQ-H with hyperbranched polyethylenimine (PEI) bearing covalently attached β-cyclodextrin spontaneously formed host–guest complexes with hydrodynamic diameters of about 260 nm. Even enlarged structures of the trifunctional AQ-H were observed via DLS. Repeated measurements show that their assembly and disassembly is reversible with a critical point at 26 °C and therefore switchable via temperature. Also superstructures up to 100 μm were detected via TEM, cryo-TEM-, and SEM. Hence, a smart colored network of switchabl…

Improvement of catalytic activity over Cu--Fe modified Al-rich Beta catalyst for the selective catalytic reduction of NOx with NH3

Copper and iron bimetal modified Al-rich Beta zeolites from template-free synthesis were prepared for selective catalytic reduction (SCR) of NOx with NH3 in exhaust gas streams. Comparing to the Cu-based and Fe-based mono-component Beta catalysts, Cu(3.0)-Fe(1.3)-Beta bi-component catalyst shows better low-temperature activity and wider reaction-temperature window. Over 80% of NO conversion can be achieved at the temperature region of 125–500 °C. Due to the synergistic effect of copper and iron evidenced by XRD, UV–Vis–NIR, EPR and XPS measurements, the dispersion state of active components as well as the ratio of Cu2+/Cu+ and Fe3+/Fe2+ were improved over Cu(3.0)-Fe(1.3)-Beta. Isolated Cu2+…

Hemin-coupled iron(III)-hydroxide nanoparticles show increased uptake in Caco-2 cells

Abstract Objectives The absorption of commonly used ferrous iron salts from intestinal segments at neutral to slightly alkaline pH is low, mainly because soluble ferrous iron is easily oxidized to poorly soluble ferric iron and ferrous iron but not ferric iron is carried by the divalent metal transporter DMT-1. Moreover, ferrous iron frequently causes gastrointestinal side effects. In iron(III)-hydroxide nanoparticles hundreds of ferric iron atoms are safely packed in nanoscaled cores surrounded by a solubilising carbohydrate shell, yet bioavailability from such particles is insufficient when compared with ferrous salts. To increase their intestinal uptake iron(III)-hydroxide nanoparticles …

Metal—Organic Chemical Vapor Deposition Synthesis of Hollow Inorganic-Fullerene-Type MoS2 and MoSe2 Nanoparticles.

VS2 nanotubes containing organic-amine templates from the NT-VOx precursors and reversible copper intercalation in NT-VS2.

Supramolecular organic-inorganic hybrid assemblies with tunable particle size: interplay of three noncovalent interactions.

Low melting Metal Catalysed Growth of Tin Disulfide Nanotubes

AbstractWe report here the synthesis of tin disulfide nanotubes by a vapour liquid solid growth using bismuth, a low melting metal, as a catalyst. The reaction was carried out in a single step process by heating SnS2 and bismuth in a horizontal tube furnace at 800oC. TEM analysis allowed proposing a plausible mechanism for the formation of SnS2 nanotubes. Pure material could be obtained by optimizing the reaction based on a product analysis using powder X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM) combined with energy dispersive X-ray spectroscopy (EDX).

Selective Synthesis of Hollow and Filled Fullerene-like (IF) WS2 Nanoparticles via Metal–Organic Chemical Vapor Deposition

The synthesis of WS2 onion-like nanoparticles by means of a high-temperature metal–organic chemical vapor deposition (MOCVD) process starting from W(CO)6 and elemental sulfur is reported. The react...

Hybrid chalcogenide nanoparticles: 2D-WS2 nanocrystals inside nested WS2 fullerenes.

The MOCVD assisted formation of nested WS2 inorganic fullerenes (IF-WS2) was performed by enhancing surface diffusion with iodine, and fullerene growth was monitored by taking TEM snapshots of intermediate products. The internal structure of the core–shell nanoparticles was studied using scanning electron microscopy (SEM) after cross-cutting with a focused ion beam (FIB). Lamellar reaction intermediates were found occluded in the fullerene particles. In contrast to carbon fullerenes, layered metal chalcogenides prefer the formation of planar, plate-like structures where the dangling bonds at the edges are stabilized by excess S atoms. The effects of the reaction and annealing temperatures o…

Automated Electron Diffraction Tomography

Ab-initio structure analysis by electron diffraction is hampered by two major problems: insufficient number of reflections sampled and an intensity alteration by dynamical scattering contribution or beam damage. Thus, in recent years the principles of automated diffraction tomography (ADT) allowing systematic reciprocal space sampling and automated data analysis were developed. Here the basic ideas of ADT and its general applicability will be discussed along with some examples of solved structures.

Electron crystallography and organic materials with non-linear optical properties

Results of electron microscopic studies of crystal structures of a number of bis-benzylidene cyclohexanones are presented. It is shown that some of these compounds are efficient crystalline non-linear optically active (NLO) chromophores with second harmonic generation (SHG) properties. Appropriately functionalized chromophores of this type can be used as a polycondensation comonomer to produce partly crystalline main-chain NLO-active polymers. Electron diffraction crystal structural data, obtained for very small crystals, allowed us to get reasonable estimations of macroscopic crystal NLO-coefficients, relating quantum-chemically calculated molecular first hyperpolarizability components to …

Iron Oxide/Hydroxide Nanoparticles with Negatively Charged Shells Show Increased Uptake in Caco-2 Cells

The absorption of commonly used ferrous iron salts from intestinal segments at neutral to slightly alkaline pH is low, mainly because soluble ferrous iron is easily oxidized to poorly soluble ferric iron and because ferrous iron, but not ferric iron, is carried by the divalent metal transporter DMT-1. Moreover, ferrous iron frequently causes gastrointestinal side effects. Iron hydroxide nanoparticles with neutral and hydrophilic carbohydrate shells are alternatively used to ferrous salts. In these formulations gastrointestinal side effects are rare because hundreds of ferric iron atoms are safely packed in nanoscaled cores surrounded by the solubilizing shell; nevertheless, iron bioavailabi…

Structure characterization of hard materials by precession electron diffraction and automatic diffraction tomography: 6H-SiC semiconductor and Ni1+xTe1 embedded nanodomains

Using a combination of automated diffraction tomography and precession electron diffraction techniques, quasi-kinematical electron diffraction data sets were collected from intermetallic Ni1+xTe1 embedded nanodomains and ion-thinned specimens of 6H–SiC semiconductor. Cell parameters and space groups were found automatically from the reconstructed 3D diffraction volume. The extracted intensities were used for fast ab initio structure determination by direct methods.

Topochemical Reduction of La2NiO3F2: The First Ni-Based Ruddlesden–Popper n = 1 T′-Type Structure and the Impact of Reduction on Magnetic Ordering

Within this study, we show that a broad range of reduced phases La2NiO3F2−Δ can be derived from Ruddlesden–Popper-type La2NiO3F2 using a reductive topochemical defluorination method based on reacti...

Half-Heusler superlattices as model systems for nanostructured thermoelectrics

The efficiency of thermoelectric materials is directly related to the dimensionless figure of merit , therefore, one of the means to improve ZT is to reduce the thermal conductivity. Our research focuses on half-Heusler superlattices (SLs) and the relationship between the SL period and the thermal conductivity. The cross-plane thermal conductivity of DC-sputtered TiNiSn/HfNiSn SLs was measured by the 3 method at room temperature and a clear reduction of was achieved for all SL periods, in particular for periods smaller than 20 nm. Moreover, the thermal conductivities of TiNiSn and HfNiSn single films display reduced values compared to the literature data for bulk materials. Furthermore, we …

Solid-State Pyrolyses of Metal Phthalocyanines: A Simple Approach towards Nitrogen-Doped CNTs and Metal/Carbon Nanocables

Solid-state pyrolysis of organometallic precursors has emerged as an alternative method for preparing carbon nanostructures such as carbon nanotubes (CNT) and carbon anions. The morphology of the tubes can be controlled by the nature of the precursors and the pyrolysis procedures, and micrometer long nanotubes, composed of metal carbide wires encased in a graphitic sheath. Cobalt phthalocyanine (CoPc) as well as iron phthalocyanine were pyrolyzed at different temperatures to obtain CNTs. HRTEM and energy-dispersion X-Ray analysis disclosed that the core consisted of long, iron-containing single crystals and that the core was fully surrounded by crystallized graphic carbon. Iron-filled carbo…

Structure analysis of titanate nanorods by automated electron diffraction tomography

A hitherto unknown phase of sodium titanate, NaTi3O6(OH)·2H2O, was identified as the intermediate species in the synthesis of TiO2 nanorods. This new phase, prepared as nanorods, was investigated by electron diffraction, X-ray powder diffraction, thermogravimetric analysis and high-resolution transmission electron microscopy. The structure was determined ab initio using electron diffraction data collected by the recently developed automated diffraction tomography technique. NaTi3O6(OH)·2H2O crystallizes in the monoclinic space group C2/m. Corrugated layers of corner- and edge-sharing distorted TiO6 octahedra are intercalated with Na+ and water of crystallization. The nanorods are typically …

Wet Chemical Synthesis and a Combined X-ray and Mössbauer Study of the Formation of FeSb2 Nanoparticles

Understanding how solids form is a challenging task, and few strategies allow for elucidation of reaction pathways that are useful for designing the synthesis of solids. Here, we report a powerful solution-mediated approach for formation of nanocrystals of the thermoelectrically promising FeSb(2) that uses activated metal nanoparticles as precursors. The small particle size of the reactants ensures minimum diffusion paths, low activation barriers, and low reaction temperatures, thereby eliminating solid-solid diffusion as the rate-limiting step in conventional bulk-scale solid-state synthesis. A time- and temperature-dependent study of formation of nanoparticular FeSb(2) by X-ray powder dif…

Asymmetric tungsten oxide nanobrushes via oriented attachment and Ostwald ripening

Tungsten oxide nanobrushes were synthesized using a solvothermal approach that lead to self-branching in the presence of citric acid and hexadecylamine as surfactants. Our synthetic approach yielded branched nanorods of tungsten oxide in a single synthetic step. Based on our results, we propose a phenomenological pathway for the formation, branching, and assembly of these tungsten oxide brushes. The formation of tungsten oxide brushes proceeds by thermal decomposition of ammonium tungstate in the presence of citric acid and hexadecylamine. The pale blue powder obtained after solvothermal reaction was analyzed by X-ray diffraction (XRD), transmission electron microscopy (TEM) and high-resolu…

Hierarchical Assembly of TiO2 Nanoparticles on WS2 Nanotubes Achieved Through Multifunctional Polymeric Ligands

Thefunctionalization of nanotubes is required in order to bene-fit from their outstanding properties, as any application inmaterials and devices is hindered by processing and manipu-lation difficulties. Only the attachment of appropriate chem-ical functionalities on the nanotube surface allows tailoringof the properties for the respective applications. As an ex-ample, the enhancement of the nanotube solubility is onemajor task since most pristine nanotubes are insoluble inboth water and organic solvents. Thus, the improvement ofthe solubility by chemical functionalization is an importantconcept for synthetic chemists and materials scientists. Tai-loring of the surface chemical bonds might a…

Structure solution with automated electron diffraction tomography data: different instrumental approaches

Summary Over the past few years automated electron diffraction tomography has become an established technique for structure solution of nano-crystalline material. The intentional choice of an arbitrary tilt axis and thus, the use of nonoriented diffraction patterns (off-zone acquisition) together with fine equidistant sampling of the reciprocal space result in high quality intensity data sets. Coupling automated electron diffraction tomography with electron beam precession (Vincent & Midgley, 1994) enables sampling of intensities between the static slices of reciprocal space and therefore enhances the quality of intensity data further; relatively complex structures have been solved using 3D…

Synthesis, characterization and functionalization of nearly mono-disperse copper ferrite CuxFe3−xO4 nanoparticles

Magnetic nanocrystals are of great interest for a fundamental understanding of nanomagnetism and for their technological applications. CuxFe3−xO4 nanocrystals (x ≈ 0.32) with sizes ranging between 5 and 7 nm were synthesized starting from Cu(HCOO)2 and Fe(CO)5 using oleic acid and oleylamine as surfactants. The nanocrystals were characterized by high-resolution transmission electron microscopy (HRTEM), electron diffraction (ED), magnetization studies and Mossbauer spectroscopy. The CuxFe3−xO4 particles are superparamagnetic at room temperature 300 K with a saturation magnetization of 30.5 emu g−1. Below their blocking temperature of 60 K, they become ferrimagnetic, and at 5 K they show a co…

ChemInform Abstract: Solution Synthesis of Nanoparticular Binary Transition Metal Antimonides.

The transition metal antimonides MSb with M: Co, Ni, and Zn and Cu2Sb with particle sizes ranging from 20 to 60 nm are prepared using presynthesized antimony nanoparticles and activated metal nanoparticles as precursors.

Supramolecular Nanocycles Comprisingβ-Cyclodextrin-click-Ferrocene Units: Rings of Rings of Rings

We applied 1,3-dipolar cycloaddition to bind ethynylferrocene onto 6I-azido-6I-deoxycyclomaltoheptaose under microwave assisted conditions. The process was investigated by (1) H NMR, FT-IR spectroscopy, and MALDI-TOF mass spectrometry. The ability of the synthesized compound to self-organize to cyclic supramolecular structures was investigated by dynamic light scattering measurements and cryo-transmission electron microscopy.

Charoite, as an example of a structure with natural nanotubes

Charoite from the Murun massif in Yakutiya, Russia (Vorob’ev 2008) was investigated using automated electron diffraction tomography (ADT) (Kolb et al. 2007, 2008; Mugnaioli et al. 2010) and precession electron diffraction (PED) (Mugnaioli et al. 2010, 2009), which allowed to determine the structure of charoite for the first time. The structure was solved ab initio in space group P21/m by direct methods using a fully kinematic approach. The least squares refinements with 2878 reflections F(hkl) >4s F converged to unweighted/weighted residuals R 1/wR 2 • 0.173/0.21 (Rozhdestvenskaya et al. 2010).

On heterocyclic systems containing bismuth(III) 2. Eight-membered heterocycles Cl/Br/I-M(CH2CH2CH2)2X with lewis acidic group 15 atoms M  As, Sb, Bi and donor atoms X  NR, S: a contribution to the value of the electronegativity of bismuth(III)

Abstract Paths to the ligands (Cl/Br-CH2CH2CH2)2NR/O/S/Se, R  Me, Bz, iPr, iBu, to the diGrignard reagents (Cl/BrMg-CH2CH2CH2)2NR/O/S, R  Me, Bz, iPr, iBu and to the eight-membered group 15 heterocycles (Cl/Br/I-As/Sb/Bi(CH2CH2CH2)2NR/S, R  Me, Bz, iBu are given. 13C-NMR, IR and Raman spectra are discussed; for the compound ClSb(CH2CH2CH2)2NMe the crystal structure analysis is given : the antimony atom is clearly Lewis acidic with ψ-trigonal-bipyramidal coordination and a transannular Sb⋯N interaction of 2.385(2) A. For such a configuration the values of the 13C-NMR chemical shifts of the α-CH2-groups (e.g. Cl-As/Sb/Bi(αCH2CH2CH2)2NMe 34.6, 25.9, 46.6 ppm) display clearly a sequence N > …

Supramolekulare organisch-anorganische Hybridaggregate mit variabler Partikelgröße: Zusammenspiel von drei nichtkovalenten Wechselwirkungen

Ni@Fe2O3 heterodimers: controlled synthesis and magnetically recyclable catalytic application for dehalogenation reactions

Ni@Fe2O3 heterodimer nanoparticles (NPs) were synthesized by thermal decomposition of organometallic reactants. After functionalization, these Ni@Fe2O3 heterodimers became water soluble. The pristine heterodimeric NPs were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), Mossbauer spectroscopy and magnetic susceptibility measurements. A special advantage of the heterodimers lies in the fact that nanodomains of different composition can be used as catalysts for the removal of environmentally hazardous halogenated pollutants.

Plasmonic Core–Satellite Assemblies as Highly Sensitive Refractive Index Sensors

Highly sensitive and spectrally tunable plasmonic nanostructures are of great demand for applications such as SERS and parallel biosensing. However, there is a lack of such nanostructures for the midvisible spectral regions as most available chemically stable nanostructures offer high sensitivity in the red to far red spectrum. In this work, we report the assembly of highly sensitive nanoparticle structures using a hydroxylamine mediated core–satellite assembly of 20 nm gold nanoparticle satellites onto 60 nm spherical gold cores. The average number of satellites allows tuning the plasmon resonance wavelength from 543 to 575 nm. The core–satellite nanostructures are stable in pH ranges from…

Expanding the Variety of Zirconium‐based Inorganic Building Units for Metal–Organic Frameworks

Two new zirconium-based metal-organic frameworks with the composition [Zr6 O4 (OH)4 (OAc)6 (BDC)3 ] (CAU-26) and [Zr5 O4 (OH)4 (OAc)4 (BDC)2 ] (CAU-27) are reported, which were synthesized from acetic acid, a rarely utilized but green and sustainable solvent (BDC2- : 1,4-benzenedicarboxylate). Structure determination aided by automated electron diffraction tomography revealed that CAU-26 is composed of layers of well-known {Zr6 O8 } clusters interconnected by terephthalate ions. In contrast CAU-27 exhibits a three-dimensional structure with a so far unknown type of one-dimensional inorganic building unit (IBU), which can be rationalized as condensed polyhedron-sharing chains of {Zr6 O8 } cl…

Lösliche Einzelmolekül-Nanogele mit kontrollierbarer Struktur als Matrix für wirksame Enzymmodelle

Quasi-parallel precession diffraction: Alignment method for scanning transmission electron microscopes.

Abstract A general method to set illuminating conditions for selectable beam convergence and probe size is presented in this work for Transmission Electron Microscopes (TEM) fitted with µs/pixel fast beam scanning control, (S)TEM, and an annular dark field detector. The case of interest of beam convergence and probe size, which enables diffraction pattern indexation, is then used as a starting point in this work to add 100 Hz precession to the beam while imaging the specimen at a fast rate and keeping the projector system in diffraction mode. The described systematic alignment method for the adjustment of beam precession on the specimen plane while scanning at fast rates is mainly based on …

Molybdenum oxide nitrides of the Mo_{2}(O,N,\square)_{5}$ type : on the way to Mo_{2}O_{5}$

Abstract: Blue-colored molybdenum oxide nitrides of the Mo-2(O,N,square)(5) type were synthesized by direct nitridation of commercially available molybdenum trioxide with a mixture of gaseous ammonia and oxygen. Chemical composition, crystal structure, and stability of the obtained and hitherto unknown compounds are studied extensively. The average oxidation state of +5 for molybdenum is proven by Mo K near-edge X-ray absorption spectroscopy; the magnetic behavior is in agreement with compounds exhibiting (MoO6)-O-v units. The new materials are stable up to similar to 773 K in an inert gas atmosphere. At higher temperatures, decomposition is observed. X-ray and neutron powder diffraction, e…

Corrosion of Heritage Objects: Collagen‐Like Triple Helix Found in the Calcium Acetate Hemihydrate Crystal Structure

Abstract Helical motifs are common in nature, for example, the DNA double or the collagen triple helix. In the latter proteins, the helical motif originates from glycine, the smallest amino acid, whose molecular confirmation is closely related to acetic acid. The combination of acetic acid with calcium and water, which are also omnipresent in nature, materializing as calcium acetate hemihydrate, was now revealed to exhibit a collagen‐like triple helix structure. This calcium salt is observed as efflorescence phase on calcareous heritage objects, like historic Mollusca shells, pottery or marble reliefs. In a model experiment pure calcium acetate hemihydrate was crystallized on the surface of…

A Zone-Casting Technique for Device Fabrication of Field-Effect Transistors Based on Discotic Hexa-peri-hexabenzocoronene

Artificial granularity in two-dimensional arrays of nanodots fabricated by focused-electron-beam-induced deposition.

We have prepared 2D arrays of nanodots embedded in an insulating matrix by means of focused-electron-beam-induced deposition using the W(CO)(6) precursor. By varying the deposition parameters, i.e. the electron beam current and energy and the raster constant, we obtain an artificial granular material with tunable electrical properties. The analysis of the temperature dependence of the conductivity and of the current-voltage characteristic suggests that the transport mechanism is governed by electron tunneling between artificial grains. In order to understand the nature of the granularity and thus the microstructural origin of the electronic transport behavior, we perform TEM and micro-Raman…

Ab-initio crystal structure analysis and refinement approaches of oligo p-benzamides based on electron diffraction data.

Ab-initio crystal structure analysis of organic materials from electron diffraction data is presented. The data were collected using the automated electron diffraction tomography (ADT) technique. The structure solution and refinement route is first validated on the basis of the known crystal structure of tri-p-benzamide. The same procedure is then applied to solve the previously unknown crystal structure of tetra-p-benzamide. In the crystal structure of tetra-p-benzamide, an unusual hydrogen-bonding scheme is realised; the hydrogen-bonding scheme is, however, in perfect agreement with solid-state NMR data.

Structural Characterisation of Complex Layered Double Hydroxides and TGA-GC-MS Study on Thermal Response and Carbonate Contamination in Nitrate- and Organic-Exchanged Hydrotalcites

Layered double hydroxides (LDHs) are versatile materials used for intercalating bioactive molecules in the fields of pharmaceuticals, nutraceuticals and cosmetics, with the purpose of protecting them from degradation, enhancing their water solubility to increase bioavailability and improving their pharmacokinetic properties and formulation stability. Moreover, LDHs are used in various technological applications to improve stability and processability. The crystal chemistry of hydrotalcite-like compounds was investigated by X-ray powder diffraction (XRPD), automated electron diffraction tomography (ADT) and thermogravimetric analysis (TGA)-GC-MS to shed light on the mechanisms involved in io…

Electron Crystallography in Mineralogy and Materials Science

The mineral aerinite is investigated by electron crystallography (NED and HREM). TEM results of aerinite are compared with X-ray and synchrotron powder diffraction data. Six selected area electron diffraction (SAED) patterns and two HREM images from Pb5MoO8 single crystals are used to solve their structure. The unit cell parameters of these crystals confirm the known powder diffraction data.

The effect of trivalent framework heteroatoms in Cu-CHA on the Selective Catalytic Reduction of NO

Abstract The effect of the trivalent framework atoms (Si4+/M3+ = 13-105) in Cu exchanged CHA-type zeolites was investigated for the selective catalytic reduction of NO with NH3. While the increased hydrophobicity of B-CHA compared to Al-CHA could make it a good candidate for low temperature SCR, the material was too unstable under reaction conditions and the exchanged Cu2+ did not remain isolated. Consequently a lower activity and selectivity than for Al-CHA were observed. Ga-CHA on the other hand showed a similar Cu2+ speciation as Al-CHA at similar Si4+/M3+ ratios. The difference in catalytic activity was remarkably small. While Ga-CHA was less stable upon hydrothermal aging, this was mar…

Combination of Confocal Raman Spectroscopy and Electron Microscopy on the Same Individual Bundles of Single-Walled Carbon Nanotubes

We report a method to investigate the same individual single-walled carbon nanotube (SWNT) bundles with both transmission electron microscopy (TEM) and Raman spectroscopy. Free-standing individual bundles are obtained by depositing a solution of suspend SWNTs on a carbon film with a regular pattern of holes, which can be localized by TEM and also by confocal Raman microscopy. While most of the TEM images predict that the bundles consist of tubes with a similar diameter, we will show that occasionally a certain tube diameter can be associated with a particular radial breathing mode frequency of the Raman spectrum. Single-walled carbon nanotubes (SWNTs) are one-dimensional molecular structure…

A simple approach towards one-dimensional mesoporous carbon with superior electrochemical capacitive activity.

One-dimensional (1D) mesoporous carbons with highly ordered 3D interconnected pore structure and large-diameter pore size (10–20 nm) have been synthesized by a simple precursor-controlled thermolysis approach; such unique carbonaceous frameworks show superior capacitive behavior in electrochemical double-layer capacitors.

A new microporous 12-ring zincosilicate THK-2 with many terminal silanols characterized by automated electron diffraction tomography.

A newly synthesized microporous zincosilicate THK-2 (estimated structural composition: |(H2O)6.7(C6H13N)0.9|[Li0.5Zn3.1Si32O62.7(OH)9.3]) was characterized by single-crystal electron diffraction using the automated electron diffraction tomography (ADT) approach in combination with powder X-ray diffraction. The lattice constants and space group of as-synthesized THK-2 were a = 2.50377(7) nm, b = 1.43866(4) nm, c = 0.505369(8) nm, and Pccn (no. 56) with orthorhombic symmetry. Because the crystal lattice was almost identical to a hexagonal lattice (), the first several peaks in its powder X-ray diffraction data severely overlapped, which suppressed the structural information to decide the fram…

An average structure model of the intermediate phase between sodalite and cancrinite

Abstract Powder samples of the intermediate phase between sodalite and cancrinite (INT) have been synthesized hydrothermally. The formation of the INT phase was proved by both PXRD and TGA analysis and its stoichiometric composition was found to be |Na6.95(1)(CO3)0.48(2) (H2O)6.18(6)|[AlSiO4]6. The comparison of the intensity ratios of PXRD data with a SCXRD measurement indicates the formation of a comparable phase with the typical strong stacking disorder. The hexagonal lattice parameters with a=1266.3(2) pm and c=1586(1) pm and the unit cell setting were determined by Pawley fits. The average lattice and the stacking disorder along c axis could be confirmed by the reconstruction of three-…

Synthesis and Structure Determination of the Hierarchical Meso-Microporous Zeolite ITQ-43

[EN] The formation of mesopores in microporous zeolites is generally performed by postsynthesis acid, basic, and steam treatments. The hierarchical pore systems thus formed allow better adsorption, diffusion, and reactivity of these materials. By combining organic and inorganic structure-directing agents and high-throughput methodologies, we were able to synthesize a zeolite with a hierarchical system of micropores and mesopores, with channel openings delimited by 28 tetrahedral atoms. Its complex crystalline structure was solved with the use of automated diffraction tomography.

Ab-initio-Strukturbestimmung von Vaterit mit automatischer Beugungstomographie

Overcoming the Insolubility of Molybdenum Disulfide Nanoparticles through a High Degree of Sidewall Functionalization Using Polymeric Chelating Ligands

Structural Characterization of Organics Using Manual and Automated Electron Diffraction

In the last decade the importance of transmission electron microscopic studies has become increasingly important with respect to the characterization of organic materials, ranging from small organic molecules to polymers and biological macromolecules. This review will focus on the use of transmission electron microscope to perform electron crystallography experiments, detailing the approaches in acquiring electron crystallographic data. The traditional selected area approach and the recently developed method of automated diffraction tomography (ADT) will be discussed with special attention paid to the handling of electron beam sensitive organic materials.

Solid-state pyrolysis of polyphenylene-metal complexes: A facile approach toward carbon nanoparticles

Novel polyphenylene-metal complexes with discotic, linear, and dendritic geometries are synthesized by using a facile approach consisting of reactions between Co2(CO)8 and ethynyl functionalities in dichloromethane. Various carbon nanoparticles (CNPs), including graphitic carbon nanotubes (CNTs), graphitic carbon rods, and carbon-metal hybrid particles are obtained from the solid-state pyrolysis of these complexes. The ultimate structures of the CNPs are found to be dependant on the structure and composition of the starting compounds. Precursors containing graphenes always result in graphitic CNTs in high yield, whereas dendritic precursors give rodlike carbon materials. Alternatively, line…

Rare-earth ion exchanged Cu-SSZ-13 zeolite from organotemplate-free synthesis with enhanced hydrothermal stability in NH3-SCR of NOx

The relatively low hydrothermal stability of Al-rich Cu-SSZ-13 catalysts hinders their practical application in ammonia selective catalytic reduction (NH3-SCR) reaction. Rare-earth ions were introduced into the Al-rich SSZ-13 zeolite using an organotemplate-free synthesis prior to the exchange of Cu2+ ions. Among the rare-earth ions tested (Ce, La, Sm, Y, Yb), Y shows significant enhancement of the hydrothermal stability and NH3-SCR activities after severe hydrothermal aging at 800 °C for 16 h when compared with Cu-SSZ-13 without Y. Cu–Y-SSZ-13 catalysts with various amounts of Y were prepared, and it is found that with increasing Y content, the low temperature NO conversions can be improve…

Exomorphism of jacobsite precipitates in bixbyite single crystals from the Thomas Range in Utah

Abstract Naturally occurring single crystals of bixbyite, (Fe,Mn)2O3, from the Thomas Mountain Range in Utah, U.S.A., were studied via (scanning) transmission electron microscopy (S)TEM. With up to 5 cm edge length, these mineral specimens are the largest bixbyite crystals found worldwide. Their hexahedral shapes are often modified by {211} facets at the corners and small {211} truncations along their cube edges. Characteristic lamellar defects, running parallel to the {100} planes, can be observed via TEM imaging. The defects are, according to EDS analyses, attributed to the tetragonal manganese silicate braunite, Mn7[SiO12]. In the present study, electron nano-diffraction and atomic resol…

Automated Diffraction Tomography for the Structure Elucidation of Twinned, Sub-micrometer Crystals of a Highly Porous, Catalytically Active Bismuth Metal-Organic Framework

Soluble Single-Molecule Nanogels of Controlled Structure as a Matrix for Efficient Artificial Enzymes

A multi-technique, micrometer- to atomic-scale description of a synthetic analogue of chukanovite, Fe-2(CO3)(OH)(2)

International audience; A synthetic analogue of chukanovite Fe-2(CO3)(OH)(2) is formed during experimental work on iron-clay interactions simulating the cooling of containers in radioactive waste repositories. Despite its small size and the mixture with other minerals it is undoubtedly identified by X-Ray Diffraction, Fourier Transform Infrared Spectroscopy, Scanning Electron Microscopy and Transmission Electron Microscopy. For the first time, the structural characterisation of a synthetic chukanovite is carried out thanks to the combination of Automated Diffraction Tomography and Precession Electron Diffraction. Refinement results and comparison with literature data show that the structure…

Precursor-Controlled Formation of Novel Carbon/Metal and Carbon/Metal Oxide Nanocomposites

Carbonaceous materials have long been considered as a high-performance material due to their light weight, high thermal resistance, tunable porosity and strength, but also because of their exciting electronic properties. When hybridized with other metal nanoparticles to form carbon/ metal nanocomposites (CMCs), multifunctionality is achieved through the combination of carbon and metal, leading to interesting magnetic materials, catalysts, battery electrodes, or chemical sensors. Various methods for preparing CMCs have been developed. In most cases, metal cations deposited on carbonaceous materials were reduced chemically or physically to form CMCs. In these processes, heterogeneous dispersi…

From Single Molecules to Nanoscopically Structured Functional Materials: Au Nanocrystal Growth on TiO2 Nanowires Controlled by Surface-Bound Silicatein

Fluorescent Nanowires Self-Assembled through Host-Guest Interactions in Modified Calcein

VS2-Nanoröhren mit Amin-Templaten der VOx-Vorstufen und reversible Cu-Einlagerung in NT-VS2

ECS-3: A Crystalline Hybrid Organic-Inorganic Aluminosilicate with Open Porosity

Inside Cover: Fluorescent Nanowires Self-Assembled through Host-Guest Interactions in Modified Calcein (Angew. Chem. Int. Ed. 32/2011)

A hydrated crystalline calcium carbonate phase: Calcium carbonate hemihydrate.

Hydrous CaCO 3 gets a new structure Calcium carbonate (CaCO 3 ) forms important minerals on Earth and is a model system for understanding crystal nucleation. Three different structures of CaCO 3 are known, along with two structures that are hydrated. Zou et al. found a third hydrated CaCO 3 structure formed from amorphous CaCO 3 in the presence of magnesium ions. The discovery illustrates the importance of amorphous precursors for producing new materials. Science , this issue p. 396

Towards automated diffraction tomography: Part I—Data acquisition

Abstract The ultimate aim of electron diffraction data collection for structure analysis is to sample the reciprocal space as accurately as possible to obtain a high-quality data set for crystal structure determination. Besides a more precise lattice parameter determination, fine sampling is expected to deliver superior data on reflection intensities, which is crucial for subsequent structure analysis. Traditionally, three-dimensional (3D) diffraction data are collected by manually tilting a crystal around a selected crystallographic axis and recording a set of diffraction patterns (a tilt series) at various crystallographic zones. In a second step, diffraction data from these zones are com…

Selective Synthesis of Monodisperse CoO Nanooctahedra as Catalysts for Electrochemical Water Oxidation

Thermal decomposition is a promising route for the synthesis of metal oxide nanoparticles because size and morphology can be tuned by minute control of the reaction variables. We synthesized CoO nanooctahedra with diameters of ∼48 nm and a narrow size distribution. Full control over nanoparticle size and morphology could be obtained by controlling the reaction time, surfactant ratio, and reactant concentrations. We show that the particle size does not increase monotonically with time or surfactant concentration but passes through minima or maxima. We unravel the critical role of the surfactants in nucleation and growth and rationalize the observed experimental trends in accordance with simu…

Structure analysis on the nanoscale: closed WS2 nanoboxes through a cascade of topo- and epitactic processes

Closed WS2 nanoboxes were formed by topotactic sulfidization of a WO3/WO3·⅓H2O intergrowth precursor. Automated diffraction tomography was used to elucidate the growth mechanism of these unconventional hollow structures. By partial conversion and structural analysis of the products, each of them representing a snapshot of the reaction at a given point in time, the overall reaction can be broken down into a cascade of individual steps and each of them identified with a basic mechanism. During the initial step of sulfidization WO3·⅓H2O transforms into hexagonal WO3 whose surface allows for the epitaxial induction of WS2. The initially formed platelets of WS2 exhibit a preferred orientation wi…

Synthesis of Microporous Carbon Nanofibers and Nanotubes from Conjugated Polymer Network and Evaluation in Electrochemical Capacitor

One-dimensional fibers and tubes are constructed through the oriented carbon-carbon cross-linking reactions towards rigid conjugated polymer networks. As the result, a template-free and one-step synthesis of CNTs and CNFs is achieved through a simple carbonization of the as-formed carbon-rich tubular and fiberlike polyphenylene precursors under argon. Microporous CNTs and CNFs with a surface area up to 900 m2 g–1 are obtained, together with HR-TEM characterizations indicating the formation of intrinsic microporous structure in these rigid carbon-rich networks. The primary electrochemical experiments reveal their promising applications as advanced electrodes in electrochemical double-layered…

Iron Oxide Superparticles with Enhanced MRI Performance by Solution Phase Epitaxial Growth

Organized three-dimensional (3D) nanomaterial architectures are promising candidates for applications in optoelectronics, catalysis, or theranostics owing to their anisotropy and advanced structural features that allow tailoring their physical and chemical properties. The synthesis of such complex but well-organized nanomaterials is difficult because the interplay of interfacial strain and facet-specific reactivity must be considered. Especially the magnetic anisotropy with controlled size and morphology plays a decisive role for applications like magnetic resonance imaging (MRI) and advanced data storage. We present a solution phase seed mediated synthesis of colloidal, well dispersible ir…

Crystal chemical characterization of mullite-type aluminum borate compounds

Abstract Al-rich aluminum borates were prepared by different synthesis routes using various Al/B ratios, characterized by diffraction methods, spectroscopy and prompt gamma activation analysis. The 11B NMR data show a small amount of BO4 species in all samples. The chemical analysis indicates a trend in the Al/B ratio instead of a fixed composition. Both methods indicate a solid solution Al5−xB1+xO9 where Al is substituted by B in the range of 1–3%. The structure of B-rich Al4B2O9 (C2/m, a=1488 pm, b=553 pm, c=1502 pm, s=90.6°), was re-investigated by electron diffraction methods, showing that structural details vary within a crystallite. In most of the domains the atoms are orderly distrib…

Self-assembly of amphiphilic imidazolium-based hexa-peri-hexabenzo-coronenes into fibreous aggregates

Imidazolium-based amphiphilic hexa-peri-hexabenzocoronenes were synthesized and shown to undergo ordered columnar self-assembly in solid-state as well as in solution to yield defined nanofibers upon solution drop casting onto solid substrate.

Bismut-katalysiertes Wachstum von SnS2-Nanoröhren und deren Stabilität

High-Pressure Synthesis of Novel Boron Oxynitride B6N4O3 with Sphalerite Type Structure

A novel crystalline boron oxynitride (BON) phase has been synthesized under static pressures exceeding 15 GPa and temperatures above 1900 °C, from molar mixtures of B2O3 and h-BN. The structure and composition of the synthesized product were studied using high-resolution transmission electron microscopy, electron diffraction, automated diffraction tomography, energy dispersive X-ray spectroscopy and electron energy-loss spectroscopy (EELS). BON shows a hexagonal cell (R3m, Z = 3) with lattice parameters a = 2.55(5) A and c = 6.37(13) A, and a crystal structure closely related to the cubic sphalerite type. The EELS quantification yielded 42 at % B, 35 at % N, and 23 at % O (B:N:O ≈ 6:4:3). E…

Synthesis of Hierarchically Grown ZnO@NT-WS2 Nanocomposites

A chemically specific and facile method for growth of ZnO nanorods on WS2 nanotubes (NT-WS2) is reported. The modification strategy is based on the chalcophilic affinity of Zn, which serves as an anchor to immobilize ZnO colloids onto the WS2 nanotubes. The surface bound ZnO colloids have been used as a seed to grow ZnO nanorods on WS2 nanotubes. The immobilization of ZnO colloids was monitored by UV−vis spectroscopy and photoluminescence spectroscopy whereas the growth of ZnO nanorods was characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM).

From Single Molecules to Nanostructured Functional Materials: Formation of a Magnetic Foam Catalyzed by Pd@FexO Heterodimers

Multicomponent nanostructures containing purely organic or inorganic as well as hybrid organic–inorganic components connected through a solid interface are, unlike conventional spherical particles, able to combine different or even incompatible properties within a single entity. They are multifunctional and resemble molecular amphiphiles, like surfactants or block copolymers, which makes them attractive for the self-assembly of complex structures, drug delivery, bioimaging, or catalysis. We have synthesized Pd@FexO heterodimer nanoparticles (NPs) to fabricate a macroporous, hydrophobic, magnetically active, three-dimensional (3D), and template-free hybrid foam capable of repeatedly separati…

Ground- and First-Excited-Singlet-State Electric Dipole Moments of Some Photochromic Spirobenzopyrans in Their Spiropyran and Merocyanine Form

The dipole moments of four photochromic derivatives of indolinospirobenzopyran have been studied in their spiro and their open merocyanine form, in dioxane. Determinations have been done by electrooptical absorption measurements (EOAM). To prepare either a pure spiropyran or a pure merocyanine form solution, the experimental setup had to be modified by addition of a second light beam. In this way thermal equilibration between the spiropyran and the merocyanine form and switching from one form to the other induced by the measuring light beam could be avoided. The ground-state dipole moment of the spiro form amounts to (10−15) × 10-30 C m and increases strongly to about 60 × 10-30 C m with th…

Using Electron Diffraction to Solve the Crystal Structure of a Laked Azo Pigment

The structure of the ζ phase of Pigment Red 53:2 was solved using electron diffraction data. The unit cell determination appeared to be more complicated due to twinning of the crystals. A series of...

Cyclodextrin and Adamantane Host-Guest Interactions of Modified Hyperbranched Poly(ethylene imine) as Mimetics for Biological Membranes

Fast-ADT: A fast and automated electron diffraction tomography setup for structure determination and refinement.

Abstract Electron crystallography has focused in the last few years on the analyses of microcrystals, mainly organic compounds, triggered by recent publications on acquisition methods based on direct detection cameras and continuous stage tilting. However, the main capability of a transmission electron microscope is the access to features at the nanometre scale. In this context, a new acquisition method, called fast and automated diffraction tomography (Fast-ADT), has been developed in form of a general application in order to get the most of the diffraction space from a TEM. It consists of two subsequent tilt scans of the goniometric stage; one to obtain a crystal tracking file and a secon…

ChemInform Abstract: Electron Crystallography and Organic Materials with Non-Linear Optical Properties

Results of electron microscopic studies of crystal structures of a number of bis-benzylidene cyclohexanones are presented. It is shown that some of these compounds are efficient crystalline non-linear optically active (NLO) chromophores with second harmonic generation (SHG) properties. Appropriately functionalized chromophores of this type can be used as a polycondensation comonomer to produce partly crystalline main-chain NLO-active polymers. Electron diffraction crystal structural data, obtained for very small crystals, allowed us to get reasonable estimations of macroscopic crystal NLO-coefficients, relating quantum-chemically calculated molecular first hyperpolarizability components to …

MZ-35, a new layered pentasil borosilicate synthesized in the presence of large alkali cations

Abstract A new layered borosilicate has been synthesized in the presence of cesium and sodium cations and its structure has been solved by a combination of automated diffraction tomography (ADT) and X-ray powder diffraction (XRPD). MZ-35 has a composition NaCs 2 [BSi 7 O 16 (OH) 2 ](OH) 2 ·4H 2 O and features space group P-4m2. The unusually small unit cell ( a 7.3081 A, c 10.7520 A) is shared by two random-stacked configurations of the structure: a network of connected pentasil units related to the layer of RUB-18 and a bidimensional checkerboard of intersecting ladders of 4-membered rings. The two configurations are related by the simple face-sharing inversion of a hydroxyl-bearing tetrah…

Cu-exchanged Al-rich SSZ-13 zeolite from organotemplate-free synthesis as NH3-SCR catalyst: Effects of Na+ ions on the activity and hydrothermal stability

Abstract The relatively low activity at lower temperatures and high cost of SSZ-13 zeolite from organotemplate synthesis are two of major problems of presently commercialized Cu-SSZ-13 catalysts for NH3-SCR reaction. Cu-exchanged Al-rich SSZ-13 catalysts with Si/Al = 4 from organotemplate-free synthesis have been prepared, and show superior NH3-SCR performance with NO conversions above 85% at wide-temperature window ranging from 150 to 650 °C. Cu-Na-SSZ-13 catalysts with varied amount of residual Na+ were prepared by partial ion-exchange of as-prepared Al-rich Na-SSZ-13, and it’s found that Cu-Na-SSZ-13 catalyst with moderate Na+ content can improve both the low-temperature activity and its…

Structural and electronic properties ofβ-FeSi2nanoparticles: The role of stacking fault domains

We use conventional and aberration-corrected transmission electron microscopy (TEM) and ab initio calculations to investigate the structural and electronic properties of \ensuremath{\beta}-FeSi${}_{2}$ nanoparticles, which are a promising material for photovoltaic applications due to a band gap of 1 eV and a high absorption coefficient. The nanoparticles have average sizes of \ensuremath{\sim}20 nm, form aggregates, and are prepared by gas-phase synthesis. Amorphous SiO${}_{x}$ shells with thicknesses of \ensuremath{\sim}1.7 nm around \ensuremath{\beta}-FeSi${}_{2}$ cores are identified on individual nanoparticles using electron energy-loss spectroscopy, while stacking fault domains in the …

The crystallisation of copper(ii) phenylphosphonates

The crystal structures and syntheses of four different copper(II) phenylphosphonates, the monophenylphosphonates α-, β-, and γ-Cu(O3PC6H5)·H2O (α-CuPhPmH (1) β-CuPhPmH (2) and γ-CuPhPmH (3)), and the diphosphonate Cu(HO3PC6H5)2·H2O (CuPhP2mH (4)), are presented. The compounds were synthesized from solution at room temperature, at elevated temperature, under hydrothermal conditions, and mechanochemical conditions. The structures of α-CuPhPmH (1) and CuPhP2mH (4) were solved from powder X-ray diffraction data. The structure of β-CuPhPmH (2) was solved by single crystal X-ray analysis. The structures were validated by extended X-ray absorption fine structure (EXAFS) and DTA analyses. Disorder …

Hierachical Ni@Fe2O3superparticles through epitaxial growth of γ-Fe2O3nanorods on: In situ formed Ni nanoplates

One endeavour of nanochemistry is the bottom-up synthesis of functional mesoscale structures from basic building blocks. We report a one-pot wet chemical synthesis of Ni@γ-Fe2O3 superparticles containing Ni cores densely covered with highly oriented γ-Fe2O3 (maghemite) nanorods (NRs) by controlled reduction/decomposition of nickel acetate (Ni(ac)2) and Fe(CO)5. Automated diffraction tomography (ADT) of the Ni-Fe2O3 interface in combination with Mossbauer spectroscopy showed that selective and oriented growth of the γ-Fe2O3 nanorods on the Ni core is facilitated through the formation of a Fe0.05Ni0.95 alloy and the appearance of superstructure features that may reduce strain at the Ni-Fe2O3 …

H-bonding schemes of di- and tri-p-benzamides assessed by a combination of electron diffraction, X-ray powder diffraction and solid-state NMR

The crystal structures of di- and tri-p-benzamides are solved by a combination of single crystal, electron and powder X-ray diffraction. Different hydrogen-bonding schemes observed in the two structures are described and classified. The hydrogen-bonding networks are correlated to complementary data obtained from multinuclear solid-state NMR.

Silica-coated Au@ZnO Janus particles and their stability in epithelial cells

Multicomponent particles have emerged in recent years as new compartmentalized colloids with two sides of different chemistry or polarity that have opened up a wide field of unique applications in medicine, biochemistry, optics, physics and chemistry. A drawback of particles containing a ZnO hemisphere is their low stability in biological environment due to the amphoteric properties of Zn2+. Therefore we have synthesized monodisperse Au@ZnO Janus particles by seed-mediated nucleation and growth whose ZnO domain was coated selectively with a thin SiO2 layer as a protection from the surrounding environment that imparts stability in aqueous media while the Au domain remained untouched. The thi…

Applications of automated diffraction tomography (ADT) on nanocrystalline porous materials

Abstract Many porous materials, both inorganic and hybrid organic–inorganic, can only be synthesized as nanocrystals. X-ray powder diffraction delivers one-dimensional data from the overall sample and is therefore often limited by peak overlap at low or medium resolution and by peak broadening. Thus, structure solution of materials with large unit cells and low symmetry, disorder or pseudosymmetry, or available only in polyphasic systems, turns out to be problematic or even impossible. Electron diffraction allows collecting three-dimensional structure information from nanocrystalline materials, but is traditionally biased by low completeness of the diffraction data, dynamical scattering and…

“Ab-initio” structure solution of nano-crystalline minerals and synthetic materials by automated electron tomography

Most of the newly discovered mineral phases, as well as many new synthesized industrial materials, appear only in the form of nano crystals, with a size not sufficient for single-crystal x-ray structure analysis. The development of techniques able to investigate the structure of nano crystalline materials is therefore one of the most important frontiers of crystallography. The most widespread technique providing relatively fast and well consolidated routes for structure analysis of bulk materials is x-ray powder diffraction (XRPD). Nevertheless, XRPD suffers from intrinsic 1-dimension reduction of information that greatly limits its applicability in presence of peak broadening and overlappi…

Fabrication of cobalt and cobalt oxide/graphene composites: towards high-performance anode materials for lithium ion batteries.

Chemical Mimicry: Hierarchical 1D TiO2@ZrO2 Core−Shell Structures Reminiscent of Sponge Spicules by the Synergistic Effect of Silicatein-α and Silintaphin-1

In nature, mineralization of hard tissues occurs due to the synergistic effect of components present in the organic matrix of these tissues, with templating and catalytic effects. In Suberites domuncula, a well-studied example of the class of demosponges, silica formation is mediated and templated by an axial proteinaceous filament with silicatein-α, one of the main components. But so far, the effect of other organic constituents from the proteinaceous filament on the catalytic effect of silicatein-α has not been studied in detail. Here we describe the synthesis of core-shell TiO(2)@SiO(2) and TiO(2)@ZrO(2) nanofibers via grafting of silicatein-α onto a TiO(2) nanowire backbone followed by …

Electron diffraction, X-ray powder diffraction and pair-distribution-function analyses to determine the crystal structures of Pigment Yellow 213, C23H21N5O9.

The crystal structure of the nanocrystalline alpha phase of Pigment Yellow 213 (P.Y. 213) was solved by a combination of single-crystal electron diffraction and X-ray powder diffraction, despite the poor crystallinity of the material. The molecules form an efficient dense packing, which explains the observed insolubility and weather fastness of the pigment. The pair-distribution function (PDF) of the alpha phase is consistent with the determined crystal structure. The beta phase of P.Y. 213 shows even lower crystal quality, so extracting any structural information directly from the diffraction data is not possible. PDF analysis indicates the beta phase to have a columnar structure with a si…

Cover Picture: Reversible Self-Assembly of Metal Chalcogenide/Metal Oxide Nanostructures Based on Pearson Hardness (Angew. Chem. Int. Ed. 41/2010)

Ba 6 P 12 N 17 O 9 Br 3 – A Column‐Type Phosphate Structure Solved from Single‐Nanocrystal Data Obtained by Automated Electron Diffraction Tomography

Oxonitridophosphate Ba6P12N17O9Br3 was synthesized by heating a multicomponent mixture of BaBr2, BaS, phosphoryl triamide and thiophosphoryl triamide in an evacuated and sealed silica-glass ampoule to 750 °C. Ba6P12N17O9Br3 was obtained as the main product as a nanocrystalline powder. The crystal structure was determined ab initio on the basis of electron diffraction data acquired from a single needle-shaped nanocrystal by automated diffraction tomography. Ba6P12N17O9Br3 crystallizes in the hexagonal space group P63/m (no. 176) with unit cell parameters a = 14.654(19), c = 8.255(9) A and Z = 2. Its structure includes triangular, column-shaped anions of ∞1{(P12N17O9)9–}, which are built from…

Soluble IF-ReS2 nanoparticles by surface functionalization with terpyridine ligands.

A major drawback in the application of layered chalcogenide nanoparticles/tubes is their inertness to chemical and biological modification and functionalization. Their potential use in composite materials might be greatly enhanced by improving the chalcogenide/matrix interface bonding. A novel modification strategy for layered chalcogenide nanoparticles based on the chalcophilic affinity of metals and the chelating terpyridine is reported. The terpyridine anchor group can be conjugated to fluorescent tags or hydrophilic/hydrophobic groups that confer solubility in various solvents to the otherwise insoluble chalcogenide nanoparticles. The functionalized particles are characterized using TEM…

Cellulose-click-ferrocenes as docking spots for cyclodextrin

A novel synthesis of ferrocene-modified cellulose, prepared from 6-azido-6-deoxy-cellulose and ethynylferrocene, is presented. The two components were coupled via copper-catalyzed click-type cycloaddition under microwave-assisted conditions. The surface structure of the cellulose derivative was investigated in comparison with that of pure, microcrystalline cellulose using electron microscopy (scanning, transmission and scanning transmission), showing iron atoms of ferrocene as homogeneously distributed particles. They are detectable as clear signals in the energy-dispersive X-ray profile. In addition, Rame-β-cyclodextrin was supramolecularly attached to cellulose and the complex formed was …

Mechanische Spannung und Valenzabsättigung in Konkurrenz: Nano-Münzrollen aus Stapeln nanoskaliger Schichten

Phase separated Cu@Fe3O4 heterodimer nanoparticles from organometallic reactants

Cu@Fe3O4 heteroparticles with distinct morphologies were synthesized from organometallic reactants. The shape of the magnetic domains could be controlled by the solvent and reaction conditions. They display magnetic and optical properties that are useful for simultaneous magnetic and optical detection. After functionalization, the Cu@Fe3O4 heterodimers become water soluble. The morphology, structure, magnetic and optical properties of the as-synthesized heterodimer nanoparticles were characterized using transmission electron microscopy (TEM), X-ray diffraction (XRD), mossbauer spectroscopy, superconducting quantum interference device (SQUID) magnetometry, and dark field imaging. A special a…

3D Electron Diffraction: The Nanocrystallography Revolution

Crystallography of nanocrystalline materials has witnessed a true revolution in the past 10 years, thanks to the introduction of protocols for 3D acquisition and analysis of electron diffraction data. This method provides single-crystal data of structure solution and refinement quality, allowing the atomic structure determination of those materials that remained hitherto unknown because of their limited crystallinity. Several experimental protocols exist, which share the common idea of sampling a sequence of diffraction patterns while the crystal is tilted around a noncrystallographic axis, namely, the goniometer axis of the transmission electron microscope sample stage. This Outlook review…

Advances in automated diffraction tomography

Crystal structure solution by means of electron diffraction or investigation of special structural features needs high quality data acquisition followed by data processing which delivers cell parameters, space group and in the end a 3D data set. The final step is the structure analysis itself including structure solution and subsequent refinement.

A consistent path for phase determination based on transmission electron microscopy techniques and supporting simulations.

This work addresses aspects for the analysis of industrial relevant materials via transmission electron microscopy (TEM). The complex phase chemistry and structural diversity of these materials require several characterization techniques to be employed simultaneously; unfortunately, different characterization techniques often lack connection to yield a complete and consistent picture. This paper describes a continuous path, starting with the acquisition of 3D diffraction data - alongside classical high-resolution imaging techniques - and linking the structural characterization of hard metal industrial samples with energy-loss fine-structure simulations, quantitative electron energy-loss (EE…

The use of maximum entropy statistics combined with simulation methods to determine the structure of 4-dimethylamino-3-cyanobiphenyl

Abstract 4-dimethylamino-3-cyanobiphenyl (4-DMA-3-CB) was characterised with respect to non-linear optical (NLO) properties in the gas phase and in the crystal. The crystal structure was solved from a series of electron diffraction patterns using both molecular modelling and ab initio maximum entropy techniques combined with log-likelihood evaluation. The agreement between the two methods is excellent and the structure evaluation permits an analysis of the major components of the hyperpolarisability tensor in the crystal framework.

Divalent metal phosphonates – new aspects for syntheses, in situ characterization and structure solution

Abstract Divalent metal phosphonates are promising hybrid materials with a broad field of application. The rich coordination chemistry of the phosphonate linkers enables the formation of structures with different dimensionalities ranging from isolated complexes and layered structures to porous frameworks incorporating various functionalities through the choice of the building blocks. In brief, metal phosphonates offer an interesting opportunity for the design of multifunctional materials. Here, we provide a short review on the class of divalent metal phosphonates discussing their syntheses, structures, and applications. We present the advantages of the recently introduced mechanochemical pa…

Small Organic Molecules and Higher Homologs

Understanding the Stability and Recrystallization Behavior of Amorphous Zinc Phosphate

Zinc phosphate, an important pigment in phosphate conversion coatings, forms protective films on rubbing surfaces. We have simulated the underlying reactions under shear by ball-milling zinc phosphate and monitored the reaction of hopeite (Zn3(PO4)2·4H2O) and the retarded recrystallization of the amorphous reaction product by powder X-ray diffraction (PXRD) and quantitative infrared (IR) spectroscopy. Abrasion of stainless steel was simulated by addition of pure 57Fe. The results provide insight into the chemistry of phosphate conversion coatings or during battery cycling of metal phosphates and give theoretical guidance for the preparation of amorphous phosphates. Thermal analysis revealed…

Snapshots of the Formation of NaTi3O6(OH)·2H2O Nanowires: A Time-Resolved XRD/HRTEM Study

Layered titanates are important intermediates during the formation of TiO2-related nanostructures in hot concentrated base solution. Microwave-assisted hydrothermal techniques allow a time-resolved ex-situ analysis of the reaction in one-minute intervals by rapid heating and quenching followed by separation and structure analysis of the intermediates. By a combination of powder X-ray diffraction, high resolution electron microscopy (HRTEM), and selected area electron diffraction (SAED) the individual stages of the reaction could be identified. Sodium titanate nanosheets are formed within several minutes by digesting the crystalline TiO2-P25 precursor in NaOH. These nanosheets with a low sod…

Frontispiece: A Novel High‐Pressure Tin Oxynitride Sn 2 N 2 O

Chemistry - a European journal 26(10), 2187-2194 (2020). doi:10.1002/chem.202081063

Controlling phase formation in solids: rational synthesis of phase separated Co@Fe2O3 heteroparticles and CoFe2O4 nanoparticles

A wet chemical approach from organometallic reactants allowed the targeted synthesis of Co@Fe(2)O(3) heterodimer and CoFe(2)O(4) ferrite nanoparticles. They display magnetic properties that are useful for magnetic MRI detection.

Synthesis and Magnetic Properties of FePt@MnO Nano-heteroparticles

Monodisperse FePt@MnO nano-heteroparticles with different sizes and morphologies were prepared by a seed-mediated nucleation and growth technique. Both size and morphology of the individual domains could be controlled by adjustment of the synthetic parameters. As a consequence, different particle constructs, including dimers, dumbbell-like particles, and flowerlike particles, could be obtained by changing the polarity of the solvent. The FePt@MnO nano-heteroparticles were thoroughly characterized by high resolution transmission electron microscopy (HR-TEM) and X-ray diffraction (XRD) analyses and superconducting quantum interference device (SQUID) magnetometry. Due to a sufficient lattice m…

Shape-persistent V-shaped mesogens—formation of nematic phases with biaxial order

A homologous series of shape-persistent V-shaped molecules has been designed to form the biaxial nematic phase. Phenyleneethynylene moieties are attached to a bent fluorenone unit to create an apex angle of about 90°, which is determined from the single crystal structure. Two mesogens, one symmetric and another unsymmetric, have been synthesized by attaching a cyano group to one or both of the peripheral phenyl units, respectively. These groups introduce local dipoles essential for the formation of the nematic phases. The tendency to form a crystalline phase is reduced by laterally substituted hexyloxy chains which allow the nematic phase to be supercooled to a glassy state. Two of the thre…

Graphene-type sheets of Nb(1-x)W(x)S2: synthesis and in situ functionalization.

Enlightened by the discovery of graphenes, a variety of inorganic analogues have been synthesized and characterized in recent years. Solvated Nb1−xWxS2 analogues of graphene-type sheets were prepared by lithiation and exfoliation of multistacked Nb1−xWxS2 coin roll nanowires (CRNWs), followed by in situ functionalization with gold nanoparticles to synthesize gold-loaded Nb1−xWxS2/Au nanocomposites. The Nb1−xWxS2 nanosheets and the corresponding Nb1−xWxS2/Au nanocomposites were characterized by high resolution electron microscopy (HRTEM), energy-dispersive X-ray spectroscopy (EDX), scanning transmission electron microscopy (STEM), dynamic light scattering (DLS) and scanning force microscopy …

Electrochemical Reduction and Oxidation of Ruddlesden–Popper-Type La2NiO3F2 within Fluoride-Ion Batteries

Within this article, it is shown that an electrochemical defluorination and additional fluorination of Ruddlesden–Popper-type La2NiO3F2 is possible within all-solid-state fluoride-ion batteries. St...

ChemInform Abstract: Hydrate Networks under Mechanical Stress - A Case Study for Co3(PO4)2·8H2O.

The mechanochemically (ball milling) induced loss of bound H2O in Co3(PO4)2·8H2O is investigated together with an associated phase transition and its kinetics by powder synchrotron XRD and quantitative IR spectroscopy.

Uniform Carbon and Carbon/Cobalt Nanostructures by Solid-State Thermolysis of Polyphenylene Dendrimer/Cobalt Complexes

Benson, J. Am. Chem. Soc. 1962, 84, 3374. b) D. L. Jeanmaire, R. P. van Duyne, J. Am. Chem. Soc. 1976, 98, 4029. c) J. P. Gong, Y. Osada, Appl. Phys. Lett. 1992, 61, 2787. d) S. Liu, Y. Liu, D. Zhu, Thin Solid Films 1996, 280, 271. e) S. Liu, Y. Liu, P. Wu, D. Zhu, H. Tian, K. Chen, Thin Solid Films 1996, 289, 300. f) S. Liu, Y. Liu, P. Wu, D. Zhu, Chem. Mater. 1996, 8, 2779. [6] a) R. S. Potember, T. O. Poehler, D. O. Cowan, F. L. Carter, P. I. Brant, in Molecular Electronic Devices (Ed: F. L. Carter), Marcel Dekker, New York 1982. b) I. Ikemoto, J. M. Thomas, H. Kuroda, Bull. Chem. Soc. Jpn. 1973, 46, 2237. [7] a) A. M. Rao, D. Jacques, R. C. Haddon, W. Zhu, C. Bower, S. Jin, Appl. Phys. …

The Bi sulfates from the Alfenza Mine, Crodo, Italy: An automatic electron diffraction tomography (ADT) study

We report about three bismuth sulfates from mineralized quartz dikes from Alfenza (Crodo, Italy), two new phases and a rare mineral, cannonite, all growing on bismuthinite. The first new phase occurs as white, "hortensia-like" aggregates of pseudo-hexagonal platelets, with perfect basal cleavage, similar to 20 mu m wide and few micrometers thick. The approximate composition is Bi2O2(SO4), and cell parameters and symmetry, as determined by automatic diffraction tomography, are a = 22.0(4), b = 16.7(3), c = 15.9(3) angstrom, beta = 102.9(5)degrees, space group Pc or P2/c. A major stacking disorder is detected by HR-SEM images and electron diffraction data.The second new phase was detected onl…

Structure Formation of Polymeric Building Blocks: Complex Polymer Architectures

This chapter describes macromolecules with a complex structure, their defined aggregation in solution, their adsorption to surfaces, and their possible aggregation on surfaces. The term “complex structure” implies that the macromolecules show different, distinct structural elements or building blocks on a supra-atomic length scale. Key to understanding the complex structure of macromolecules, their aggregation, and adsorption to surfaces are intra- and intermolecular interactions such as van der Waals, electrostatic, π–π interactions, and hydrogen bonds.

Towards automated diffraction tomography. Part II--Cell parameter determination.

Automated diffraction tomography (ADT) allows the collection of three-dimensional (3d) diffraction data sets from crystals down to a size of only few nanometres. Imaging is done in STEM mode, and diffraction data are collected with quasi-parallel beam nanoelectron diffraction (NED). Here, we present a set of developed processing steps necessary for automatic unit-cell parameter determination from the collected 3d diffraction data. Cell parameter determination is done via extraction of peak positions from a recorded data set (called the data reduction path) followed by subsequent cluster analysis of difference vectors. The procedure of lattice parameter determination is presented in detail f…

Nucleophilic attack within Ge, Sn and Pb complexes containing Me2N(CH2)(3) - as a potential intramolecular donor ligand

Abstract Thirteen tin compounds LxPhySnClz and LPh2SnPhX (x=1–4, y=0–3, z=0–2, XPh, F, Cl, Br, I, OPh), six germanium compounds LxPhyGeClz and four lead compounds LPh2PbPhX (XPh, Cl, Br, I) containing the potential intramolecular donor LMe2N(CH2)3—have been synthesized by Grignard reactions, redistribution, halogenation, exchange of halide and phenylation. Evidence for 1,5-chelation in which the donor Me2N intramolecularly attacks the Lewis-acidic atoms Ge, Sn or Pb is provided by six crystal structure determinations: Me2N(CH2)3SnPh2Cl, 5; Me2N(CH2)3SnPh2Br, 5a; Me2N(CH2)3SnPh2I, 5b; Me2N(CH2)3SnPh2OPh, 5d; Me2N(CH2)3SnPh3·HCl·H2O. 1a; Me2N(CH2)3PbPh2I, 17b), and by solution 13C, 119Sn a…

SrP3N5O: a highly condensed layer phosphate structure solved from a nanocrystal by automated electron diffraction tomography.

The oxonitridophosphate SrP(3)N(5)O has been synthesized by heating a multicomponent reactant mixture that consisted of phosphoryl triamide OP(NH(2))(3), thiophosphoryl triamide SP(NH(2))(3), SrS, and NH(4)Cl enclosed in evacuated and sealed silica-glass ampoules up to 750 °C. The compound was obtained as nanocrystalline powder with needle-shaped crystallites. The crystal structure was solved ab initio on the basis of electron diffraction data by means of automated electron diffraction tomography (ADT) and verified by Rietveld refinement with X-ray powder diffraction data. SrP(3)N(5)O crystallizes in the orthorhombic space group Pnma (no. 62) with unit-cell data of a=18.331(2), b=8.086(1), …

Highly stable and porous porphyrin-based zirconium and hafnium phosphonates – electron crystallography as an important tool for structure elucidation

The Ni-metallated porphyrin-based tetraphosphonic acid (Ni-tetra(4-phosphonophenyl)porphyrin, Ni-H8TPPP) was used for the synthesis of highly porous metal phosphonates containing the tetravalent cations Zr4+ and Hf4+. The compounds were thoroughly characterized regarding their sorption properties towards N2 and H2O as well as thermal and chemical stability. During the synthesis optimization the reaction time could be substantially decreased under stirring from 24 to 3 h in glass vials. M-CAU-30, [M2(Ni-H2TPPP)(OH/F)2]·H2O (M = Zr, Hf) shows exceptionally high specific surface areas for metal phosphonates of aBET = 1070 and 1030 m2 g-1 for Zr- and Hf-CAU-30, respectively, which are very clos…

The structure of charoite, (K,Sr,Ba,Mn)(15-16)(Ca,Na)(32)[(Si-70(O,OH)(180))](OH,F)(4.0)center dot nH(2)O, solved by conventional and automated electron diffraction

AbstractCharoite, ideally (K,Sr,Ba,Mn)15–16(Ca,Na)32[(Si70(O,OH)180)](OH,F)4.0·nH2O, a rare mineral from the Murun massif in Yakutiya, Russia, was studied using high-resolution transmission electron microscopy, selected-area electron diffraction, X-ray spectroscopy, precession electron diffraction and the newly developed technique of automated electron-diffraction tomography. The structure of charoite (a= 31.96(6) Å,b= 19.64(4) Å,c= 7.09(1) Å, β = 90.0(1)°,V= 4450(24) Å3, space groupP21/m) was solvedab initioby direct methods from 2878 unique observed reflections and refined toR1/wR2= 0.17/0.21. The structure can be visualized as being composed of three different dreier silicate chains: a d…

Micelle Formation from Amphiphilic“Cylindrical Brush”—Coil Block Copolymers Prepared by Metallocene Catalysis

Hypervalent tin-organic compounds: Vibrational spectroscopy in the solid as a tool for structure determination

Abstract A full set of IR- and Raman spectra down from 600 cm1 has been determined and assigned for 60 penta- or hexacoordinated tin-compounds in the groups RSn(CH2CH2CH2)3N (R = Cl, Br, I, Me), RR'Sn(MCH2CH2)2X (R,R′ = Cl, Br, I, Me, Ph, M = CH2 S; X = NMe, O, S), RPh2SnCH2CH2CH2NMe2 (R = Cl, Br, I) and RMe2Sn—CHD—COOMe (R = F, Cl, Br, I, Me). In these hypervalent compounds an approach of the donor atom X to the central atom tin outlines a ‘path’ of nucleophilic attack from a tetrahedron to a trigonal bipyramid. Along this ‘reaction path’ the bond lengths of the axial ligand increase continuously while the bond lengths of the equatorial ligands slightly decrease. The number of similar hype…

Transformation synthesis of aluminosilicate SSZ-39 zeolite from ZSM-5 and beta zeolite

Aluminosilicate SSZ-39 zeolite has been successfully prepared by transformation from ZSM-5 and beta zeolite in the presence of N,N-diethyl-cis-2,6-dimethylpiperidinium hydroxide (DMPOH) under hydrothermal conditions. Catalytic tests in the selective catalytic reduction of NOx with NH3 (NH3-SCR) show that the copper-exchanged products synthesized from the interzeolite transformation exhibit excellent catalytic performance.

Using FOCUS to solve zeolite structures from three-dimensional electron diffraction data

The programFOCUS[Grosse-Kunstleve, McCusker &amp; Baerlocher (1997).J. Appl. Cryst.30, 985–995] was originally developed to solve zeolite structures from X-ray powder diffraction data. It uses zeolite-specific chemical information (three-dimensional 4-connected framework structure with known bond distances and angles) to supplement the diffraction data. In this way, it is possible to compensate, at least in part, for the ambiguity of the reflection intensities resulting from reflection overlap, and the program has proven to be quite successful. Recently, advances in electron microscopy have led to the development of automated diffraction tomography (ADT) and rotation electron diffraction (R…

A Cationic Oligomer as an Organic Template for Direct Synthesis of Aluminosilicate ITH Zeolite

There are a large number of zeolites, such as ITH, that cannot be prepared in the aluminosilicate form. Now, the successful synthesis of aluminosilicate ITH zeolite using a simple cationic oligomer as an organic template is presented. Key to the success is that the cationic oligomer has a strong complexation ability with aluminum species combined with a structural directing ability for the ITH structure similar to that of the conventional organic template. The aluminosilicate ITH zeolite has very high crystallinity, nanosheet-like crystal morphology, large surface area, fully four-coordinated Al species, and abundant acidic sites. Methanol-to-propylene (MTP) tests reveal that the Al-ITH zeo…

How to Determine Reliable Intensities Using Film Methods?

The basis of a successful structure analysis is to obtain reliable intensities. In the field of electron crystallography intensity data can be collected on-line with a CCD-camera as well as off-line using image plates or film material. Whereas image plates are read out with a laser, film material is analysed via a densitometer or digitised using a CCD-camera or a scanner. Both, CCD-camera and scanner, uses CCDtechnology and we show that both systems can be used for intensity evaluation. In order to obtain reliable intensities from film media it is important to define and calibrate the experimental conditions, the digitization process and the evaluation of intensity data exactly. A high opti…

Rational assembly and dual functionalization of Au@MnO heteroparticles on TiO2 nanowires

Au–MnO heteroparticles were immobilized on the surface of TiO2 nanowires and tagged subsequently with a fluorescent ligand. The immobilization of the Au@MnO heteroparticles was achieved by functionalizing the TiO2 nanowire support with a polymer containing catechol anchor groups for binding to the metal oxide surface and amine groups for conjugation to the Au domains of the Au@MnO heteroparticles. The Au domain of the resulting TiO2@Au–MnO nanocomposite could be functionalized selectively with a thiol-tagged 24 mer oligomer containing Texas red (SH-ODN-TXS red), whereas a green dye (NBD–Cl) could be anchored selectively to the TiO2 “support” using the free amine groups of the polymeric liga…

From Well-Defined Carbon-Rich Precursors to Monodisperse Carbon Particles with Hierarchic Structures

The creation of nanoscale particles with well-defined structures has long been considered as a promising approach to generate materials with novel properties. Carbonaceous nanoparticles (CNPs) with defined architectures, such as carbon nanotubes (CNTs), C60, carbon onions, carbon spheres, and carbon rods are particularly attractive owing to their unique electronic properties and many potential applications. At the same time, when these CNPs are regularly organized, additional functions appear. Such materials are believed to have hierarchic structures, in which the organization of the CNPs forms the first-order structure (FOS) and the configuration of the single CNP forms the secondor higher…

Structural anisotropy and annealing-induced nanoscale atomic rearrangements in metamict titanite

The structural state of metamict titanite was studied by Raman spectroscopy, complementary high-resolution transmission electron microscopy, and single-crystal X-ray diffraction. The results show that Raman scattering collected from metamict titanite is highly anisotropic, which is typical of single crystals. But surprisingly, the observed Raman-scattering dependence on the sample orientation is much more pronounced for heavily metamict than for weakly metamict titanite samples. These radiation-induced anisotropic effects are related to the specific atomic arrangements in metamict titanite. The Raman spectra collected in backscattering geometry from a plane nearly perpendicular to the chain…

Electron Crystallography – New Methods to Explore Structure and Properties of the Nano World

Electron crystallography, as the branch of science that uses electron scattering, developed in the last century into a manifold and powerful approach to study the structure of matter. Major historical milestones of this development are discussed. Especially electron diffraction experienced recently a renaissance and grew into an established method of structure analysis. The techniques of data collection and processing available nowadays are described.

A comparative study of the physicochemical properties of iron isomaltoside 1000 (Monofer®), a new intravenous iron preparation and its clinical implications

Abstract The treatment of iron deficiency anemia with polynuclear iron formulations is an established therapy in patients with chronic kidney disease but also in other disease areas like gastroenterology, cardiology, oncology, pre/post operatively and obstetrics’ and gynecology. Parenteral iron formulations represent colloidal systems in the lower nanometer size range which have traditionally been shown to consist of an iron core surrounded by a carbohydrate shell. In this publication, we for the first time describe the novel matrix structure of iron isomaltoside 1000 which differs from the traditional picture of an iron core surrounded by a carbohydrate. Despite some structural similaritie…

Distribution of molecularly imprinted polymer layers on macroporous silica gel particles by STEM and EDX

Abstract Using transmission electron microscopy (TEM) in parallel and scanning mode (STEM) combined with energy dispersive X-ray spectroscopy (EDX) the distribution of molecularly imprinted polymer layers covalently grafted on the inner and outer surface of macroporous silica gel particles was observed. The grafting was achieved using a special initiator system ( iniferter ) and applied on a well known model system producing molecularly imprinted layers with l -phenyl alanine analide ( l -PA) as template. By staining the sample with RuO 4 before its embedment in epoxy resin and cutting ultra thin slices it was possible to identify the stained grafted polymer on the silica matrix by EDX. Bas…

Automated electron diffraction tomography – development and applications

Electron diffraction tomography, a potential method for structure analysis of nanocrystals, and, in more detail, the strategies to use automated diffraction tomography (ADT) technique are described. Examples of ADT application are discussed according to the material class.

Evidence of noncentrosymmetry of human tooth hydroxyapatite crystals

Herein, we investigate human single hydroxyapatite crystals (enamel and dentine) by convergent-beam electron diffraction (CBED) and automated electron-diffraction tomography (ADT). The CBED pattern shows the absence of the mirror plane perpendicular to the c axis leading to the P63 space group instead of the P63 /m space group considered for larger-scale crystals, this is confirmed by ADT. This experimental evidence is of prime importance for understanding the morphogenesis and the architectural organization of calcified tissues.

Studies of structures and properties of polymeric systems containing bis-(hydroxy-arylidene)alkanones as NLO-active chromophores

Abstract NLO-properties of polymer systems containing bis-(hydroxy-arylidene)alkanone chromophores were studied experimentally and analyzed using ab initio quantum chemical calculations. A monoclinic crystal structure (space group P2111) of the polyester containing fragments of such chromophores in the backbone was simulated and a reasonable agreement between the experimental and simulated X-ray powder diffraction patterns was achieved. Ab initio quantum-mechanical estimations of the SHG-observable macroscopic second-order non-linearity tensor coefficients, obtained for the polymer crystal structure at the HF SCF level, led to the major dXZZ-coefficient of 1.9 pm/V. Films of ionic complexes…

From Single Molecules to Nanoscopically Structured Materials: Self-Assembly of Metal Chalcogenide/Metal Oxide Nanostructures Based on the Degree of Pearson Hardness

A chemically specific and facile method for the immobilization of metal oxide nanoparticles onto the surface of IF-MoS2 nested fullerenes is reported. The modification strategy is based on the chalcophilic affinity of transition metals such as Fe2+/Fe3+, Fe3+, or Zn2+ as described by the Pearson HSAB concept. The binding capabilities of the 3d metals are dictated by their Pearson hardness. Pearson hard cations such as Fe3+ (Fe2O3) do not bind to the chalcogenide surfaces; borderline metals such as Fe2+ (Fe3O4) or Zn2+ (ZnO) bind reversibly. Pearson-soft metals like Au bind irreversibly. The immobilization of metal oxide nanoparticle colloids was monitored by transmission electron microscopy…

Structure determination to calculate nonlinear optical coefficients in a class of organic material

A class of molecules with intramolecular two-dimensional charge transfer upon excitation has been synthesized. It is expected that these materials should be prospective candidates for nonlinear optical (NLO) applications such as second harmonic (SHG) generation. In order to optimize the macroscopic NLO properties of the compounds, it is necessary to relate their first hyperpolarizability tensors at a molecular level to those at a crystal bulk level. This requires a complete structure determination and refinement. However, the growth of sufficiently large single crystals, which are needed for structural analysis and refinement by x-ray methods, is a time-consuming and sometimes impossible ta…

Total-scattering pair-distribution function of organic material from powder electron diffraction data.

AbstractThis paper shows that pair-distribution function (PDF) analyses can be carried out on organic and organometallic compounds from powder electron diffraction data. Different experimental setups are demonstrated, including selected area electron diffraction and nanodiffraction in transmission electron microscopy or nanodiffraction in scanning transmission electron microscopy modes. The methods were demonstrated on organometallic complexes (chlorinated and unchlorinated copper phthalocyanine) and on purely organic compounds (quinacridone). The PDF curves from powder electron diffraction data, called ePDF, are in good agreement with PDF curves determined from X-ray powder data demonstrat…

Glycine-functionalized copper(ii) hydroxide nanoparticles with high intrinsic superoxide dismutase activity

Superoxide dismutases (SOD) are a group of enzymes that catalyze the dismutation of superoxide (O2−) radicals into molecular oxygen (O2) and H2O2 as a first line of defense against oxidative stress. Here, we show that glycine-functionalized copper(II) hydroxide nanoparticles (Gly-Cu(OH)2 NPs) are functional SOD mimics, whereas bulk Cu(OH)2 is insoluble in water and catalytically inactive. In contrast, Gly-Cu(OH)2 NPs form water-dispersible mesocrystals with a SOD-like activity that is larger than that of their natural CuZn enzyme counterpart. Based on this finding, we devised an application where Gly-Cu(OH)2 NPs were incorporated into cigarette filters. Cigarette smoke contains high concent…

Solid State Fluorination on the Minute Scale: Synthesis of WO 3− x F x with Photocatalytic Activity

ChemInform Abstract: Solution Synthesis of a New Thermoelectric Zn1+xSb Nanophase and Its Structure Determination Using Automated Electron Diffraction Tomography.

Thermoelectric nanoparticles of the nominal composition Zn4Sb3 are prepared by heating Sb nanoparticles with a 9-fold excess of Zn particles (synthesized by reaction of SbCl3 or ZnCl2 with Li[Et3BH] in THF at room temperature, and about 65 °C, respectively) in trioctylamine at about 300 °C for 225 min.

The Elusive Structure of Magadiite, Solved by 3D Electron Diffraction and Model Building

In addition to a great swelling ability, layered silicates also allow the functionalization of their interlayer region to form various robust green materials that are used as CO2 adsorbents, drug c...

Carbon-doped titania as a precursor for titanate nanotubes

Carbon-doped titania was fabricated via carbothermal treatment in nitrogen–acetylene gas flow and further used as a precursor for multiwalled titanate nanotube (TNT) synthesis via alkaline hydrothermal route. Investigation of the reaction products after hydrothermal treatment of carbon-doped titania using Transmission electron microscopy, X-ray diffraction, and Brunauer–Emmett–Teller method shows the successful formation of TNTs. The presence of carbon was proved although the type of incorporation could not be certified. All samples show approximately the same carbon content before and after hydrothermal treatment. An increasing pretreatment temperature of titania precursor powders yields m…

Solving Challenging Crystallographic Problems with Automated Electron Diffraction Tomography (ADT)

Controlling the Morphology of Au–Pd Heterodimer Nanoparticles by Surface Ligands

Controlling the morphology of noble-metal nanoparticles is mandatory to tune specific properties such as catalytic and optical behavior. Heterodimers consisting of two noble metals have been synthesized, so far mostly in aqueous media using selective surfactants or chemical etching strategies. We report a facile synthesis for Au@Pd and Pd@Au heterodimer nanoparticles (NPs) with morphologies ranging from segregated domains (heteroparticles) to core-shell structures by applying a seed-mediated growth process with Au and Pd seed nanoparticles in 1-octadecene (ODE), which is a high-boiling organic solvent. The as-synthesized oleylamine (OAm) functionalized Au NPs led to the formation of OAm-Au@…

Subamorphous thermal conductivity of crystalline half-Heusler superlattices

The quest to improve the thermoelectric figure of merit has mainly followed the roadmap of lowering the thermal conductivity while keeping unaltered the power factor of the material. Ideally an electron-crystal phonon-glass system is desired. In this work, we report an extraordinary reduction of the cross-plane thermal conductivity in crystalline (TiNiSn):(HfNiSn) half-Heusler superlattices (SLs). We create SLs with thermal conductivities below the effective amorphous limit, which is kept in a large temperature range (120–300 K). We measured thermal conductivity at room temperature values as low as 0.75 W m−1 K−1, the lowest thermal conductivity value reported so far for half-Heusler compou…

Solving the Hydrogen and Lithium Substructure of Poly(triazine imide)/LiCl Using NMR Crystallography

Poly(triazine imide) with incorporated lithium chloride has recently attracted substantial attention due to its photocatalytic activity for water splitting. However, an apparent H/Li disorder prevents the delineation of structure–property relationships, for example, with respect to band-gap tuning. Herein, we show that through a combination of one- and two-dimensional, multinuclear solid-state NMR spectroscopy, chemical modelling, automated electron diffraction tomography, and an analysis based on X-ray pair distribution functions, it is finally possible to resolve the H/Li substructure. In each cavity, one hydrogen atom is bound to a bridging nitrogen atom, while a second one protonates a …

Synthesis of Fullerene- and Nanotube-Like SnS2 Nanoparticles and Sn/S/Carbon Nanocomposites

SnS2 nested fullerene-type (IF) nanoparticles, nanotubes, and SnS2/C hybrid nanostructures were obtained by vapor transport starting from elemental tin and CS2. The reaction was carried out in a single-step process by heating elemental tin metal powder in a horizontal tube furnace at 800−1000 °C. TEM analysis allowed proposing a plausible mechanism for the formation of fullerene-like particles of SnS2 as well as tubes and scrolls from nanosheets of SnS2. Pure material could be obtained by optimizing the reaction based on a product analysis using powder X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM) combined with energy-dispersive X-ray spectroscopy (EDX…

IF-ReS2 with Covalently Linked Porphyrin Antennae

The preparation of inorganic and organic hybrid materials, of metals or semiconductor systems which are functionalized with functional molecules to fabricate devices — nanotechnology — is currently an area of intense activity in both fundamental science and applied science on an international scale. Principally, nanotechnology aims at manipulating atoms, molecules, and nanosize particles in a precise and controlled manner in order to build materials with a fundamentally new organization and novel properties. The embryonic stage of nanotechnology is atomic assembly, whereas the mature form of nanotechnology will be molecular assembly to make nano-building blocks for the design of nanocomposi…

High Electron Mobility and Disorder Induced by Silver Ion Migration Lead to Good Thermoelectric Performance in the Argyrodite Ag8SiSe6

Superionic chalcopyrites have recently attracted interest in their use as potential thermoelectric materials because of extraordinary low thermal conductivities. To overcome long-term stability issues in thermoelectric generators using superionic materials at evaluated temperatures, materials need to be found that show good thermoelectric performance at moderate temperatures. Here, we present the structural and thermoelectric properties of the argyrodite Ag8SiSe6, which exhibits promising thermoelectric performance close to room temperature.

Application of clustering techniques to electron-diffraction data: determination of unit-cell parameters.

A new approach to determining the unit-cell vectors from single-crystal diffraction data based on clustering analysis is proposed. The method uses the density-based clustering algorithm DBSCAN. Unit-cell determination through the clustering procedure is particularly useful for limited tilt sequences and noisy data, and therefore is optimal for single-crystal electron-diffraction automated diffraction tomography (ADT) data. The unit-cell determination of various materials from ADT data as well as single-crystal X-ray data is demonstrated.

Automated diffraction tomography combined with electron precession: a new tool forab initionanostructure analysis

AbstractThree-dimensional electron diffraction data was collected with our recently developed module for automated diffraction tomography and used to solve inorganic as well as organic crystal structuresab initio. The diffraction data, which covers nearly the full relevant reciprocal space, was collected in the standard nano electron diffraction mode as well as in combination with the precession technique and was subsequently processed with a newly developed automated diffraction analysis and processing software package. Non-precessed data turned out to be sufficient forab initiostructure solution by direct methods for simple crystal structures only, while precessed data allowed structure s…

Reduced thermal conductivity of TiNiSn/HfNiSn superlattices

Diminution of the thermal conductivity is a crucial aspect in thermoelectric research. We report a systematic and significant reduction of the cross-plane thermal conductivity in a model system consisting of DC sputtered TiNiSn and HfNiSn half-Heusler superlattices. The reduction of $\kappa$ is measured by the 3$\omega$ method and originates from phonon scattering at the internal interfaces. Heat transport in the superlattices is calculated based on Boltzmann transport theory, including a diffusive mismatch model for the phonons at the internal interfaces. Down to superlattice periodicity of 3 nm the phonon spectrum mismatch between the superlattice components quantitatively explains the re…

Melt processing of hexa-peri-hexabenzocoronene on the water surface

A discotic polycyclic aromatic hydrocarbon, hexa-peri-hexabenzocoronene, was oriented by slow cooling from the isotropic phase on a water surface as a film. For melt processing at low temperatures, an HBC derivative with long swallow-tailed alkyl side chains was chosen. The supramolecular organization in the resulting thin layer was investigated by electron microscopy. In high-resolution mode, the structural study showed large domains in which the columnar structures were oriented uniaxially with an edge-on arrangement of the hydrophobic molecules. The length of the stacks exceeded several hundred nanometers without obvious defects. The small-area analysis by TEM allowed the direct visualiz…

The solid-state architecture of a metallosupramolecular polyelectrolyte

Self-assembly of Fe(II) and the ditopic ligand 1,4-bis(2,2′:6′,2″-terpyridine-4′-yl)benzene results in equilibrium structures in solutions, so-called metallosupramolecular coordination polyelectrolytes (MEPEs). It is exceedingly difficult to characterize such macromolecular assemblies, because of the dynamic nature. Therefore, hardly any structural information is available for this type of material. Here, we show that from dilute solutions, where small aggregates predominate, it is possible to grow nanoscopic crystals at an interface. A near atomic resolution structure of MEPE is obtained by investigating the nanoscopic crystals with electron diffraction in combination with molecular model…

Introduction to ADT/ADT3D

ADT approach was successfully used within the last years to solve crystal structure of nanocrystalline material ab-inito using programs initially written for X-ray diffraction data. The methodology of ADT data analysis including data extraction in a format suitable for established structure solution programs was developed. A collection of processing routines was implemented into dedicated software ADT3D. Here the main steps of ADT data processing are explained, and the complete sequence of steps from importing raw data to saving the hklI file is demonstrated.

Polystyrene Sulfonate–Porphyrin Assemblies: Influence of Polyelectrolyte and Porphyrin Structure

In this study, electrostatic self-assembly of different polystyrene sulfonates and a set of tetravalent cationic porphyrins is investigated. It is shown that association of linear polystyrene sulfonates of different molar masses yields finite size nanoscale assemblies that are stable in aqueous solution. Aggregates are compared to the ones of cylindrical brushes, revealing that both form assemblies in the 100 nm range with the charge ratio (molar ratio of porphyrin charges to polyelectrolyte charges) being determining, while the morphology of the resulting network-like assemblies is different for both polyelectrolyte architectures. For the smallest 8k polystyrene sulfonate, in addition, sto…

Electron diffraction tomography and X-ray powder diffraction on photoredox catalyst PDI

N,N-Bis(2,6-diisopropylphenyl)-perylene-3,4,9,10-bis(dicarboximide) (PDI-iPr) is starting to be widely used as a metal-free homogeneous photoredox catalyst. The crystal structure was determined by a combination of electron diffraction tomography and X-ray powder diffraction and further validated by DFT-D calculations. Surprisingly, the molecular geometry of PDI-iPr leads to voids in the packing.

Efficient and rapid transformation of high silica CHA zeolite from FAU zeolite in the absence of water

High silica CHA zeolite plays an important role in selective catalytic reduction of NOx with NH3 (NH3-SCR), but its synthesis is not highly efficient due to the use of a relatively high-cost structural directing agent (SDA) N,N,N-trimethyl-adamantammonium hydroxide (TMAdaOH) and relatively long crystallization time under hydrothermal conditions. Herein, we report an efficient and rapid synthesis of a high silica CHA zeolite possessing good crystallinity and uniform crystals (CHA-ST). The method includes interzeolite transformation of high silica FAU zeolite in the absence of water but the presence of zeolite seeds and a bromide form of the SDA. The absence of water in the synthesis signific…

Heterocyclic systems containing tin(IV)—XIII [1]. Possible ceasing or inversion of the structuraltrans influence during the course of a bimolecular nucleophilic attack of a donor group in a series of SnIV rings

Abstract In the series of the heterocycles X[(CH2)3]2SnR2 (16 newly synthesized compounds and two taken from the literature) and in the germanium analog BuiN[(CH2)3]2GeCl2, the donor group X (= NMe, NBz, NBui, NPri, O, S) intramolecularly attacks the Lewis acidic atoms Sn or Ge. Eight structure determinations (and, in addition, 2 taken from the literature) are compared. The nucleophilic attack at Sn is stronger for the ligands R2 =Cl2 than for the more electronegative R2 = (OSiPh3)2. Overall the familiartrans influence holds: simultaneous approach of X and weakening of the ligand R (trans). In three cases of subtly graded donor strength a slight inversion or ceasing is observed: shorter dis…

Mismatch strain versus dangling bonds: formation of "coin-roll nanowires" by stacking nanosheets.

Heusler compounds as ternary intermetallic nanoparticles: Co2FeGa

This work describes the preparation of ternary nanoparticles based on the Heusler compound Co2FeGa. Nanoparticles with sizes of about 20?nm were synthesized by reducing a methanol impregnated mixture of CoCl2 ? 6H2O, Fe(NO3)3 ? 9H2O and Ga(NO3)3 ? xH2O after loading on fumed silica. The dried samples were heated under pure H2 gas at 900??C. The obtained nanoparticles?embedded in silica?were investigated by means of x-ray diffraction (XRD), transmission electron microscopy, temperature dependent magnetometry and M??bauer spectroscopy. All methods clearly revealed the Heusler-type L21 structure of the nanoparticles. In particular, anomalous XRD data demonstrate the correct composition in addi…

Cu-Exchanged CHA-Type Zeolite from Organic Template-Free Synthesis: An Effective Catalyst for NH3-SCR

A Cu-containing CHA-type zeolite was prepared via aqueous ion exchange of the CHA zeolite from organic template-free synthesis. The thus-obtained template-free Cu-CHA showed the best catalytic perf...

Synthesis and Characterization of Highly Luminescent CdSe—Core CdS/Zn0.5Cd0.5S/ZnS Multishell Nanocrystals.

We report on the preparation and structural characterization of CdSe nanocrystals, which are covered by a multishell structure from CdS and ZnS. By using the newly developed successive ion layer adhesion and reaction (SILAR) technique, we could gradually change the shell composition from CdS to ZnS in the radial direction. Because of the stepwise adjustment of the lattice parameters in the radial direction, the resulting nanocrystals show a high crystallinity and are almost perfectly spherical, as was investigated by X-ray diffraction and electron microscopy. Also, due to the radial increase of the respective valence- and conduction-band offsets, the nanocrystals are well electronically pas…

IM-17: a new zeolitic material, synthesis and structure elucidation from electron diffraction ADT data and Rietveld analysis

International audience; The synthesis and the structure of IM-17, a new germanosilicate with a novel zeolitic topology, prepared hydrothermally with decamethonium as the organic structure directing agent, are reported. The structure of calcined and partially rehydrated IM-17 of chemical formula per unit cell |(H2O)14.4|[Si136.50Ge39.50O352] was solved ab initio using electron diffraction ADT data in the acentric Amm2 (setting Cm2m) space group and refined by the Rietveld method. This new zeolite framework type contains a 3D pore system made of intersecting 12, 10 and 8-ring channels.

Snapshots of calcium carbonate formation – a step by step analysis

Abstract Recent advances in our understanding of CaCO3 nucleation from solution have provoked new and challenging questions. We have studied CaCO3 formation using precipitation by carbonate ester hydrolysis which ensures precipitation from a strictly homogeneous solution state and allows “titrating” carbonate to a solution with a given Ca2+ concentration on a timescale suited for kinetic studies. Nucleation and crystallization were traced by combining dynamic light scattering (DLS) and transmission electron microscopy (TEM). DLS served as in situ technique to identify the nucleation time, to monitor particle size evolution, to discriminate different precipitation mechanisms and to validate …

Two new members of the Silica-X family of materials: RUB-5, a silica zeolite with a very high framework density and RUB-6, a hydrous layer silicate

Abstract The new zeolite RUB-5 and the new phyllo silicate RUB-6 were synthesized at temperatures between 130 °C and 200 °C from reaction mixtures consisting of SiO2/LiOH/B(OH)3/OA/H2O or SiO2/KOH/OA/H2O (OA = organic additive). Physico-chemical characterization using solid-state NMR spectroscopy, SEM, TG-DTA, and ATR-FTIR spectroscopy confirmed that RUB-5 is a framework silicate while RUB-6 is a layer silicate. The XRD powder patterns were indexed in monoclinic symmetry (space group: C2) with lattice parameters of a0 = 10.2699 (4) A, b0 = 10.6556 (4) A, c0 = 18.1551 (7) A and β = 106.35 (1)° (RUB-5), and a0 = 10.1100 (43) A, b0 = 10.6956 (51) A, c0 = 20.5448 (44) A and β = 105.79 (1)° (RUB…

New zeolite-like RUB-5 and its related hydrous layer silicate RUB-6 structurally characterized by electron microscopy.

RUB-5 and its related hydrous layer silicate RUB-6 were synthesized in the 1990s, but so far their structures have remained unknown due to their low crystallinity and disorder. The combination of 3D electron diffraction, X-ray powder diffraction, high-resolution transmission electron microscopy, structural modelling and diffraction simulations has enabled a comprehensive description of these two nanomaterials, revealng a new framework topology and a unique silica polymorph.

A water-soluble hexa-peri-hexabenzocoronene: synthesis, self-assembly and role as template for porous silica with aligned nanochannels

A water-soluble hexa-peri-hexabenzocoronene was prepared and shown to undergo ordered columnar self-assembly either in water solution or bulk and therefore served as template for the fabrication of porous silica with aligned nanochannels.

Structure solution of zeolites by automated electron diffraction tomography - Impact and treatment of preferential orientation

Abstract In this paper the reliability of structure solution of nano-crystalline porous compounds with preferred orientation based on automated electron diffraction tomography (ADT) is discussed. It will be shown that the limitations of the data acquisition geometry can be overcome by completing the missing diffraction data with additional diffraction information. Apart from different ways of sample preparation, data merging with either additional ADT data sets or intensities derived from X-ray powder diffraction comprise an effective way to improve the accuracy of the structure solution.

Macromol. Rapid Commun. 24/2010

Application of delta recycling to electron automated diffraction tomography data from inorganic crystalline nanovolumes

δ Recycling is a simple procedure for directly extracting phase information from Patterson-type functions [Rius (2012). Acta Cryst. A68, 399-400]. This new phasing method has a clear theoretical basis and was developed with ideal single-crystal X-ray diffraction data. On the other hand, introduction of the automated diffraction tomography (ADT) technique has represented a significant advance in electron diffraction data collection [Kolb et al. (2007). Ultramicroscopy, 107, 507-513]. When combined with precession electron diffraction, it delivers quasi-kinematical intensity data even for complex inorganic compounds, so that single-crystal diffraction data of nanometric volumes are now availa…

Korrosion von Kulturgut: Entdeckung einer kollagenartigen Tripelhelix in der Kristallstruktur von Calciumacetat‐Hemihydrat

Reactive Polymers: A Versatile Toolbox for the Immobilization of Functional Molecules on TiO2 Nanoparticles

Essential features of the polytypic charoite-96 structure compared to charoite-90

AbstractCharoite, ideally (K,Sr,Ba,Mn)15–16(Ca,Na)32[(Si70(O,OH)180)](OH,F)4·nH20, is a rock-forming mineral from the Murun massif in Yakutia, Sakha Republic, Siberia, Russia, where it occurs in a unique alkaline intrusion. Charoite occurs as four different polytypes, which are commonly intergrown in nanocrystallme fibres. We report the structure of charoite-96(a =32.11(6),b =19.77(4),c =7.23(1) Å, β = 95.85(9)°,V =4565(24) Å3, space groupP21/m),which was solvedab initioby direct methods on the basis of 2676 unique electron diffraction reflections collected by automated diffraction tomography and refined toR1/wR2=0.34/0.37. The structure of charoite-96 is related to that of the charoite-90,…

Facile synthesis and characterization of monocrystalline cubic ZrO2 nanoparticles

Abstract Crystalline ZrO2 nanoparticles were prepared from zirconium isopropoxide by slow hydrolysis and subsequent hydrothermal treatment of solutions containing various amounts of sodium hydroxide at 180 °C. Whereas moderately basic solutions lead to the formation of nanoparticles of monoclinic ZrO2 with plate-like morphology, and nanoparticles of the cubic ZrO2 high-temperature polymorph with diameters of approx. 5 nm were obtained from strongly basic solutions. The morphology, structure and properties of as-synthesized nanoparticles were characterized using HRTEM, XRD, Raman spectroscopy, UV–vis, PL spectroscopy and BET measurements. The formation of both, the monoclinic and the cubic p…

Nanostructuring with a crosslinkable discotic material.

A high-yielding synthesis afforded a hexa-peri-hexabenzocoronene carrying acrylate units at the end of six attached alkyl spacers. The polymerization of these acrylate moieties could be initiated with thermal energy and through direct photoactivation without the addition of a photoinitiator. This allowed the organization of the liquid-crystalline material to be fixed in either the crystalline state or the mesophase, which preserved the organization in the respective phase. The use of a focused synchrotron beam permitted selected regions of a thin film to be rendered insoluble. After "developing" the film in this lithographic process by dissolving the soluble, unpolymerized material, defined…

Facile synthesis and characterization of functionalized, monocrystalline rutile TiO2 nanorods.

Functionalized, monocrystalline rutile TiO2 nanorods were prepared from TiCl4 in aqueous solution under acidic conditions in the presence of dopamine, followed by aging and hydrothermal treatment at 150 degrees C. The surface-bound organic ligand controls the morphology as well as the crystallinity and the phase selection of TiO2. The presence of monocrystalline rutile TiO2 was confirmed by X-ray powder diffraction and HRTEM investigations. The as-prepared nanorods are soluble in water at pH3. The surface functionalization was analyzed by IR and 1H NMR, confirming the presence of dopamine on the surface. The surface amine groups can be tailored further with functional molecules such as dyes…

Pd@Fe2O3 Superparticles with Enhanced Peroxidase Activity by Solution Phase Epitaxial Growth

Compared to conventional deposition techniques for the epitaxial growth of metal oxide structures on a bulk metal substrate, wet-chemical synthesis based on a dispersible template offers advantages such as low cost, high throughput, and the capability to prepare metal/metal oxide nanostructures with controllable size and morphology. However, the synthesis of such organized multicomponent architectures is difficult because the size and morphology of the components are dictated by the interplay of interfacial strain and facet-specific reactivity. Here we show that solution-processable two-dimensional Pd nanotetrahedra and nanoplates can be used to direct the epitaxial growth of γ-Fe2O3 nanoro…

Haloperoxidase Mimicry by CeO2−xNanorods Combats Biofouling

CeO2-x nanorods are functional mimics of natural haloperoxidases. They catalyze the oxidative bromination of phenol red to bromophenol blue and of natural signaling molecules involved in bacterial quorum sensing. Laboratory and field tests with paint formulations containing 2 wt% of CeO2-x nanorods show a reduction in biofouling comparable to Cu2 O, the most typical biocidal pigment.

Surface Defects as a Tool to Solubilize and Functionalize WS 2 Nanotubes

Layered transition metal dichalcogenides contain a number of crystal defects which significantly change their properties may be beneficial or detrimental for a specific application. We have prepared defect-rich multiwalled WS2 nanotubes by reductive sulfidization of W18O49 nanowires that were obtained solvothermally from tungsten chloride in different alcohols. The synthesis of the W18O49 nanowires was monitored and their morphological characteristics (e. g. length, rigidity and aspect ratio) are described in detail. The effect of morphology of the nanowires on the synthesis of WS2 nanotubes was investigated in order to obtain WS2 nanotubes that are highly solvent dispersible. Dispersions o…

Hydrate Networks under Mechanical Stress – A Case Study for Co 3 (PO 4 ) 2 ·8H 2 O

The nature of the bound water in solids with hydrogen-bonded networks depends not only on temperature and pressure but also on the nature of the constituents. The collapse and reorientation of these network structures determines the stability of hydrated solids and transitions to other crystalline or amorphous phases. Here, we study the mechanochemically induced loss of bound water in Co₃(PO₄)₂·8H₂O and compare this process to the behavior under hydrostatic pressure. The associated phase transition and its kinetics were monitored by X-ray powder diffraction with Synchrotron radiation and quantitative IR spectroscopy. High shearing forces are responsible for the degradation of the hydrogen-b…

One-Dimensional Porous Carbon/Platinum Composites for Nanoscale Electrodes

A Novel High‐Pressure Tin Oxynitride Sn 2 N 2 O

Chemistry - a European journal in Press(in Press), chem.201904529 (2019). doi:10.1002/chem.201904529

Carbonization of disclike molecules in porous alumina membranes: toward carbon nanotubes with controlled graphene-layer orientation.

CCDC 1880628: Experimental Crystal Structure Determination

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CCDC 1042437: Experimental Crystal Structure Determination

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CCDC 930933: Experimental Crystal Structure Determination

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CSD 1995979: Experimental Crystal Structure Determination

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CCDC 1490687: Experimental Crystal Structure Determination

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CCDC 1857633: Experimental Crystal Structure Determination

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CCDC 1490689: Experimental Crystal Structure Determination

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CCDC 1490688: Experimental Crystal Structure Determination

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CCDC 1991689: Experimental Crystal Structure Determination

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CCDC 1429729: Experimental Crystal Structure Determination

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CCDC 1880629: Experimental Crystal Structure Determination

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CCDC 1429728: Experimental Crystal Structure Determination

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CCDC 1831844: Experimental Crystal Structure Determination

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CCDC 1958904: Experimental Crystal Structure Determination

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