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…

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.…

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.

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.

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

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…

Unexpected multivalent display of proteins by temperature triggered self-assembly of elastin-like polypeptide block copolymers

We report herein the unexpected temperature triggered self-assembly of proteins fused to thermally responsive elastin-like polypeptides (ELPs) into spherical micelles. A set of six ELP block copolymers (ELP(BC)) differing in hydrophilic and hydrophobic block lengths were genetically fused to two single domain proteins, thioredoxin (Trx) and a fibronectin type III domain (Fn3) that binds the α(v)β(3) integrin. The self-assembly of these protein-ELP(BC) fusions as a function of temperature was investigated by UV spectroscopy, light scattering, and cryo-TEM. Self-assembly of the ELP(BC) was unexpectedly retained upon fusion to the two proteins, resulting in the formation of spherical micelles …

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…

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

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…

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…

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…

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…

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

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

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…

Surface complexation modeling of arsenate adsorption by akagenéite (β-FeOOH)-dominant granular ferric hydroxide

Abstract A surface complexation model has been set up for the first time with akaganeite (β-FeOOH), a major compound of granular ferric hydroxide (GFH) used in groundwater purification units worldwide for arsenic and other toxic pollutant removal. Unlike the situation for the α-FeOOH polymorph goethite, there is yet no published surface complexation model to predict competing oxyanion effects. This is due to a linked bulk-surface reactivity by which excess protons released in an unknown amount from tunnel sites hamper quantification of surface protonation by acid titration. The measured proton uptake thus exceeds what can be expected from OH groups active in surface protonation. However, ch…

Helix–Coil Transition in Cylindrical Brush Polymers with Poly-l-lysine Side Chains

Cylindrical brush polymers with poly-l-lysine side chains were prepared by grafting lysine NCA from a macroinitiator via living ring-opening polymerization. The main chain degree of polymerization of the methacrylate main chain was Pw = 870, the side chains consisted of 25 and 55 lysine repeat units, respectively. Upon deprotection, the cylindrical brush polymers in 0.005 M NaBr exhibited an almost rodlike conformation with a Kuhn statistical segment length of several hundred nanometers. Cryo-TEM as well as AFM in aqueous solution clearly demonstrated pronounced undulations along the main chain at low ionic strength which could not be detected at higher salt concentrations. With increasing …

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

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 …

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 …

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…

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…

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 …

Interaction of Alkaline Metal Cations with Oxidic Surfaces: Effect on the Morphology of SnO2 Nanoparticles

Reaction pathways to SnO(2) nanomaterials through the hydrolysis of hydrated tin tetrachloride precursors were investigated. The products were prepared solvothermally starting from hydrated tin tetrachloride and various (e.g., alkali) hydroxides. The influence of the precursor base on the final morphology of the nanomaterials was studied. X-ray powder diffraction (XRD) data indicated the formation of rutile-type SnO(2). Transmission electron microscopy (TEM) studies revealed different morphologies that were formed with different precursor base cations. Data from molecular dynamics (MD) simulations provide theoretical evidence that the adsorption of the cations of the precursor base to the f…

The interplay of crystallization kinetics and morphology during the formation of SnO2 nanorods: snapshots of the crystallization from fast microwave reactions

A microwave-assisted reaction pathway to rutile SnO2nanorods was investigated. The microwave-treatment significantly reduces the reaction time compared to standard hydro-/solvothermal techniques. By moving the overall process into a shorter time slot, the growth and crystal formation during the reaction could be monitored via snapshots by trapping the intermediates through quenching. To gain a better insight into the template-free growth of one-dimensional (1D) nanostructures, a parameter-dependent (various temperatures/pressures and times were investigated) study was carried out. For all materials, the phase purity and crystallite sizes were determined by X-ray powder diffraction (XRD). Th…

Adsorption of the herbicide 4-chloro-2-methylphenoxyacetic acid (MCPA) by goethite.

Interaction between the goethite surface and 4-chloro-2-methylphenoxyacetic acid (MCPA) herbicide was studied using density functional theory (DFT) calculations combined with molecular dynamics (MD). The important step made here lies in the use of a periodic DFT method enabling the study of a mineral surface of different protonation states, in strong contrast with previous molecular modeling studies limited to single protonation state corresponding to the point of zero charge. Different surface OH groups and MCPA proton states were used to mimic the strong effects of pH on the outer- and inner-sphere surface complexes that are theoretically possible, together with their binding energies, an…

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 …

Macromol. Rapid Commun. 24/2010

Microstructures in shells of the freshwater gastropod Viviparus viviparus: a potential sensor for temperature change?

Abstract Mollusk shells contain a plethora of information on past climate variability. However, only a limited toolkit is currently available to reconstruct such data from the shells. The environmental data of some proxies (e.g. Sr/Ca ratios) is obscured by physiological effects, whereas other proxies, such as δ 18 O, simultaneously provide information on two or more different environmental variables. The present study investigates whether microstructures of the freshwater gastropod Viviparus viviparus provide an alternative means to reconstruct past water temperature. Cold and highly variable temperature regimes resulted in the precipitation of highly unordered first-order lamellae of simp…

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…