Amine functionalized ZrO2 nanoparticles as biocompatible and luminescent probes for ligand specific cellular imaging

Surface functionalized ZrO2 nanoparticles show strong photoluminescence and are a versatile tool for cellular targeting due to their chemical functionality. They are highly photostable, biocompatible and amenable to coupling with bioligands (e.g. secondary goat anti-rabbit antibody (GAR) and tri-phenyl phosphine (TPP)) via carbodiimide chemistry. Antibody (GAR) functionalized ZrO2 nanoparticles were used to image the nuclear protein Sirt6, whereas triphenyl phosphonium ion (TPP) functionalized ZrO2 nanoparticles specifically targeted the mitochondria. The versatility and easiness of the ZrO2 surface modification opens up new possibilities for designing non-toxic water dispersible and photos…

Block copolymers from ionic liquids for the preparation of thin carbonaceous shells

This paper describes the controlled radical polymerization of an ionic-liquid monomer by RAFT polymerization. This allows the control over the molecular weight of ionic liquid blocks in the range of 8000 and 22000 and of the block-copolymer synthesis. In this work we focus on block copolymers with an anchor block. They can be used to control the formation of TiO2 nanoparticles, which are functionalized thereafter with a block of ionic-liquid polymer. Pyrolysis of these polymer functionalized inorganic nanoparticles leads to TiO2 nanoparticles coated with a thin carbonaceous shell. Such materials may, e.g., be interesting as battery materials.

Multi-photon imaging of amine-functionalized silica nanoparticles.

A convenient and simple strategy for preparing water soluble, photoluminescent functionalized silica nanoparticles (M-dots) in the absence of fluorophores or metal doping is demonstrated. These M-dots can be used for bioimaging using one and two-photon microscopy. Because of their high photostability, low toxicity and high biocompatibility compared with Lumidot™ CdSe/ZnS quantum dots, functionalized silica particles are superior alternatives for current bioimaging platforms. Moreover, the presence of a free amine group at the surface of the M-dots allows biomolecule conjugation (e.g. with antibodies, proteins) in a single step for converting these photoluminescent SiO(2) nanoparticles into …

Polyacrylonitrile block copolymers for the preparation of a thin carbon coating around TiO2 nanorods for advanced lithium-ion batteries.

Herein, a new method for the realization of a thin and homogenous carbonaceous particle coating, made by carbonizing RAFT polymerization derived block copolymers anchored on anatase TiO2 nanorods, is presented. These block copolymers consist of a short anchor block (based on dopamine) and a long, easily graphitizable block of polyacrylonitrile. The grafting of such block copolymers to TiO2 nanorods creates a polymer shell, which can be visualized by atomic force microscopy (AFM). Thermal treatment at 700 °C converts the polyacrylonitrile block to partially graphitic structures (as determined by Raman spectroscopy), establishing a thin carbon coating (as determined by transmission electron m…

Functional Enzyme Mimics for Oxidative Halogenation Reactions that Combat Biofilm Formation

Transition-metal oxide nanoparticles and molecular coordination compounds are highlighted as functional mimics of halogenating enzymes. These enzymes are involved in halometabolite biosynthesis. Their activity is based upon the formation of hypohalous acids from halides and hydrogen peroxide or oxygen, which form bioactive secondary metabolites of microbial origin with strong antibacterial and antifungal activities in follow-up reactions. Therefore, enzyme mimics and halogenating enzymes may be valuable tools to combat biofilm formation. Here, halogenating enzyme models are briefly described, enzyme mimics are classified according to their catalytic functions, and current knowledge about th…

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…

Fabrication of Single Cylindrical Au-Coated Nanopores with Non-Homogeneous Fixed Charge Distribution Exhibiting High Current Rectifications

We have designed and characterized a cylindrical nanopore that exhibits high electrochemical current rectification ratios at low and intermediate electrolyte concentrations. For this purpose, the track-etched single cylindrical nanopore in polymer membrane is coated with a gold (Au) layer via electroless plating technique. Then, a non-homogeneous fixed charge distribution inside the Au-coated nanopore is obtained by incorporating thiol-terminated uncharged poly(N-isopropylacrylamide) (PNIPAM) chains in series to poly(4-vinyl pyridine) (PVP) chains, which are positively charged at acidic pH values. The functionalization reaction is checked by measuring the current–voltage (I–V) curves prior …

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…

Particle size and morphology control of the negative thermal expansion material cubic zirconium tungstate

Cubic ZrW2O8 is a negative thermal expansion (NTE) material that is of interest as filler in controlled thermal expansion composites. It is easily accessible from a hydrated precursor, ZrW2O7(OH)2·2H2O, which can be obtained by hydrothermal synthesis. Different reaction conditions were investigated to gain control over the morphology, and to minimize the particle size. Optimized procedures resulted in rod-shaped particles with widths of 10–30 nm and lengths of 200–500 nm, which showed little agglomeration. The particle size and morphology of the precursor are preserved during conversion to the NTE phase at 600–650 °C.

Synthesis of Au, Ag, and Au–Ag Bimetallic Nanoparticles Using Pulicaria undulata Extract and Their Catalytic Activity for the Reduction of 4-Nitrophenol

Plant extract of Pulicaria undulata (L.) was used as both reducing agent and stabilizing ligand for the rapid and green synthesis of gold (Au), silver (Ag), and gold&ndash

A highly reduced graphene oxide/ZrOx–MnCO3 or –Mn2O3 nanocomposite as an efficient catalyst for selective aerial oxidation of benzylic alcohols

Highly reduced graphene oxide (HRG) nanocomposites of manganese carbonate doped with (1%) zirconia (ZrOx) nanoparticles [ZrOx(1%)–MnCO3/(X%)HRG (where X = 0–7)] were prepared employing a facile co-precipitation method in which the percentage of HRG was varied. The resulting nanocomposite was calcined at 300 °C. Further calcination of the catalyst at 500 °C resulted in the conversion of manganese carbonate to manganese oxide [ZrOx(1%)–Mn2O3/(X%)HRG]. The effect of the inclusion of HRG on the catalytic activity along with its comparative performance between carbonates and their respective oxides was studied for the liquid-phase selective oxidation of benzylic alcohols into corresponding aldeh…

Superparamagnetic γ-Fe2O3 nanoparticles with tailored functionality for protein separation

Polymer coated superparamagnetic gamma-Fe(2)O(3) nanoparticles were derivatized with a synthetic double-stranded RNA [poly(IC)], a known allosteric activator of the latent (2-5)A synthetase, to separate a single 35 kDa protein from a crude extract which cross reacted with antibodies raised against the sponge enzyme.

Cover Picture: Advanced Complex Inorganic Nanomaterials (Eur. J. Inorg. Chem. 13‐14/2016)

Multifunctional polymer-derivatized γ-Fe2O3 nanocrystals as a methodology for the biomagnetic separation of recombinant His-tagged proteins

Abstract Multifunctional polymer-derivatized superparamagnetic iron oxide (γ-Fe2O3) nanoparticles were prepared for biomagnetic separation of histidine-tagged recombinant proteins building up a faster and efficient method for protein separation by making use of their intrinsic magnetic properties. Using polymer bound γ-Fe2O3 nanocrystals, a 6× histidine-tagged recombinant protein (silicatein) with a molecular weight of 24 kDa has been isolated and purified. The supermagnetic iron oxide nanocrystals were characterized by transmission electron microscopy (TEM), high-resolution TEM (HRTEM), SQUID and Mossbauer and the polymer functionalization of the γ-Fe2O3 nanocrystals was monitored by UV–vi…

Green synthesis of silver nanoparticles mediated by Pulicaria glutinosa extract

Mujeeb Khan,1 Merajuddin Khan,1 Syed Farooq Adil,1 Muhammad Nawaz Tahir,2 Wolfgang Tremel,2 Hamad Z Alkhathlan,1 Abdulrahman Al-Warthan,1 Mohammed Rafiq H Siddiqui1 1Department of Chemistry, College of Science, King Saud University, Riyadh, Kingdom of Saudi Arabia; 2Institute of Inorganic and Analytical Chemistry, Johannes Gutenberg-University of Mainz, Mainz, Germany Abstract: The green synthesis of metallic nanoparticles (NPs) has attracted tremendous attention in recent years because these protocols are low cost and more environmentally friendly than standard methods of synthesis. In this article, we report a simple and eco-friendly method for the synthesis of silver NPs using an aqueous…

Fabrication, characterization, thermal stability and nanoassemblies of novel pullulan-aspirin conjugates

Abstract Present study deals with homogeneous and one-pot synthesis of novel macromolecular prodrugs (MPDs) of aspirin onto naturally occurring hydrophilic biopolymer pullulan. Pullulan-aspirin conjugates were synthesized by using green carboxylic acid activating reagent 1,1′-carbonyldiimidazole (CDI). The aspirin was first reacted with CDI to prepare aspirin-imidazolide at RT for 24 h which in situ reacted with pre-dissolved pullulan and the reaction preceded further for 24 h at 80 °C under nitrogen. Degree of substitution (DS 0.32–0.40) of aspirin onto pullulan was calculated from 1H NMR spectroscopy. Spectroscopic techniques confirmed the high covalent drug loading and purity. Thermal an…

Synthetic Approaches to Functionalized Chalcogenide Nanotubes

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…

ChemInform Abstract: Synthesis and Functionalization of Chalcogenide Nanotubes

New synthetic approaches to MS 2 (M = Sn, Nb, Mo, W) chalcogenide nanostructures are highlighted. Most chalcogenide particles can be functionalized directly with inorganic nanoparticles such as Au, ZnO or MnO. Depending on the Pearson hardness of the metal involved, the functionalization may be reversible or irreversible. A covalent functionalization strategy is based on a steric shielding of the coordination sphere of transition metal atoms in such a way that only coordination sites are available for bonding to the chalcogenide surface. This allows the immobilization of fluorophors, redox active groups or proteins onto chalcogenide nanoparticle.

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…

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

Cell Specific Targeting of Multifunctional γ-Fe2O3 Nanoparticles Through Surface Binding of dsDNA

AbstractThe immobilization of polyinosinic-polycytidylic acid [poly(IC)] on ã-Fe2O3 maghemite nanoparticles via the phosphor-amidate route using a multifunctional polymer is reported. The dsRNA coupled nanoparticles were used to visualize the Toll-like (TLR3) receptors at the cell surface. The presence of TLR3 was demonstrated independently in the Caki-1 cell line by RT-PCR and immunostaining techniques

Synthesis and Comparative Catalytic Study of Zirconia-MnCO3or -Mn2O3for the Oxidation of Benzylic Alcohols

Abstract We report on the synthesis of the zirconia–manganese carbonate ZrO x (x  %)–MnCO3 catalyst (where x=1–7) that, upon calcination at 500 °C, is converted to zirconia–manganese oxide ZrO x (x  %)–Mn2O3. We also present a comparative study of the catalytic performance of the both catalysts for the oxidation of benzylic alcohol to corresponding aldehydes by using molecular oxygen as the oxidizing agent. ZrO x (x  %)–MnCO3 was prepared through co‐precipitation by varying the amounts of Zr(NO3)4 (w/w %) in Mn(NO3)2. The morphology, composition, and crystallinity of the as‐synthesized product and the catalysts prepared upon calcination were studied by using scanning electron microscopy, tr…

Intrinsic superoxide dismutase activity of MnO nanoparticles enhances the magnetic resonance imaging contrast

Superoxide radicals are associated with the development of many severe diseases, such as cancer. Under nonpathogenic conditions, the natural enzyme superoxide dismutase (SOD) regulates the intracellular superoxide concentrations, but nearly all tumor tissues show reduced SOD levels. Selective imaging in early progression stages remains a key requirement for efficient cancer diagnosis and treatment. Magnetic resonance imaging (MRI) as a noninvasive tool with high spatial resolution may offer advantages here, but MRI contrast agents exhibiting a redox-triggered change in the image contrast towards superoxide radicals have not been reported so far. Here we show that manganese oxide (MnO) nanop…

Monitoring Thiol–Ligand Exchange on Au Nanoparticle Surfaces

Surface functionalization of nanoparticles (NPs) plays a crucial role in particle solubility and reactivity. It is vital for particle nucleation and growth as well as for catalysis. This raises the quest for functionalization efficiency and new approaches to probe the degree of surface coverage. We present an (in situ) proton nuclear magnetic resonance (1H NMR) study on the ligand exchange of oleylamine by 1-octadecanethiol as a function of the particle size and repeated functionalization on Au NPs. Ligand exchange is an equilibrium reaction associated with Nernst distribution, which often leads to incomplete surface functionalization following “standard” literature protocols. Here, we show…

Fractal-related assembly of the axial filament in the demosponge Suberites domuncula: relevance to biomineralization and the formation of biogenic silica,

Abstract The siliceous spicules of sponges (Porifera) show great variations of sizes, shapes and forms; they constitute the chief supporting framework of these animals; these skeletal elements are synthesized enzymatically by silicatein. Each sponge species synthesizes at least two silicateins, which are termed − α and − β . In the present study, using the demosponge Suberites domuncula , we studied if the silicateins of the axial filament contribute to the shape formation of the spicules. For these experiments native silicateins have been isolated by a new Tris/glycerol extraction procedure. Silicateins isolated by this procedure are monomeric (24 kDa), but readily form dimers through non-…

Pulicaria glutinosa Extract: A Toolbox to Synthesize Highly Reduced Graphene Oxide-Silver Nanocomposites

A green, one-step approach for the preparation of graphene/Ag nanocomposites (PE-HRG-Ag) via simultaneous reduction of both graphene oxide (GRO) and silver ions using Pulicaria glutinosa plant extract (PE) as reducing agent is reported. The plant extract functionalizes the surfaces of highly reduced graphene oxide (HRG) which helps in conjugating the Ag NPs to HRG. Increasing amounts of Ag precursor enhanced the density of Ag nanoparticles (NPs) on HRG. The preparation of PE-HRG-Ag nanocomposite is monitored by using ultraviolet-visible (UV-Vis) spectroscopy, powder X-ray diffraction (XRD), and energy dispersive X-ray (EDX). The as-prepared PE-HRG-Ag nanocomposities display excellent surfac…

Au@MnO-“Nanoblumen” - Hybrid-Nanokomposite zur selektiven dualen Funktionalisierung und Bildgebung

In j ngster Vergangenheit hat das Interesse f r die Entwicklung von Hybrid-Nanostrukturen, die sich aus verschiedenen Materialien zusammensetzen, in erheblichem Mase zugenommen. Es wurde berichtet, dass die Zusammenf hrung verschiedener Nanomaterialien, die ihrerseits spezifische optische, magnetische oder elektronische Eigenschaften aufweisen, zu Kompositen aus mehreren dieser Komponenten, deren individuelle Eigenschaften ver ndern oder sogar verbessern k nnen. Durch gezielte Optimierung der Struktur und der Grenzfl chenwechselwirkung innerhalb der Nanokomposite k nnte eine breite Basis f r zuk nftige Technologien geschaffen werden, beispielweise f r die synchrone Biomarkierung, Proteintre…

A Generalized Method for High‐Speed Fluorination of Metal Oxides by Spark Plasma Sintering Yields Ta 3 O 7 F and TaO 2 F with High Photocatalytic Activity for Oxygen Evolution from Water

A general method to carry out the fluorination of metal oxides with poly(tetrafluoroethylene) (PTFE, Teflon) waste by spark plasma sintering (SPS) on a minute scale with Teflon is reported. The potential of this new approach is highlighted by the following results. i) The tantalum oxyfluorides Ta3 O7 F and TaO2 F are obtained from plastic scrap without using toxic or caustic chemicals for fluorination. ii) Short reaction times (minutes rather than days) reduce the process time the energy costs by almost three orders of magnitude. iii) The oxyfluorides Ta3 O7 F and TaO2 F are produced in gram amounts of nanoparticles. Their synthesis can be upscaled to the kg range with industrial sintering …

An efficient esterification of pullulan using carboxylic acid anhydrides activated with iodine

Received August 9, 2009Accepted January 12, 2010Published online February 11, 2010Acylation of alcohols (esterification) with anhydride is an important and routinely utilizedtransformation in organic synthesis. Iodine is a cheap and one of the most powerful anhy-dride activating agents for the esterification of alcohols. Therefore, an efficient and cost ef-fective method was developed for the acylation of pullulan polysaccharide by using differentacid anhydrides activated with iodine. A series of organo-soluble pullulan esters were suc-cessfully synthesized, purified and characterized. Under solvent free conditions, it was feasi-ble to fabricate pullulan nonaacetate and pullulan stearate. A…

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…

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…

Advances in biogenic synthesis of palladium nanoparticles

Green approaches for the synthesis of nanoparticles provide advantages due to the fact that green protocols are benign and environmentally friendly. Among various green recipes, biogenic synthesis of nanoparticles has recently emerged as an active area of research due to the simplicity of this method, with cost effective protocols, higher potential of reduction and low toxic effect on human health and the environment. Moreover, the biogenic reduction occurs at physiological conditions of temperature and pressure. The raw materials are easily available and therefore, the reaction can easily be scaled up. This paper presents a review to give an idea about the most reliable, cost-effective and…

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…

Calixarene: A Versatile Material for Drug Design and Applications

The therapy of various diseases by the drugs entrapped in calixarene derivatives is gaining attraction of researchers nowadays. Calixarenes are macrocyclic nano-baskets which belong to cavitands class of host-guest chemistry. They are the marvelous hosts with distinct hydrophobic three dimensional cavities to entrap and encapsulate biologically active guest drugs. Calixarene and its derivatives develop inclusion complexes with various types of drugs and vitamins for their sustained/targeted release. Calixarene and its derivatives are used as carriers for anti-cancer, anti-convulsant, anti-hypertensive, anthelmentic, anti-inflammatory, antimicrobial and antipsychotic drugs. They are the impo…

The surface chemistry of iron oxide nanocrystals: surface reduction of γ-Fe2O3 to Fe3O4 by redox-active catechol surface ligands

The effect of surface functionalization on the structural and magnetic properties of catechol-functionalized iron oxide magnetic (γ-Fe2O3) nanocrystals was investigated. γ-Fe2O3 nanocrystals (NCs) were synthesized from iron acetyl acetonate in phenyl ether with 1,2-tetradecanediol, oleic acid, and oleylamine. X-ray powder diffraction in combination with Mossbauer spectroscopy revealed the presence of γ-Fe2O3 (maghemite) particles only. Replacement of oleic acid (OA) with catechol-type 3,4-dihydroxyhydrocinnamic acid (DHCA) or polydentate polydopamine acrylate (PDAm) surface ligands leads to a pronounced change of the magnetic behavior of the γ-Fe2O3 nanocrystals and separated them into two …

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

HPMC-salicylate conjugates as macromolecular prodrugs: Design, characterization, and nano-rods formation

The design, characterization, and nano-rods formation of hydroxypropylmethylcellulose (HPMC)-salicylate conjugates as macromolecular prodrugs, was described. HPMC, obtained from Zhejiang Zhongbao Imp and Exp Corp, was dried under vacuum at 110°C for 8 hr. Nanoparticles were prepared using dialysis process in which 170 mg of HPMC-salicylate sample was dissolved in 5 mL of purified DMSO and was dialyzed against distilled water for 4 days. HPMC-salicylic acid conjugates reveal the absence of sulfur in all of the samples showing that there is no introduction to tosylate groups either covalently bounded or as an impurity.

An efficient acetylation of dextran using in situ activated acetic anhydride with iodine

A facile, efficient, cost-effective and solvent-free acetylation method has been developed for the acetylation of dextran. Dextran acetates were successfully synthesized using different molar ratios of acetic anhydride in the presence of iodine as a catalyst without the use of any solvent. The reactions were realized at 50?C for 3 h under stirring and nitrogen. This efficient method yielded highly pure and organosoluble dextran esters. The reaction appears highly effective for obtaining higher degrees of substitution (DS) with great efficiency. Under solvent-free conditions, dextran triacetates were efficiently synthesized. It was also observed that the molar ratio can easily control the DS…

Frontispiece: A Step into the Future: Applications of Nanoparticle Enzyme Mimics

dsRNA-funktionalisierte γ-Fe2O3-Nanokristalle: ein Instrument zur gezielten Adressierung von Rezeptoren an der Zelloberfläche

Co-expression and Functional Interaction of Silicatein with Galectin

Sponges (phylum Porifera) of the class of Demospongiae are stabilized by a siliceous skeleton. It is composed of silica needles (spicules), which provide the morphogenetic scaffold of these metazoans. In the center of the spicules there is an axial filament that consists predominantly of silicatein, an enzyme that catalyzes the synthesis of biosilica. By differential display of transcripts we identified additional proteins involved in silica formation. Two genes were isolated from the marine demosponge Suberites domuncula; one codes for a galectin and the other for a fibrillar collagen. The galectin forms aggregates to which silicatein molecules bind. The extent of the silicatein-mediated s…

Ultrastrong composites from dopamine modified-polymer-infiltrated colloidal crystals

Although strong and stiff synthetic composites have long been developed, the microstructure of today's most advanced composites has yet to achieve the sophisticated hierarchy of hybrid materials built up by living organisms. We have assembled hard and tough multilayered nanocomposites, which contain alternating layers of Fe3O4 nanoparticles and a 3-hydroxy-tyramine (dopamine) substituted polymer (dopamine modified polymer), strongly cemented together by chelation through infiltration of the polymer into the Fe3O4 mesocrystal. With a Young's modulus of 17 ± 3 GPa and a hardness of 1.3 ± 0.4 GPa the nanocomposite exhibits high resistance against elastic as well as plastic deformation. Key fea…

Benzyl Alcohol Assisted Synthesis and Characterization of Highly Reduced Graphene Oxide (HRG)@ZrO2 Nanocomposites

We demonstrate a one-step solvothermal synthesis of HRG@ZrO2 nanocomposites using benzyl alcohol as solvent and stabilizing ligand. The as-synthesized HRG@ZrO2 hybrid nanocomposites showed a homogeneous distribution of the ZrO2 NPs (≈ 5 nm) onto HRG nanosheets. High resolution (HR)TEM, X-ray diffraction (XRD), and Raman spectroscopy confirmed the presence of cubic ZrO2. The presence of benzyl alcohol as stabilizing ligand was demonstrated by ultraviolet-visible (UV-vis), Fourier-transform infrared (FT-IR) spectroscopy and thermogravimetric analysis (TGA). The reduction of graphene oxide to HRG was also realized by X-ray photoelectron spectroscopy (XPS). A study of the HRG@ZrO2 formation mec…

Bioinspired synthesis of multifunctional inorganic and bio-organic hybrid materials

Owing to their physical and chemical properties, inorganic functional materials have tremendous impacts on key technologies such as energy generation and storage, information, medicine, and automotive engineering. Nature, on the other hand, provides evolution-optimized processes, which lead to multifunctional inorganic–bio-organic materials with complex structures. Their formation occurs under physiological conditions, and is goverened by a combination of highly regulated biological processes and intrinsic chemical properties. Nevertheless, insights into the molecular mechanisms of biomineralization open up promising perspectives for bioinspired and biomimetic design and the development of …

A High-Performance Asymmetric Supercapacitor Based on Tungsten Oxide Nanoplates and Highly Reduced Graphene Oxide Electrodes.

Tungsten oxide/graphene hybrid materials are attractive semiconductors for energy-related applications. Herein, we report an asymmetric supercapacitor (ASC, HRG//m-WO3 ASC), fabricated from monoclinic tungsten oxide (m-WO3 ) nanoplates as a negative electrode and highly reduced graphene oxide (HRG) as a positive electrode material. The supercapacitor performance of the prepared electrodes was evaluated in an aqueous electrolyte (1 m H2 SO4 ) using three- and two-electrode systems. The HRG//m-WO3 ASC exhibits a maximum specific capacitance of 389 F g-1 at a current density of 0.5 A g-1 , with an associated high energy density of 93 Wh kg-1 at a power density of 500 W kg-1 in a wide 1.6 V ope…

Localization and Characterization of Ferritin in Demospongiae: A Possible Role on Spiculogenesis

Iron, as inorganic ion or as oxide, is widely used by biological systems in a myriad of biological functions (e.g., enzymatic, gene activation and/or regulation). In particular, marine organisms containing silica structures—diatoms and sponges—grow preferentially in the presence of iron. Using primary sponge cell culture from S. domuncula–primmorphs—as an in vitro model to study the Demospongiae spiculogenesis, we found the presence of agglomerates 50 nm in diameter exclusively inside sponge specialized cells called sclerocytes. A clear phase/material separation is observed between the agglomerates and the initial stages of intracellular spicule formation. STEM-HRTEM-EDX analysis of the agg…

Extended release and enhanced bioavailability of moxifloxacin conjugated with hydrophilic cellulose ethers.

Macromolecular prodrugs (MPDs) of moxifloxacin were fabricated based on hydroxypropylcellulose (HPC) and hydroxyethylcellulose (HEC). UV/Vis spectrophotometry was employed to determine covalently loaded drug content (DC) of each conjugate. The degree of substitution (DS) of moxifloxacin attained ranged from 0.27 to 0.38 (HPC) and 0.19 to 0.26 (HEC) per anhydroglucose unit (AGU), respectively. Transmission electron microscopic analyses showed that HPC-moxifloxacin conjugates self-assembled into nanowires of ∼ 30 nm diameters while HEC-moxifloxacin conjugates self-assembled into nanoparticles of 150-350 nm. In vitro drug release studies revealed that 15 and 49% moxifloxacin release occurred f…

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@…

CeO2−x nanorods with intrinsic urease-like activity

The large-scale production and ecotoxicity of urea make its removal from wastewater a health and environmental challenge. Whereas the industrial removal of urea relies on hydrolysis at elevated temperatures and high pressure, nature solves the urea disposal problem with the enzyme urease under ambient conditions. We show that CeO2−x nanorods (NRs) act as the first and efficient green urease mimic that catalyzes the hydrolysis of urea under ambient conditions with an activity (kcat = 9.58 × 101 s−1) about one order of magnitude lower than that of the native jack bean urease. The surface properties of CeO2−x NRs were probed by varying the Ce4+/Ce3+ ratio through La doping. Although La substit…

Plant extracts as green reductants for the synthesis of silver nanoparticles: lessons from chemical synthesis.

The increasing use of silver (Ag) nanoparticles (NPs) in daily-life applications, electronics, or catalysis calls for green and cost-efficient synthetic methods. Ag NPs are used especially in biomedicine because of their antibacterial, antifungal, or anticancer properties. Chemical synthesis allows tuning the particle morphology, size, and crystallinity, but requires toxic and hazardous chemicals. Bioinspired synthetic protocols have shown promise to minimize environmental impact, but biological protocols for the synthesis of Ag NPs lack control on the morphology and crystallinity. This review briefly compiles the chemical synthesis of Ag NPs and contrasts it with "green" protocols based on…

Carbon-Coated Anatase TiO2Nanotubes for Li- and Na-Ion Anodes

aInstitute of Physical Chemistry and MEET Battery Research Centre, University of Muenster, 48149 Muenster, Germany bHelmholtz-Institute Ulm (HIU), Electrochemistry I, 89081 Ulm, Germany cKarlsruher Institute of Technology (KIT), 76021 Karlsruhe, Germany dInstitute for Organic Chemistry, University of Mainz, 55128 Mainz, Germany eGraduate School Materials Science in Mainz, 55128 Mainz, Germany fInstitute for Inorganic and Analytical Chemistry, University of Mainz, 55128 Mainz, Germany gMax Planck Institute for Polymer Research, 55128 Mainz, Germany

High-speed solid state fluorination of Nb2O5 yields NbO2F and Nb3O7F with photocatalytic activity for oxygen evolution from water

Solid state reactions are slow because the diffusion of atoms or ions through the reactant, intermediate and crystalline product phases is the rate-limiting step. This requires days or even weeks of high temperature treatment, and consumption of large amounts of energy. We employed spark-plasma sintering, an engineering technique that is used for high-speed consolidation of powders with a pulsed electric current passing through the sample to carry out the fluorination of niobium oxide in minute intervals. The approach saves time and large amounts of waste energy. Moreover, it allows the preparation of fluorinated niobium oxides on a gram scale using poly(tetrafluoroethylene) (®Teflon) scrap…

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…

Structural and Optical Study of Ga3+ Substitution in CuInS2 Nanoparticles Synthesized by a One-Pot Facile Method

A one-pot method was used to synthesize CuInxGa1–xS2 nanoparticles by substituting In3+ with Ga3+. The samples with composition of gallium ranging from 0% to 100% were synthesized by solving copper chloride, indium trichloride, gallium acetylacetonate, and thiourea as precursors in 1-octadecene, oleylamine, and oleic acid as noncoordinating, coordinating, and capping agent solvents, respectively. Depending on the chemical composition and synthesis conditions, the morphology of the as-synthesized nanoparticles obtained was trigonal, semitrigonal, hexagonal, and quasi-spherical. X-ray photoelectron spectroscopy and X-ray diffraction confirmed that Ga3+ substituted In3+ without any segregation…

CCDC 1408448: Experimental Crystal Structure Determination

Related Article: Faiza Asghar, Shamsa Munir, Saira Fatima, Babar Murtaza, Jahangeer Patujo, Amin Badshah, Ian S. Butler, Muhammad Babar Taj, Muhammad Nawaz Tahir|2022|J.Mol.Struct.|1249|131632|doi:10.1016/j.molstruc.2021.131632

CCDC 1915190: Experimental Crystal Structure Determination

Related Article: Faiza Asghar, Shamsa Munir, Saira Fatima, Babar Murtaza, Jahangeer Patujo, Amin Badshah, Ian S. Butler, Muhammad Babar Taj, Muhammad Nawaz Tahir|2022|J.Mol.Struct.|1249|131632|doi:10.1016/j.molstruc.2021.131632