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Agglomeration of copper nanowires (aspect ratios on the order of 1000) in polyethylene, commonly a major problem, could be prevented by modification of the nanowires with a surface layer of oleylamine. Nanocomposite films were prepared by mixing nanowire dispersions in organic solvents with polyethylene solutions followed by casting, drying, and sometimes hot pressing. Orientation of the copper nanowires by solid-state drawing of the composites at elevated temperatures led to preferential alignment of the nanowires in the drawing direction. This arrangement gave rise to a uniform dichroism in the near-infrared (NIR) region, which is uncommon in the case of the hitherto reported dichroic nanocomposites. The NIR dichroism is ascribed to the high aspect ratio of the metal wires. Hence, drawing of isotropic nanocomposites with metal wires may serve for the manufacture of NIR polarization filters., Competing Interests: The authors declare no competing financial interest.

In this work, we report a versatile approach for the development of an in-flow purification water system under solar illumination. Cellulose nanofibrils (CNFs) were impregnated with TiO 2 nanoparticles using water as a solvent to obtain hybrid CNF/TiO 2 monoliths with 98% porosity. The opposite surface potential enables an electrostatically induced direct conjugation between TiO 2 and CNFs. Scanning electron microscopy analysis of the surface morphology of the CNF/TiO 2 monolith shows a homogeneous dense coating of titania nanoparticles onto the interconnected nanofibril network, providing a Brunauer-Emmett-Teller surface area of about 80 m 2 ·g -1 for the hybrid monolith. Furthermore, compression tests reveal a good shape recovery after unloading, thanks to the highly flexible and mechanically stable three-dimensional structure. Finally, the CNF-based hybrids were tested as catalysts for the decomposition of organic pollutants under solar illumination. The tests were performed using a continuous flow reactor with a customized holder, allowing the solution to pass through the monolith. The results reveal a good photocatalytic activity and a long-term stability of the hybrid CNF/TiO 2 monolith toward the decomposition of methyl orange and paracetamol. These features provide a proof of concept for the applicability of the hybrid CNF/TiO 2 monoliths for in-flow purification of water under solar illumination, not only for model dyes but also for organic pollutants of high practical relevance.

Poly(phenylene methylene)s (PPMs) with high molar masses were isolated by polymerization of benzyl chloride catalyzed with tungsten(II) compounds and subsequent fractionation. Four different tungsten(II) catalysts were successfully exploited for the polymerization, for which a strict temperature profile was developed. The PPMs possessed roughly a trimodal molar mass distribution. Simple fractionation by phase separation of 2-butanone solutions allowed to effectively segregate the products primarily into PPM of low molar mass ( M n = 1600 g mol -1 ) and high molar mass ( M n = 167,900 g mol -1 ); the latter can be obtained in large quantities up to 50 g. The evolution of the trimodal distribution and the monomer conversion was monitored by gel permeation chromatography (GPC) and ¹H NMR spectroscopy, respectively, over the course of the polymerization. The results revealed that polymerization proceeded via a chain-growth mechanism. This study illustrates a new approach to synthesize PPM with hitherto unknown high molar masses which opens the possibility to explore new applications, e.g., for temperature-resistant coatings, fluorescent coatings, barrier materials or optical materials.

We report a solution-phase approach to the synthesis of crystalline copper nanowires (Cu NWs) with an aspect ratio >1000 via a new catalytic mechanism comprising copper ions. The synthesis involves the reaction between copper(II) chloride and copper(II) acetylacetonate in a mixture of oleylamine and octadecene. Reaction parameters such as the molar ratio of precursors as well as the volume ratio of solvents offer the possibility to tune the morphology of the final product. A simple low-cost spray deposition method was used to fabricate Cu NW films on a glass substrate. Post-treatment under reducing gas (5% H 2 + 95% N 2 ) atmosphere resulted in Cu NW films with a low sheet resistance of 24.5 Ω/sq, a transmittance of T = 71% at 550 nm (including the glass substrate), and a high oxidation resistance. Moreover, the conducting Cu NW networks on a glass substrate can easily be transferred onto a polycarbonate substrate using a simple hot-press transfer method without compromising on the electrical performance. The resulting flexible transparent electrodes show excellent flexibility ( R/ R o < 1.28) upon bending to curvatures of 1 mm radius.

Luminescent nanoparticles are researched for their potential impact in medical science, but no materials approved for parenteral use have been available so far. To overcome this issue, we demonstrate that Eu3+-doped hafnium dioxide nanocrystals can be used as non-toxic, highly stable probes for cellular optical imaging and as radiosensitive materials for clinical treatment. Furthermore, viability and biocompatibility tests on artificially stressed cell cultures reveal their ability to buffer reactive oxygen species, proposing an anti-cytotoxic feature interesting for biomedical applications.

Mixed methods studies (MMS) play an increasingly important role in the health sciences. Its potential lies in the acquisition of causal conditions and in the intersubjective understanding of diverse and new phenomena. The holistic and multi-perspective analysis strategy of MMS also allows a subject-oriented and an evidence-based approach to clinical practice. The article reviews the use of MMS in the health sciences on the basis of various reviews, and it highlights current methodological developments and research gaps., (Copyright © 2018. Published by Elsevier GmbH.)

A general method for preparing nano-sized metal oxide nanoparticles with highly disordered crystal structure and their processing into stable aqueous dispersions is presented. With these nanoparticles as building blocks, a series of nanoparticles@reduced graphene oxide (rGO) composite aerogels are fabricated and directly used as high-power anodes for lithium-ion hybrid supercapacitors (Li-HSCs). To clarify the effect of the degree of disorder, control samples of crystalline nanoparticles with similar particle size are prepared. The results indicate that the structurally disordered samples show a significantly enhanced electrochemical performance compared to the crystalline counterparts. In particular, structurally disordered Ni x Fe y O z @rGO delivers a capacity of 388 mAh g -1 at 5 A g -1 , which is 6 times that of the crystalline sample. Disordered Ni x Fe y O z @rGO is taken as an example to study the reasons for the enhanced performance. Compared with the crystalline sample, density functional theory calculations reveal a smaller volume expansion during Li + insertion for the structurally disordered Ni x Fe y O z nanoparticles, and they are found to exhibit larger pseudocapacitive effects. Combined with an activated carbon (AC) cathode, full-cell tests of the lithium-ion hybrid supercapacitors are performed, demonstrating that the structurally disordered metal oxide nanoparticles@rGO||AC hybrid systems deliver high energy and power densities within the voltage range of 1.0-4.0 V. These results indicate that structurally disordered nanomaterials might be interesting candidates for exploring high-power anodes for Li-HSCs.

Titanium dioxide (TiO 2 ) nanoparticles were synthesized by nonaqueous sol-gel route using titanium tetrachloride and benzyl alcohol as the solvent. The obtained 4 nm-sized anatase nanocrystals were readily dispersible in various polar solvents allowing for simple preparation of colloidal dispersions in water, isopropyl alcohol, dimethyl sulfoxide, and ethanol. Results showed that dispersed nanoparticles have acidic properties and exhibit positive zeta-potential which is suitable for their deposition by cathodic electrophoresis. Aluminum substrates were anodized in phosphoric acid in order to produce porous anodic oxide layers with pores ranging from 160 to 320 nm. The resulting nanopores were then filled with TiO 2 nanoparticles by electrophoretic deposition. The influence of the solvent, the electric field, and the morphological characteristics of the alumina layer (i.e., barrier layer and porosity) were studied.

Aim: The aim was to evaluate the impact of staff training and wearing safety vests as a combined intervention on interruptions during medication preparation and double-checking., Background: Interruptions and errors during the medication process are common and an important issue for patient safety in the hospital setting., Methods: We performed a pre- and post-intervention pilot-study using direct structured observation of 26 nurses preparing and double-checking 431 medication doses (225 pre-intervention and 206 post-intervention) for 36 patients (21 pre-intervention and 15 post-intervention)., Results: With staff training and the introduction of safety vests, the interruption rate during medication preparation was reduced from 36.8 to 28.3 interruptions per hour and during double-checking from 27.5 to 15 interruptions per hour., Conclusion: This pilot-study showed that the frequency of interruptions decreased during the critical tasks of medication preparation and double-checking after the introduction of staff training and wearing safety vests as part of a quality improvement process., Implications for Nursing Management: Nursing management should acknowledge interruptions as an important factor potentially influencing medication safety. Unnecessary interruptions can be successfully reduced by considering human and system factors and increasing both staff and nursing managers' awareness of 'interruptive communication practices' and implementing physical barriers. This is the first pilot-study specifically evaluating the impact of staff training and wearing safety vests on the reduction of interruptions during medication preparation and double-checking., (© 2017 John Wiley & Sons Ltd.)

We present a sol-gel processed hematite-titania-based photoanode, which exhibits a photocurrent of up to 2.5 mA/cm 2 at 1.23 V RHE under simulated AM 1.5 G illumination (100 mW/cm 2 ) thanks to the addition of an amorphous cocatalyst with the nominal composition Fe 20 Cr 40 Ni 40 O x . To unveil the role of the cocatalyst interconnected to the photoanode, we performed impedance measurements. According to the one order of magnitude higher value for the capacitance associated with surface states ( C SS ) compared to the bare photoanode, the function of the catalyst-photoanode interface resembles that of a p-n-like junction. In addition, the charge transfer resistance associated with charge transfer processes from surface states ( R ct,ss ) was unchanged at potentials between 0.8 and 1.1 V RHE after adding the cocatalyst, indicating that the catalyst has a negligible effect on the hole transport to the electrolyte. The understanding of the role of oxygen evolution catalysts (OECs) in conjunction with the photoanodes is particularly important for water splitting because most OECs are studied separately at considerably higher potentials compared to the potentials at which photoanode materials are operated., Competing Interests: The authors declare no competing financial interest.

The synthesis of metal oxide nanoparticles in organic solvents, so-called nonaqueous (or nonhydrolytic) processes represent powerful alternatives to aqueous approaches and have become an independent research field. 10 Years ago, when we published our first review on organic reaction pathways in nonaqueous sol-gel approaches, the number of examples was relatively limited. Nowadays, it is almost impossible to provide an exhaustive overview. Here we review the development of the last few years, without neglecting pioneering examples, which help to follow the historical development. The importance of a profound understanding of mechanistic aspects of nanoparticle crystallization and formation mechanisms can't be overestimated, when it comes to the design of rational synthesis concepts under minimization of trial-and-error experiments. The main reason for the progress in mechanistic understanding lies in the availability of characterization tools that make it possible to monitor chemical reactions from the dissolution of the precursor to the nucleation and growth of the nanoparticles, by ex situ methods involving sampling after different reaction times, but more and more also by in situ studies. After a short introduction to experimental aspects of nonaqueous sol-gel routes to metal oxide nanoparticles, we provide an overview of the main and basic organic reaction pathways in these approaches. Afterwards, we summarize the main characterization methods to study formation mechanisms, and then we discuss in great depth the chemical formation mechanisms of many different types of metal oxide nanoparticles. The review concludes with a paragraph on selected crystallization mechanisms reported for nonaqueous systems and a few illustrative examples of nonaqueous sol-gel concepts applied to surface chemistry., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A major obstacle in the introduction of luminescent nanoparticles (NPs) for medical applications is that quantum dots, the most widely studied luminescent materials, despite being biologically safe after coating with a bioshell, still contain a toxic core mostly consisting of semi-conductor NPs, which are not approved by regulatory agencies. Here we point to a potential solution of this problem by using rare-earth (RE) doped hafnia NPs. Hafnia is approved for medical injections as an effective means for the treatment of radiosensitive and radioresistant tumors and can significantly decrease potential toxicity of RE ions. As a step towards the achievement of this goal we describe the development of a bio-friendly method for the preparation of a stable doped hafnia hydrosol with an isoelectric point (IEP) of 8.2, which shows high fluorescence and biocompatibility in regular coagulant tests and cytotoxic assays., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Although aerogels prepared by the colloidal assembly of nanoparticles are a rapidly emerging class of highly porous and low-density materials, their ambient dried counterparts, namely xerogels, have hardly been explored. Here we report the use of nanoparticle-based BaTiO 3 xerogels as green bodies, which provide a versatile route to ceramic materials under the minimization of organic additives with a significant reduction of the calcination temperature compared to that of conventional powder sintering. The structural changes of the xerogels are investigated during ambient drying by carefully analyzing the microstructure at different drying stages. For this purpose, the shrinkage was arrested by a supercritical drying step under full preservation of the intermediate microstructure, giving unprecedented insight into the structural changes during ambient drying of a nanoparticle-based gel. In a first step, the large macropores shrink because of capillary forces, followed by the collapse of residual mesopores until a dense xerogel is obtained. The whole process is accompanied by a volume shrinkage of 97% and a drop in surface area from 300 to 220 m 2 g -1 . Finally, the xerogels are sintered, causing another shrinkage of up to 8% with a slight increase in the average pore and crystal sizes. At temperatures higher than 700 °C, an unexpected phase transition to BaTi 2 O 5 is observed.

Colloidal nanocrystals are extensively used as building blocks in nanoscience, and amazing results have been achieved in assembling them into ordered, close-packed structures. But in spite of great efforts, the size of these structures is typically restricted to a few micrometers, and it is very hard to extend them into the macroscopic world. In comparison, aerogels are macroscopic materials, highly porous, disordered, ultralight and with immense surface areas. With these distinctive characteristics, they are entirely contrary to common nanoparticle assemblies such as superlattices or nanocrystal solids, and therefore cover a different range of applications. While aerogels are traditionally synthesized by molecular routes based on aqueous sol-gel chemistry, in the last few years the gelation of nanoparticle dispersions became a viable alternative to improve the crystallinity and to widen the structural, morphological and compositional complexity of aerogels. In this Review, the different approaches to inorganic non-siliceous and non-carbon aerogels are addressed. We start our discussion with wet chemical routes involving molecular precursors, followed by processing methods using nanoparticles as building blocks. A unique feature of many of these routes is the fact that a macroscopic, often monolithic body is produced by pure self-assembly of nanosized colloids without the need for any templates.

Nanocomposites represent an interesting class of materials because their applications are of multidisciplinary importance. Herein, interactions at the interface of heterostructures, leading to superior performance and sometimes to synergistic interactions, are highlighted. Although the types of junctions seem to be similar in different fields, the requirements for their function is device-dependent and thus no generally valid recipe can be utilized. Nonetheless, the overlap between research fields unveils the unique opportunity to combine the different knowledge and expertise as an inspiration to designing new composites for photoelectrochemical water splitting, photocatalysis, chemoresistive sensors, batteries, and composite multiferroics. A non-comprehensive overview is provided with focus on selected examples to highlight the concepts behind these nanojunctions., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Multiferroic composite materials combining ferroelectric and ferromagnetic order at room temperature have great potential for emerging applications such as four-state memories, magnetoelectric sensors, and microwave devices. In this paper, we report an effective and facile liquid phase deposition route to create multiferroic composite thin films involving the spin-coating of nanoparticle dispersions of BaTiO 3 , a well-known ferroelectric, and CoFe 2 O 4 , a highly magnetostrictive material. This approach offers great flexibility in terms of accessible film configurations (co-dispersed as well as layered films), thicknesses (from 100 nm to several μm) and composition (5-50 wt % CoFe 2 O 4 with respect to BaTiO 3 ) to address various potential applications. A detailed structural characterization proves that BaTiO 3 and CoFe 2 O 4 remain phase-separated with clear interfaces on the nanoscale after heat treatment, while electrical and magnetic studies indicate the simultaneous presence of both ferroelectric and ferromagnetic order. Furthermore, coupling between these orders within the films is demonstrated with voltage control of the magnetism at ambient temperatures.

WO 3 photoanodes with remarkable photocurrent densities are presented. These photoanodes were prepared from three different commercially available WO 3 nanopowders. Doctor blading of the nanopowders followed by a short annealing in air led to nanostructured films. The best photoanode showed a photocurrent density of 3.5 mA cm -2 at 1.23 V vs. RHE in 1 m CH 3 SO 3 H under AM 1.5 G illumination (100 mW cm -2 ), surpassing values reported so far for bare WO 3 photoanodes. The study also showed that the photocurrent was strongly dependent on the electrolyte, indicating oxidation of the electrolyte rather than of water. Oxygen evolution measurements performed in different electrolytes revealed that the amounts of oxygen were highly dependent on the electrolyte. By comparing the photocurrent values in the different electrolytes with the amount of evolving oxygen, it was found that the electrolyte producing the highest photocurrent was the electrolyte with the lowest oxygen evolution. Stability measurements showed that the more oxygen is produced, the less stable is the photoanode. These results clearly underline the difficulty to correlate the photocurrent values with oxygen evolution, drawing the attention to one of the major limitations of photoelectrochemical water splitting., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Here we present a strategy to assemble one-dimensional nanostructures into a three-dimensional architecture with macroscopic size. With the assistance of centrifugation, we successfully gel ultrathin W18O49 nanowires with diameters of 1 to 2 nm and aspect ratios larger than 100 into 3D networks, which are transformed into monolithic aerogels by supercritical drying.

We present for the first time the synthesis of transition metal nitride aerogels, specifically Cu3N aerogels by destabilizing colloidal Cu3N nanoparticles into gels using controlled heat treatment. The resulting aerogels consist of interconnected three-dimensional networks with ultrasmall-sized nanoparticle bridges of a surface area of 381 m(2) g(-1) and only 5% relative density.

Self-assembly of inorganic nanowires on a large scale directly on a substrate represents a great challenge. Starting from colloidally stable dispersions of ultrathin tungsten oxide nanowires, we successfully assemble the nanowires on a centimeter scale on flat or patterned substrates by a simple evaporation-induced self-assembly method. The capillary flow generated during the evaporation is responsible for the assembly of the nanowires. The concentration of the nanowire dispersion has a significant influence on the self-assembly behavior. Well-aligned tungsten oxide nanowire thin films are achieved when the concentration of the dispersion is in the range from 0.5 to 3.0 mg/mL. While at higher concentrations disordered nanowire thin films with cracks are formed, lower concentrations do not result in the formation of a continuous thin film. A macroscopic device based on the self-assembled tungsten oxide nanowires is fabricated, exhibiting good performance for UV light detection. Our results may pave the road for integrating aligned ultrathin semiconductor nanowires into macroscopic devices for optoelectronic applications.

The preparation of macroscopic materials from two-dimensional nanostructures represents a great challenge. Restacking and random aggregation to dense structures during processing prevents the preservation of the two-dimensional morphology of the nanobuilding blocks in the final body. Here we present a facile solution route to ultrathin, crystalline Y2O3 nanosheets, which can be assembled into a 3D network by a simple centrifugation-induced gelation method. The wet gels are converted into aerogel monoliths of macroscopic dimensions via supercritical drying. The as-prepared, fully crystalline Y2O3 aerogels show high surface areas of up to 445 m(2)/g and a very low density of 0.15 g/cm(3), which is only 3% of the bulk density of Y2O3. By doping and co-doping the Y2O3 nanosheets with Eu(3+) and Tb(3+), we successfully fabricated luminescent aerogel monoliths with tunable color emissions from red to green under UV excitation. Moreover, the as-prepared gels and aerogels exhibit excellent adsorption capacities for organic dyes in water without losing their structural integrity. For methyl blue we measured an unmatched adsorption capacity of 8080 mg/g. Finally, the deposition of gold nanoparticles on the nanosheets gave access to Y2O3-Au nanocomposite aerogels, proving that this approach may be used for the synthesis of catalytically active materials. The broad range of properties including low density, high porosity, and large surface area in combination with tunable photoluminescence makes these Y2O3 aerogels a truly multifunctional material with potential applications in optoelectronics, wastewater treatment, and catalysis.

During the past decade, tremendous attention has been given to the development of new electrode materials with high capacity to meet the requirements of electrode materials with high energy density in lithium ion batteries. Very recently, cobalt silicate has been proposed as a new type of high capacity anode material for lithium ion batteries. However, the bulky cobalt silicate demonstrates limited electrochemical performance. Nanostructure engineering and carbon coating represent two promising strategies to improve the electrochemical performance of electrode materials. Herein, we developed a template method for the synthesis of amorphous cobalt silicate nanobelts which can be coated with carbon through the deposition and thermal decomposition of phenol formaldehyde resin. Tested as an anode material, the amorphous cobalt silicate nanobelts@carbon composites exhibit a reversible high capacity of 745 mA h g -1 at a current density of 100 mA g -1 , and a long life span of up to 1000 cycles with a stable capacity retention of 480 mA h g -1 at a current density of 500 mA g -1 . The outstanding electrochemical performance of the composites indicates their high potential as an anode material for lithium ion batteries. The results here are expected to stimulate further research into transition metal silicate nanostructures for lithium ion battery applications.

TiO2 has been considered as a promising anode material for lithium ion batteries. However, its poor rate capability originating from the intrinsically low lithium ion diffusivity and its poor electronic conductivity hampers putting such an application into practice. Both issues can be addressed by nanostructure engineering and conductive surface coating. Herein, we report a template-assisted synthesis of micron sized TiO2 fibers consisting of a mesoporous network of anatase nanoparticles of about 7.5 nm and coated by N doped carbon. In a first step, an amorphous layer of TiO2 was deposited on cobalt silicate nanobelts and subsequently transformed into crystalline anatase nanoparticles by hydrothermal treatment. The N doped carbon coating was realized by in situ polymerization of dopamine on the crystalline TiO2 followed by annealing under N2. After removal of the template, we obtained the final mesoporous TiO2 fibers@N doped carbon composite. Electrochemical tests revealed that the composite electrode exhibited excellent electrochemical properties in terms of specific capacity, rate performance and long term stability.

Water splitting with hematite is negatively affected by poor intrinsic charge transport properties. However, they can be modified by forming heterojunctions to improve charge separation. For this purpose, charge dynamics of TiO2:α-Fe2O3 nanocomposite photoanodes are studied using transient absorption spectroscopy to monitor the evolution of photogenerated charge carriers as a function of applied bias voltage. The bias affects the charge carrier dynamics, leading to trapped electrons in the submillisecond time scale and an accumulation of holes with a lifetime of 0.4 ± 0.1 s. By contrast, slower electron trapping and only few long-lived holes are observed in a bare hematite photoanode. The decay of the long-lived holes is 1 order of magnitude faster for the composite photoanodes than previously published for doped hematite, indicative of higher catalytic efficiency. These results illustrate the advantages of using composite materials to overcome poor charge carrier dynamics, leading to a 30-fold enhancement in photocurrent.

Experimental confirmation for the stronger interaction of Ni with multi-walled carbon nanotubes (MWCNTs) compared to Cu with MWCNTs is presented. The interfaces between Cu (Ni) nanoparticles side-on oriented onto MWCNTs are analyzed with high spatial resolution electron energy-loss spectroscopy (EELS) of the carbon K-edge. The EEL spectra reveal a rehybridization from sp(2) to sp(3) hybridized carbon of the outermost MWCNT layer at the Ni interface, but no such rehybridization can be observed at the Cu interface. The EELS results are supported by transmission electron microscopy (TEM) images, which show a better wetting behavior of Ni and a smaller gap at the Ni-MWCNT interface, as compared to the corresponding Cu interfaces. The different behavior of Cu and Ni can be explained in terms of differing valence d-orbital occupancy. For the successful experimental demonstration of this effect the use of a soft chemical metal deposition technique is crucial., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

High-capacity anode materials for lithium ion batteries (LIBs), such as spinel-type metal oxides, generally suffer from poor Li(+) and e(-) conductivities. Their drastic crystal structure and volume changes, as a result of the conversion reaction mechanism with Li, severely impede the high-rate and cyclability performance toward their practical application. In this article, we present a general and facile approach to fabricate flexible spinel-type oxide/reduced graphene oxide (rGO) composite aerogels as binder-free anodes where the spinel nanoparticles (NPs) are integrated in an interconnected rGO network. Benefiting from the hierarchical porosity, conductive network and mechanical stability constructed by interpenetrated rGO layers, and from the pillar effect of NPs in between rGO sheets, the hybrid system synergistically enhances the intrinsic properties of each component, yet is robust and flexible. Consequently, the spinel/rGO composite aerogels demonstrate greatly enhanced rate capability and long-term stability without obvious capacity fading for 1000 cycles at high rates of up to 4.5 A g(-1) in the case of CoFe2O4. This electrode design can successfully be applied to several other spinel ferrites such as MnFe2O4, Fe3O4, NiFe2O4 or Co3O4, all of which lead to excellent electrochemical performances.

Monodisperse, water-dispersible Co3O4 quantum dots with sizes of around 4.5 nm are prepared through a simple solution method. The resultant cobalt oxide quantum dots exhibit excellent visible-light-driven oxygen evolution activities in the [Ru(bpy)3](2+)-persulfate system under mild pH conditions.

Alignment of nanowires over a large area of flat and patterned substrates is a prerequisite to use their collective properties in devices such as gas sensors. In this work, uniform single-crystalline ultrathin W18 O49 nanowires with diameters less than 2 nm and aspect ratios larger than 100 have been synthesized, and, despite their flexibility, assembled into thin films with high orientational order over a macroscopic area by the Langmuir-Blodgett technique. Alignment of the tungsten oxide nanowires was also possible on top of sensor substrates equipped with electrodes. Such sensor devices were found to exhibit outstanding sensitivity to H2 at room temperature., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

We present the assembly of preformed antimony doped tin oxide nanobuilding blocks into centimeter sized aerogels with surface areas exceeding 340 m(2) g(-1). After calcination, the resistivity of the aerogels was decreased by 4 orders of magnitude to a few kΩ cm, with the primary conducting structures measuring only a few nanometers.

Texturing of magnetic ceramics and composites by aligning and fixing of colloidal particles in a magnetic field is a powerful strategy to induce anisotropic chemical, physical and especially mechanical properties into bulk materials. If porosity could be introduced, anisotropically structured magnetic materials would be the perfect supports for magnetic separations in biotechnology or for magnetic field-assisted chemical reactions. Aerogels, combining high porosity with nanoscale structural features, offer an exceptionally large surface area, but they are difficult to magnetically texture. Here we present the preparation of anatase-magnetite aerogel monoliths via the assembly of preformed nanocrystallites. Different approaches are proposed to produce macroscopic bodies with gradient-like magnetic segmentation or with strongly anisotropic magnetic texture.

Aerogels with their low density and high surface area are fascinating materials. However, their advantageous morphology is still far from being fully exploited owing to their limited compositional variety and low crystallinity. Replacing the sol-gel process by a particle-based assembly route is a powerful alternative to expand the accessible functionalities of aerogels. A strategy is presented for the controlled destabilization of concentrated dispersions of BaTiO3 nanoparticles, resulting in the assembly of the fully crystalline building blocks into cylindrically shaped monolithic gels, thereby combining the inherent properties of ternary oxides with the highly porous microstructure of aerogels. The obtained aerogels showed an unprecedentedly high surface area of over 300 m(2)  g(-1)., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Silica-natural rubber nanocomposites were obtained through a novel non-aqueous in situ sol-gel synthesis, producing the amount of water necessary to induce the hydrolysis and condensation of a tetraethoxysilane precursor by esterification of formic acid with ethanol. The method allows the synthesis of low hydrophilic silica nanoparticles with ethoxy groups linked to the silica surface which enable the filler to be more dispersible in the hydrophobic rubber. Thus, high loaded silica composites (75 phr, parts per hundred rubber) were obtained without using any coupling agent. Transmission Electron Microscopy (TEM) showed that the silica nanoparticles are surrounded by rubber layers, which lower the direct interparticle contact in the filler-filler interaction. At the lowest silica loading (up to 30 phr) silica particles are isolated in rubber and only at a large amount of filler (>60 phr) the interparticle distances decrease and a continuous percolative network, connected by thin polymer films, forms throughout the matrix. The dynamic-mechanical properties confirm that the strong reinforcement of the rubber composites is related to the network formation at high loading. Both the improvement of the particle dispersion and the enhancement of the silica loading are peculiar to the non-aqueous synthesis approach, making the method potentially interesting for the production of high-loaded silica-polymer nanocomposites.

The fundamental mission of materials science is the description of matter over all length scales. In this review, we apply this concept to particle research. Based on metal oxides, we show that every size range offers its specific features, and every size range had its era, when it was in the center of the research activities. In the first part of the review, we discuss on three metal oxides as examples, how and why the research focus changed its targeted size regime from the micrometer to the nanometer scale and back to the macroscopic world. Next, we present the distinct advantages of using nanoparticles over micrometer-sized particles in selected devices and we point out how such a shift in the size regime opens up new research directions. Finally, we exemplify the methods to introduce nanoparticles into macroscopic objects to make functional ceramics., (© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Nonaqueous synthesis routes have emerged as a powerful platform for directly obtaining diverse metal oxide nanoparticles with high crystallinity and tunable compositions. The benzyl alcohol (BA) route, for example, has been applied toward dozens of oxides including binary, ternary, and even more complex multimetal systems. Here we compare anatase nanoparticles made from the BA route with the traditional hydrothermal route. XPS measurements indicated that the BA route resulted in more reduced Ti states, corresponding to additional oxygen vacancies. These defects resulted in additional trap states, slower recombination, and slower charge transport. The performance of BA anatase was improved by incorporating niobium intended to suppress oxygen vacancies. The higher performance Nb-containing films were post-treated to yield a 7.96% power conversion efficiency (AM 1.5), similar to the state-of-the-art hydrolytic TiO2 in the same configuration.

Macroscopic monoliths of copper foams have been prepared by a template-assisted wet-chemical process. The method offers subtle control over the pore size and size distribution, density and macroscopic size and shape of the metal foam. Uniaxial compression tests revealed different deformation behavior depending on the relative density. Non-vacuum-based and low-temperature routes are attractive for the cost-effective production of metal foams., (© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

We present a detailed study on the nonaqueous synthesis of tungstite nanostructures with the focus on crystallization processes and the evolution of particle morphology. Time-dependent transmission electron microscopy (TEM) revealed a complex, particle-based crystallization mechanism involving first the formation of spherical and single-crystalline primary particles of 2-8 nm, which are cross-linked to large and unordered agglomerates, followed by their organization into rod-like structures of 40 × 200-400 nm. These rods undergo an internal ordering process, during which crystallographically oriented stacks of platelets develop. In situ small angle X-ray scattering (SAXS) experiments confirm this pathway of particle formation. The scattering intensity is dominated by the fast formation of rod-like particles, which cause an inter-platelet peak in the SAXS pattern with ongoing internal ordering. With continuous reaction time, the platelet stacks start to fall apart forming shorter assemblies of just a few platelets or even single platelets.

Among all the functional materials, ZnO plays an outstanding role in terms of chemical and physical properties, but also in terms of morphological variety and the number of reported synthesis approaches. Complex shapes and hierarchical architectures make ZnO a perfect example to study chemical and crystallization mechanisms. In this review article, we will discuss the nucleation and growth of ZnO nanostructures in liquid media by classical and non-classical (i.e., particle-based) crystallization pathways. We elaborate the chemical conditions and parameters that are responsible for the occurrence of one or the other pathway.

In this work a strategy for the control of structure and optical properties of inorganic luminescent oxide-based nanoparticles is presented. The nonaqueous sol-gel route is found to be suitable for the synthesis of hafnia nanoparticles and their doping with rare earths (RE) ions, which gives rise to their luminescence either under UV and X-ray irradiation. Moreover, we have revealed the capability of the technique to achieve the low-temperature stabilization of the cubic phase through the effective incorporation of trivalent RE ions into the crystal lattice. Particular attention has been paid to doping with europium, causing a red luminescence, and with lutetium. Structure and morphology characterization by XRD, TEM/SEM, elemental analysis, and Raman/IR vibrational spectroscopies have confirmed the occurrence of the HfO2 cubic polymorph for dopant concentrations exceeding a threshold value of nominal 5 mol %, for either Lu(3+) or Eu(3+). The optical properties of the nanopowders were investigated by room temperature radio- and photoluminescence experiments. Specific features of Eu(3+) luminescence sensitive to the local crystal field were employed for probing the lattice modifications at the atomic scale. Moreover, we detected an intrinsic blue emission, allowing for a luminescence color switch depending on excitation wavelength in the UV region. We also demonstrate the possibility of changing the emission spectrum by multiple RE doping in minor concentration, while deputing the cubic phase stabilization to a larger concentration of optically inactive Lu(3+) ions. The peculiar properties arising from the solvothermal nonaqueous synthesis here used are described through the comparison with thermally treated powders.

Dopant atoms are used to tailor the properties of materials. However, whether the desired effect is achieved through selective doping depends on the dopant distribution within the host material. The clustering of dopant atoms can have a deleterious effect on the achievable properties because a two-phase material is obtained instead of a homogeneous material. Thus, the examination of dopant fluctuations in nanodevices requires a reliable method to chemically probe individual atoms within the host material. This is particularly challenging in the case of functionalized nanoparticles where the characteristic length scale of the particles demands the use of a high-spatial-resolution and high-sensitivity technique. Here we demonstrate a chemically sensitive atomic resolution imaging technique which delivers direct site-specific information on the dopant distribution in nanoparticles. We employ electron energy-loss spectroscopy imaging in a scanning transmission electron microscope combined with multivariate statistical analysis to map the distribution of Ba dopant atoms in SrTiO(3) nanoparticles. Our results provide direct evidence for clustering of the Ba dopants in the SrTiO(3) nanoparticles outlining a possible explanation for the presence of polar nanoregions in the Ba:SrTiO(3) system. The results we present constitute the first example of site-specific atomic resolution spectroscopy of foreign atoms in doped nanoparticles and suggest a general strategy to ascertain the spatial distribution of impurity atoms in nanocrystals and hence improve the performance of nanoparticle-based devices.

A time-dependent study on the formation of LiFePO₄ with olivine-type structure is presented. The material is synthesized through a non-aqueous route in benzyl alcohol assisted by microwave radiation. The LiFePO₄ forms with an anisotropic morphology of microscale stick-like particles. The detailed structure of these particles and their evolution with reaction time is revealed by transmission electron microscopy; a 3D reconstruction of a particle by electron tomography provides insight into the formation mechanism of these sticks. Without applying a thermal post-annealing treatment or a carbon coating, the electrochemical behavior of the LiFePO₄ microsticks is assessed for the preparation of cathodes in lithium-ion batteries., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Functional superparamagnetic core-shell nanoparticles are synthesized by a microwave assisted route and can be used as colloidal supports for peptide synthesis in "quasi solution".

Zinc oxide nanostructures are known to exist in a great variety of morphologies. However, the underlying mechanisms leading to these architectures are far from being fully understood. Here, we present a time dependent study of the generation of zinc oxide nanorods, which arrange into bundles with a fan- or bouquet-like structure, using the benzyl alcohol route. The structural evolution of the nanoparticles was monitored by electron microscopy techniques, whereas the progress of the chemical reaction was followed by quantification of the organic by-products using gas chromatography. With this study we give a detailed insight into the formation of the zinc oxide structures, which involves a complex pathway based on many in parallel occurring processes such as crystallization of primary particles, their oriented attachment and surface reconstruction inside the nanoparticulate agglomerates. However, in spite of such an intricate growth behavior, the ZnO nanostructures are surprisingly uniform in size and shape., (This journal is © The Royal Society of Chemistry 2012)

Insight into the complex chemical mechanism for the formation of tungstite nanoparticles obtained by the reaction of tungsten hexachloride with benzyl alcohol is presented herein. The organic and inorganic species involved in the formation of the nanoparticles were studied by time-dependent gas chromatography and X-ray diffraction as well as by time-resolved in situ X-ray absorption near-edge structure and extended X-ray absorption fine structure spectroscopy. Principal component analysis revealed two intermediates, which were identified as WCl(4) and WOCl(4) by using linear combination analysis. Quick-scanning extended X-ray absorption fine structure spectroscopy enabled the time-dependent evolution of the starting compound, the intermediates and the product to be monitored over the full reaction period. The reaction starts with fast chlorine substitution and partial reduction during the dissolution of the tungsten hexachloride in benzyl alcohol followed by the generation of intermediates with W=O double bonds and finally the construction of the W-O-W network of the tungstite structure., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Crystalline ZnS and SnS(2) particles were synthesized by a modified benzyl alcohol route using benzyl mercaptan as solvent., (© The Royal Society of Chemistry 2011)

The clinical signs, pathological and laboratory findings of cattle suffering from a tremorgenic syndrome are described. Animals on a farm with a total of 22 cows, 18 heifers and 9 calves were fed mouldy grass and spent malt-grain silage. Five heifers were affected with muscular tremor, hyperexcitability and hypersensitivity. They were ataxic or in sternal recumbency, while their appetite remained normal. Haematology and blood chemistry in two heifers as well as cerebrospinal fluid from one sick animal were unremarkable. The pathological examination of one animal brought no macroscopic changes to light. Histological examination, however, revealed the degeneration of motor neurones in the midbrain, brain stem and spinal cord. Analysis of a silage sample provided evidence of the presence of Aspergillus clavatus, a mould capable of producing neurotoxic tremorgenic mycotoxins. Epidemiology, clinical findings, pathology and microbiological examination suggest that the five cattle were suffering from neuromycotoxicosis.

A detailed study is presented on the formation of MoO(2) nanoparticles from the dissolution of the precursor to the final rodlike product, with a focus on the exploration of the inorganic reaction occurring ahead of the nucleation step, and interplay between size and crystal structure of MoO(2). In situ X-ray absorption spectroscopy experiments show that the crystallization and the growth process of MoO(2) nanorods is initiated by rapid reduction of the MoO(2) Cl(2) precursor in benzyl alcohol and acetophenone. This reaction triggers the nucleation of 2 nm MoO(2) particles with spherical shape and hexagonal crystal structure. The transformation from spheres into rods emerges as a complex process driven by oriented attachment. High-resolution transmission electron microscopy and X-ray diffraction results provide evidence that the 2 nm particles first aggregate into 5-20 nm-large oriented assemblies. The increase in particle size induces the phase transition from hexagonal to the less symmetrical monoclinic crystal structure, and finally the transformation into rods. Is it shown that electrodes for lithium-ion batteries based on MoO(2) nanorods have a long-term cycling life. The specific discharge capacity even after 200 cycles at a discharge rate of 1 C is about 300 Ah kg(-1) ., (Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)