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The development of amorphous phosphate-based materials is of major interest in the field of biomaterials science, and especially for bone substitution applications. In this context, we herein report the synthesis of gel-derived hydrated amorphous calcium/sodium ortho/pyrophosphate materials at ambient temperature and in water. For the first time, such materials have been obtained in a large range of tunable orthophosphate/pyrophosphate molar ratios. Multi-scale characterization was carried out thanks to various techniques, including advanced multinuclear solid state NMR. It allowed the quantification of each ionic/molecular species leading to a general formula for these materials: [(Ca 2+ y Na + z H + 3+ x -2y-z )(PO 4 3- ) 1-x (P 2 O 7 4- ) x ](H 2 O) u . Beyond this formula, the analyses suggest that these amorphous solids are formed by the aggregation of colloids and that surface water and sodium could play a role in the cohesion of the whole material. Although the full comprehension of mechanisms of formation and structure is still to be investigated in detail, the straightforward synthesis of these new amorphous materials opens up many perspectives in the field of materials for bone substitution and regeneration. STATEMENT OF SIGNIFICANCE: The metastability of amorphous phosphate-based materials with various chain length often improves their (bio)chemical reactivity. However, the control of the ratio of the different phosphate entities has not been yet described especially for small ions (pyrophosphate/orthophosphate) and using soft chemistry, whereas it opens the way for the tuning of enzyme- and/or pH-driven degradation and biological properties. Our study focuses on elaboration of amorphous gel-derived hydrated calcium/sodium ortho/pyrophosphate solids at 70 °C with a large range of orthophosphate/pyrophosphate ratios. Multi-scale characterization was carried out using various techniques such as advanced multinuclear SSNMR ( 31 P, 23 Na, 1 H, 43 Ca). Analyses suggest that these solids are formed by colloids aggregation and that the location of mobile water and sodium could play a role in the material cohesion., (Copyright © 2019 Acta Materialia Inc. All rights reserved.)

The gold abundance in basic rocks, which normally varies between 0.5 and 5 ppb, has served as a very important indicator in many geoscience studies, including those focused on the planetary differentiation, redistribution of elements during the crustal process, and ore genesis. However, because gold is a monoisotopic element that exhibits a nugget effect, it is very difficult to quantify its ultra-low levels in rocks, which significantly limits our understanding of the origin of gold and its circulation between the Earth crust, mantle, and core. In this work, we summarize various sample digestion and combined preconcentration methods for the determination of gold amounts in rocks. They include fire assay, fire assay combined with Te coprecipitation and instrumental neutron activation analysis (INAA) or laser ablation inductively coupled plasma mass spectrometry, fusion combined with Te coprecipitation and anion exchange resins, dry chlorination, wet acid digestion combined with precipitation, ion exchange resins, solvent extraction, polyurethane foam, extraction chromatography, novel solid adsorbents, and direct determination by INAA. In addition, the faced challenges and future perspectives in this field are discussed.

High-silica zeolites, some of the most important and widely used catalysts in industry, have potential for application across a wide range of traditional and emerging technologies. The many structural topologies of zeolites have a variety of potential uses, so a strong drive to create new zeolites exists. Here, we present a protocol, the assembly-disassembly-organization-reassembly (ADOR) process, for a relatively new method of preparing these important solids. It allows the synthesis of new high-silica zeolites (Si/Al >1,000), whose synthesis is considered infeasible with traditional (solvothermal) methods, offering new topologies that may find novel applications. We show how to identify the optimal conditions (e.g., duration of reaction, temperature, acidity) for ADOR, which is a complex process with different possible outcomes. Following the protocol will allow researchers to identify the different products that are possible from a reaction without recourse to repetitive and time-consuming trial and error. In developing the protocol, germanium-containing UTL zeolites were subjected to hydrolysis conditions using both water and hydrochloric acid as media, which provides an understanding of the effects of temperature and pH on the disassembly (D) and organization (O) steps of the process that define the potential products. Samples were taken from the ongoing reaction periodically over a minimum of 8 h, and each sample was analyzed using powder X-ray diffraction to yield a time course for the reaction at each set of conditions; selected samples were analyzed using transmission electron microscopy and solid-state NMR spectroscopy.

Bioorthogonal chemistry largely relies on the use of abiotic metals to catalyze new-to-nature reactions in living systems. Over the past decade, metal complexes and metal-encapsulated systems such as nanoparticles have been developed to unravel the reactivity of transition metals, including ruthenium, palladium, iridium, copper, iron, and gold in biological systems. Thanks to these remarkable achievements, abiotic catalysts are able to fluorescently label cells, uncage or form cytotoxic drugs and activate enzymes in cellulo/vivo. Recently, strategies for the delivery of such catalysts to specific cell types, cell compartments or proteins were established. These studies reveal the enormous potential of this emerging field and its application in both medicinal chemistry and in synthetic biology., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Unlabelled: The development of bioactive phosphate-based glasses is essential in biomaterials science, and especially for bone substitution applications. In this context, the preparation of amorphous calcium-phosphorus hydroxide/oxide monoliths at low temperature is a key challenge for being able to develop novel hybrid materials for these applications. We herein report for the first time the synthesis and physical chemical characterisation of a novel family of pyrophosphate-based glasses (with the formula: {[(Ca(2+))1-x(H(+)/K(+))2x]2[(P2O7(4-))1-y(PO4(3-))4y/3]} n(H2O)), which were prepared by soft chemistry using low temperatures (T<70°C) and water as a solvent. The effect of the initial Ca/Pyrophosphate ratio on the structure and morphology of these pyrophosphate glasses was investigated in detail. Depending on this ratio, a glass (mixed calcium pyro- and orthophosphate) or a glass-ceramic (Ca10K4(P2O7)6·9H2O crystals embedded in the amorphous phase) was obtained. The proportion of the crystalline phase increased with an increase in the Ca/Pyrophosphate ratio in the batch solution. As expected for a glass, the formation of the glassy material was demonstrated not to be thermodynamically but rather kinetically driven, and the washing step was found to be crucial to prevent crystallisation. The stability of the amorphous phase was discussed considering the structural degrees of freedom of pyrophosphate entities, ionic strength of the initial solution and the inhibitory effect of orthophosphate ions. Overall, this new strategy of preparation of monolithic calcium-(pyro)phosphate based glasses using soft chemistry in water is highly promising in view of preparing new functional organic-inorganic hybrids for bone substitution applications., Statement of Significance: Phosphate-based glasses have gradually emerged as a potential alternative to silicate bioactive glasses in order to induce different biological mechanisms of degradation. The synthesis of such monolithic glasses at low temperature is a key step to allow new inorganic glass compositions to be reached and hybrid materials to be prepared. Although sol-gel and coacervate methods (respectively orthophosphate and metaphosphate precursors) have already been described to prepare such glasses, the use of toxic solvents and/or the final temperature treatment associated to these processes could limit the use of these materials for biomedical applications and/or the further development of hybrids. It is shown here that pyrophosphate precursors are an alternative strategy to obtain monolithic calcium (pyro)phosphate glasses under soft conditions (water solvent, 70°C)., (Copyright © 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.)

Two process models for carbon dioxide utilized gas-to-liquids (GTL) process (CUGP) mainly producing light olefins and Fischer-Tropsch (F-T) synthetic oils were developed by Aspen Plus software. Both models are mainly composed of a reforming unit, an F-T synthesis unit and a recycle unit, while the main difference is the feeding point of fresh CO2. In the reforming unit, CO2 reforming and steam reforming of methane are combined together to produce syngas in flexible composition. Meanwhile, CO2 hydrogenation is conducted via reverse water gas shift on the Fe-based catalysts in the F-T synthesis unit to produce hydrocarbons. After F-T synthesis, the unreacted syngas is recycled to F-T synthesis and reforming units to enhance process efficiency. From the simulation results, it was found that the carbon efficiencies of both CUGP options were successfully improved, and total CO2 emissions were significantly reduced, compared with the conventional GTL processes. The process efficiency was sensitive to recycle ratio and more recycle seemed to be beneficial for improving process efficiency and reducing CO2 emission. However, the process efficiency was rather insensitive to split ratio (recycle to reforming unit/total recycle), and the optimum split ratio was determined to be zero.

Immediately after its opening in 1855, Bunsen's Heidelberg laboratory became iconic as the most modern and best equipped laboratory in Europe. Although comparatively modest in size, the laboratory's progressive equipment made it a role model for new construction projects in Germany and beyond. In retrospect, it represents an intermediate stage of development between early teaching facilities, such as Liebig's laboratory in Giessen, and the new 'chemistry palaces' that came into existence with Wöhler's Göttingen laboratory of 1860. As a 'transition laboratory,' Bunsen's Heidelberg edifice is of particular historical interest. This paper explores the allocation of spaces to specific procedures and audiences within the laboratory, and the hierarchies and professional rites of passage embedded within it. On this basis, it argues that the laboratory in Heidelberg was tailored to Bunsen's needs in inorganic and physical chemistry and never aimed at a broad-scale representation of chemistry as a whole. On the contrary, it is an example of early specialisation within a chemical laboratory preceding the process of differentiation into chemical sub-disciplines. Finally, it is shown that the relatively small size of this laboratory, and the fact that after ca. 1860 no significant changes were made within the building, are inseparably connected to Bunsen's views on chemistry teaching.

The discovery of gigantic molecular nanostructures like coordination and polyoxometalate clusters is extremely time-consuming since a vast combinatorial space needs to be searched, and even a systematic and exhaustive exploration of the available synthetic parameters relies on a great deal of serendipity. Here we present a synthetic methodology that combines a flow reaction array and algorithmic control to give a chemical 'real-space' search engine leading to the discovery and isolation of a range of new molecular nanoclusters based on [Mo(2)O(2)S(2)](2+)-based building blocks with either fourfold (C4) or fivefold (C5) symmetry templates and linkers. This engine leads us to isolate six new nanoscale cluster compounds: 1, {Mo(10)(C5)}; 2, {Mo(14)(C4)4(C5)2}; 3, {Mo(60)(C4)10}; 4, {Mo(48)(C4)6}; 5, {Mo(34)(C4)4}; 6, {Mo(18)(C4)9}; in only 200 automated experiments from a parameter space spanning ~5 million possible combinations.

We present an evolutionary algorithm which predicts stable atomic structures and phase diagrams by searching the energy landscape of empirical and ab initio Hamiltonians. Composition and geometrical degrees of freedom may be varied simultaneously. We show that this method utilizes information from favorable local structure at one composition to predict that at others, achieving far greater efficiency of phase diagram prediction than a method which relies on sampling compositions individually. We detail this and a number of other efficiency-improving techniques implemented in the genetic algorithm for structure prediction code that is now publicly available. We test the efficiency of the software by searching the ternary Zr-Cu-Al system using an empirical embedded-atom model potential. In addition to testing the algorithm, we also evaluate the accuracy of the potential itself. We find that the potential stabilizes several correct ternary phases, while a few of the predicted ground states are unphysical. Our results suggest that genetic algorithm searches can be used to improve the methodology of empirical potential design.

Thin films of antimony doped tin sulphide (SnS:Sb) with different antimony concentrations have been prepared by the spray pyrolysis technique at the substrate temperature of 350°C. The physical properties of the films were studied as a function of increase in antimony dopant concentration (up to 10at.%). The films were characterized by different techniques to study their structural, optical and electrical properties. The X-ray diffraction analysis revealed that the films were polycrystalline in nature and having orthorhombic crystal structure with a preferred orientation in (111) direction. Due to Sb doping, the crystalline quality and the preferential orientation of SnS films were improved up to 6at.% of doping concentration. However, when doping concentration was increased above 6at.%, the crystalline quality and the preferential orientation of SnS films was deteriorated. Atomic force microscopy images revealed that the surface roughness of the films increased due to Sb doping. Optical measurements showed that the band gap values decreased from 1.60eV to 1.15eV with increase in Sb concentration. The photoluminescence spectra displayed that all the samples have an emission peak centered at 760nm. At 6at.% of Sb doping, the film has the lowest resistivity of 2.598×10(-2)Ωcm while the carrier concentration was high., (Copyright © 2013 Elsevier B.V. All rights reserved.)

The nitrogen conversions in relation to NH3 and HCN were investigated during microwave pyrolysis of sewage sludge. The nitrogen distributions and evolution of nitrogen functionalities in the char, tar, and gas fractions were conducted. The results suggested that the thermal cracking of protein in sludge produced three important intermediate compounds, including the amine-N, heterocyclic-N, and nitrile-N compounds. The deamination of amine-N compounds resulted from labile proteins cracking led to the formation of NH3 (about 7.5% of SS-N) between 300 and 500 °C. The cracking of nitrile-N and heterocyclic-N compounds in the tars from the dehydrogenation and polymerization of amine-N generated HCN (6.6%) from 500 to 800 °C, respectively. Moreover, the ring-opening of heterocyclic-N in the char and tar contributed to the release of NH3 accounting for about 18.3% of SS-N with the temperature increasing from 500 to 800 °C. Specifically, the thermal cracking of amine-N, heterocyclic-N and nitrile-N compounds contributed to above 80% of the total (HCN+NH3) productions. Consequently, it might be able to reduce the HCN and NH3 emissions through controlling the three intermediates production at the temperature of 500-800 °C.

The purpose of this study was to develop a simple and quick method of evaluating the physicochemical properties of carbonated apatite preparations (CAP) as an index of the bioaffinity of implantable materials based on Fourier-transformed-infrared (IR) spectra by chemometrics. The wet-synthesized CAPs contained various levels of carbonate content (CO(3)), and were analyzed microstrain parameter (MS), crystallite size parameter (CP), specific surface area (Sw), CO(3), and solubility parameter (pK(HAP)) using by X-ray powder diffraction, nitrogen gas adsorption, IR, and UV absorption. The IR spectral results of CAPs suggested that the peak intensities of CAP reflected the physicochemical properties of the samples. The IR data sets were calculated to obtain calibration models evaluating the physicochemical properties of CAPs by a partial least squares regression analysis (PLS). As validation of the calibration model, physicochemical properties of CAP could be evaluated based on validation IR data sets of independent samples, and those values had sufficient accuracy. The regression vector of each calibration model suggested that the physicochemical properties of CAP, such as CO(3), Sw, MS, CP, and pK(HAP), were affected by phosphate, hydroxyl, and carbonate groups., (Copyright © 2012 Wiley Periodicals, Inc.)

Cosmochemistry is the chemical analysis of extraterrestrial materials. This term generally is taken to mean laboratory analysis, which is the cosmochemistry gold standard because of the ability for repeated analysis under highly controlled conditions using the most advanced instrumentation unhindered by limitations in power, space, or environment. Over the past 40 y, advances in technology have enabled telescopic and spacecraft instruments to provide important data that significantly complement the laboratory data. In this special edition, recent advances in the state of the art of cosmochemistry are presented, which range from instrumental analysis of meteorites to theoretical-computational and astronomical observations.

Iron valence-to-core Fe Kβ X-ray emission spectroscopy (V2C XES) is established as a means to identify light atoms (C, N, O) within complex multimetallic frameworks. The ability to distinguish light atoms, particularly in the presence of heavier atoms, is a well-known limitation of both crystallography and EXAFS. Using the sensitivity of V2C XES to the ionization potential of the bound ligand, energetic shifts of ~10 eV in the ligand 2s ionization energies of bound C, N, and O may be observed. As V2C XES is a high-energy X-ray method, it is readily applicable to samples in any physical form. This method thus has great potential for application to multimetallic inorganic frameworks involved in both small molecule storage and activation., (© 2011 American Chemical Society)

The reaction of neodymium, europium, or terbium nitrate with cucurbit[6]uril (CB6) in the presence of the α-amino acid L-cysteine (L-cys) gives the complexes [Nd(L-cys)(CB6)(NO(3))(H(2)O)(4)]·2NO(3)·10H(2)O (1) and {[Ln(L-cys)(CB6)(H(2)O)(5)][Ln(L-cys)(CB6)(NO(3))(H(2)O)(4)]}·5NO(3)·22H(2)O with Ln = Eu (2) or Tb (3). 2 and 3 only differ from 1 by the presence of two independent metal ions in slightly different environments. In all cases, each metal atom is bound to the bidentate CB6 and the monodentate L-cys molecules, with the latter being in its zwitterionic form. The ammonium group of L-cys is directed away from CB6 and is involved in ion-dipole and hydrogen bonding interactions with the uncomplexed portal of the neighboring molecule, which gives rise to the formation of chiral one-dimensional assemblies of columnar shape., (© 2011 American Chemical Society)

Two explosive triazides of phosphorus(V), OP(N(3))(3) and SP(N(3))(3), have been prepared as neat substances and structurally characterized. Both compounds can be handled in gas, liquid, and solid states in submillimolar quantities. The melting points of OP(N(3))(3) and SP(N(3))(3) are +22 and -30 °C, respectively. The two triazides have been characterized by IR (Ar matrix and gas phase) and Raman (solid) spectroscopies. Their single-crystal structures were obtained by X-ray diffraction and found to be significantly distorted from the predicted ideal C(3) symmetry because of intermolecular interactions. The spectroscopic and structural properties are discussed in combination with density functional theory calculations., (© 2011 American Chemical Society)

The influence of the formal electrostatic interaction on the cis/trans coordination mode at a PdCl(2) center is investigated in a family of isostructural flexible diphosphine ligands Ph(2)P-X-C(6)H(4)-Y-PPh(2), where X and Y stand for neutral or cationic N,C-imidazolylene linkers. While the neutral and monocationic diphosphine spontaneously behave as classical cis-chelating ligands, only the dicationic diphosphine, where the electrostatic repulsion between the formal positive charges specifically takes place, is observed to behave as a trans-chelating ligand. The crucial role of electrostatics is analyzed on the basis of (31)P NMR data in solution and X-ray diffraction data in the crystal state. Comparative theoretical studies of the cis- and trans-chelated complexes, including EDA, static (31)P NMR, MESP, and AIM analyses, have been undertaken on the basis of DFT calculations in the gas phase or in the acetonitrile continuum. Whereas the cis-coordination mode is shown to be thermodynamically favored for the neutral ligand, the trans-coordination mode is found to be preferred for the dicationic homologue. The stereochemical preference is thus shown to be parallel to the expected effect of the formal electrostatic interaction. The results open perspectives for control of the cis- and trans-chelating behavior of flexible bidentate ligands by more or less reversible charge transfer at the periphery of the coordination sphere of a metallic center., (© 2011 American Chemical Society)

A series of heterocyclic compounds containing trivalent iodine, oxygen, and boron in a five-membered ring were prepared and structurally investigated by X-ray crystallography. 1-Chloro-4-fluoro-1H-1λ(3)-benzo[d][1,2,3]iodoxoborol-3-ol was synthesized by chlorination of 2-fluoro-6-iodophenylboronic acid followed by treatment of the intermediate iododichloride with water. 1-Acetoxy-4-fluoro-1H-1λ(3)-benzo[d][1,2,3]iodoxoborol-3-ol, 1-acetoxy-1H-1λ(3)-benzo[d][1,2,3]iodoxoborol-3-ol, and similar 1-substituted trifluoroacetate derivatives of benziodoxaborole were prepared the hypochlorite oxidation of 2-fluoro-6-iodophenylboronic acid or 2-iodophenylboronic acid in acetic or trifluoroacetic acid, respectively. 1-Acetoxy substituted benziodoxaborole can be further converted to the respective trifluoroacetate by treatment with trifluoroacetic acid or to the 1-hydroxy derivative by basic hydrolysis with aqueous NaHCO(3). X-ray structural studies of 1-chloro- and 1-trifluoroacetoxy substituted benziodoxaboroles 13, 17, and 18 have shown the presence of a planar five-membered heterocyclic ring with unusually short endocyclic I-O bond distance of 2.04-2.09 Å. Slow crystallization of 4-fluoro-1-trifluoroacetoxy-1H-1λ(3)-benzo[d][1,2,3]iodoxoborol-3-ol from methanol resulted in the formation of a tetrameric macrocyclic structure 21 resulting from self-assembly of the initially formed 4-fluoro-1,3-dimethoxy-1H-1λ(3)-benzo[d][1,2,3]iodoxoborol. Structural parameters of the five-membered iodoxoborol ring, such as the planar geometry and the short B-O and O-I bonds lengths in 13, 17, and 18 compared to those in 21 and known benziodoxoles are indicative of partially aromatic character of this ring. Density functional theory (DFT) predicted NIST (0) and NIST (1) indexes for 1-chloro- and 1-trifluoroacetoxy substituted benziodoxaboroles, however, are indicative of significantly lower aromaticity compared to the classic aromatic systems., (© 2011 American Chemical Society)

Amorphous SiO2 thin films were prepared on glass and silicon substrates by cost effective sol-gel method. Tetra ethyl ortho silicate (TEOS) was used as the precursor material, ethanol as solvent and concentrated HCl as a catalyst. The films were characterized at different annealing temperatures. The optical transmittance was slightly increased with increase of annealing temperature. The refractive index was found to be 1.484 at 550 nm. The formation of SiO2 film was analyzed from FT-IR spectra. The MOS capacitors were designed using silicon (100) substrates. The current-voltage (I-V), capacitance-voltage (C-V) and dissipation-voltage (D-V) measurements were taken for all the annealed films deposited on Si (100). The variation of current density, resistivity and dielectric constant of SiO2 films with different annealing temperatures was investigated and discussed for its usage in applications like MOS capacitor. The results revealed the decrease of dielectric constant and increase of resistivity of SiO2 films with increasing annealing temperature., (Copyright © 2010 Elsevier B.V. All rights reserved.)

A study was conducted to demonstrate that nanometer-thick titanium dioxide (TiO(2)) thin films could be prepared by the hydrolysis of titanium potassium oxalate using octadecylamine (ODA) Langmuir-Blodgett (LB) films as templates. The amount of TiO(2) generated in the LB film was found to be proportional to the number of deposited ODA layers, which enables precise control of the TiO(2) film thickness. After heat treatment of the LB films at 300-600°C, the photocatalytic activities of the resulting TiO(2) films were determined from the decomposition of stearic acid cast films when irradiated with UV light for different time periods. Higher photocatalytic activity was observed in TiO(2) films heat treated at lower temperatures.

This review article surveys recent experimental and theoretical advances in the gas-phase ion chemistry of the noble gases. Covered issues include the interaction of the noble gases with metal and non-metal cations, the conceivable existence of covalent noble-gas anions, the occurrence of ion-molecule reactions involving singly-charged xenon cations, and the occurrence of bond-forming reactions involving doubly-charged cations. Research themes are also highlighted, that are expected to attract further interest in the future.

An environmentally friendly and highly efficient procedure for the preparation of quinolines and fused polycyclic quinolines has been developed by a simple Friedlander annulation reaction of 2-aminoaryl ketone with carbonyl compounds in presence of zinc triflate under microwave irradiation and solvent-free conditions. The reaction also proceeds effectively when In(OTf)(3) was used in lieu of Zn(OTf)(2) as the catalyst. The catalyst can be recovered after the reaction and reused efficiently in subsequent runs.

Boronic acids have been widely used in a wide range of organic reactions, in the preparation of sensors for carbohydrates, and as potential pharmaceutical agents. With the growing importance of click reactions, inevitably they are also applied to the synthesis of compounds containing the boronic acid moiety. However, such applications have unique problems. Chief among them is the issue of copper-mediated boronic acid degradation in copper-assisted [2,3]-cycloadditions involving an alkyne and an azido compound as the starting materials. This review summarizes recent developments, analyzes potential issues, and discusses known as well as possible solutions.

The present work reports the successful synthesis of nano-hydroxyapatite, Ca(10)(PO(4))(6)(OH)(2) (denoted HAP) from calcined eggshell by hydrothermal method using cationic surfactant (CTAB) as regulator of nucleation and crystal growth. The reaction involved in the synthesis was studied elaborately. The influence of reaction temperature, ageing time and CTAB concentration on the synthesis of nano-HAP are also studied in addition to the effect of sintering temperature on the crystal growth. Spectral characterization involving Fourier transform infrared spectroscopy (FT-IR) and X-ray diffraction (XRD) techniques were performed for functional group analysis and phase identification of the materials, respectively. Thermal stability of nano-HAP was investigated by thermal analysis (TG/DTA). The physical characteristics, such as morphology and particle size of the synthesized nano-HAP were assessed thoroughly by scanning electron microscopy (SEM) and atomic force microscopy (AFM) techniques. The results have revealed that well-crystallized nano-HAP was synthesized by hydrothermal treatment at 160 degrees C for 10 h with the addition of CTAB at critical micelle concentration (CMC). It was also found that the synthesized nano-HAP was thermally stable up to 1100 degrees C.

A flame synthesis method has been used to prepare nanosized, high-surface-area Cu-Ce-O, Ni-Ce-O, and Fe-Ce-O catalysts from aqueous solutions of metal acetate precursors. The particles were formed by vaporization of the precursors followed by reaction and then gas to particle conversion. The specific surface areas of the synthesized powders ranged from 127 to 163 m(2)/g. High-resolution transmission electron microscope imaging showed that the particle diameters for the ceria materials are in the range of 3-10 nm, and a thin layer of amorphous material was observed on the surface of the particles. The presence and surface enrichment of the transition-metal oxides (CuO, NiO, and Fe(2)O(3)) on the ceria particles were detected using X-ray photoelectron spectroscopy. Electron energy-loss spectroscopic studies suggest the formation of a core-shell structure in the as-prepared particles. Extended X-ray absorption fine structure studies suggest that the dopants in all M-Ce-O systems are almost isostructural with their oxide counterparts, indicating the doping materials form separate oxide phases (CuO, Fe(2)O(3), NiO) within the host matrix (CeO(2)). Etching results confirm that most of the transition-metal oxides are present on the surface of CeO(2), easily dissolved by nitric acid. The performance of the flame-synthesized catalysts was examined toward water-gas shift (WGS) activity for fuel processing applications. The WGS activity of metal ceria catalysts decreases in the order Cu-Ce-O > Ni-Ce-O > Fe-Ce-O > CeO(2) with a feed mixture having a hydrogen to carbon monoxide (H(2)/CO) ratio of 1. There was no methane formation for these catalysts under the tested conditions.

Glass ionomer cements (GICs) have potential orthopaedic applications. Solgel processing is reported as having advantages over the traditional melt-quench route for synthesizing the glass phase of GICs, including far lower processing temperatures and higher levels of glass purity and homogeneity. This work investigates a novel glass formulation, BT 101 (0.48 SiO(2)-0.36 ZnO-0.12 CaO-0.04 SrO) produced by both the melt-quench and the solgel route. The glass phase was characterised by X-ray diffraction (XRD) to determine whether the material was amorphous and differential thermal analysis (DTA) to measure the glass transition temperature (T (g)). Particle size analysis (PSA) was used to determine the mean particle size and X-ray photoelectron spectroscopy (XPS) was used to investigate the structure and composition of the glass. Both glasses, the melt-quench BT 101 and the solgel BT 101, were mixed with 50 wt% polyacrylic acid (M (w), 80,800) and water to form a GIC and the working time (T (w)) and the setting time (T (s)) of the resultant cements were then determined. The cement based on the solgel glass had a longer T (w) (78 s) as compared to the cement based on the melt derived glass (19 s). T (s) was also much longer for the cement based on the solgel (1,644 s) glass than for the cement based on the melt-derived glass (25 s). The cements based on the melt derived glass produced higher strengths in both compression (sigma(c)) and biaxial flexure (sigma(f)), where the highest strength was found to be 63 MPa in compression, at both 1 and 7 days. The differences in setting and mechanical properties can be associated to structural differences within the glass as determined by XPS which revealed the absence of Ca in the solgel system and a much greater concentration of bridging oxygens (BO) as compared to the melt-derived system.

Porous NaO(2)-MgO-CaO-P(2)O(5) bioglass doped beta-tri-calcium phosphate (beta-TCP) bioceramic possessing high mechanical properties and well pore structure with high porosity and high pore connectivity has been prepared through dipping method with the porous polyurethane as the pore forming template. The sintering mechanism and the mechanical properties of the bioglass doped beta-TCP scaffold have been investigated by the X-ray diffraction (XRD) analysis, Scanning electron microscope (SEM) and thermal differential analysis (DTA). The scaffold's in vivo osteoconductivity has been evaluated by implantation of scaffolds into the femurs of New Zealand rabbits. The results show that the porous structure can achieve the densification process at a low temperature about 950 degrees C by a solid solution sintering mechanism and hence dense macropore scaffold with a compressive strength of 4.32 MPa when the porosity is 75% has been obtained. The in vivo test shows that the Na(2)O-MgO-CaO-P(2)O(5) bioglass doped porous beta-TCP bioceramic has a relatively fast bone formation after implantation; after 1 month implantation new deposited bone tissue has been detected on the strut of the porous scaffold and degraded particles also has been found on the surface of the new formed bone. After 6 months implantation the porous scaffold has been thoroughly covered with new formed bone. Results show that the Na(2)O-MgO-CaO-P(2)O(5) bioglass doped porous beta-TCP bioceramic is potential bone tissue engineering scaffold for orthopedic use.

Currently there is no standard method for measurement of atmospheric mercury dry deposition. While all operationally defined forms of atmospheric mercury (elemental, oxidized, and particulate) can be dry deposited, oxidized forms are of concern due to high deposition velocities, water solubility, and reactivity. This paper describes the development of a surrogate surface for characterizing potential dry deposition of gaseous oxidized mercury (GOM). Laboratory tests showed that the surface collected HgCl2, HgBr2, and HgO with equal efficiency, and deposition was not significantly influenced by temperature, humidity, or ozone concentrations. Deposition of mercury to surfaces in field deployments was correlated with GOM concentrations (r2 = 0.84, p < 0.01, n = 326. Weekly mean GOM deposition velocities from surface deployments (1.1 +/- 0.6 cm s(-1)) were higher than modeled values (0.4 +/- 0.2 cm s(-1)) at four field sites, but were within the range reported for direct measurements. Although the surfaces do not simulate the heterogeneity of natural surfaces and need to be validated by direct measurements, they do provide a physical means for estimating temporal trends and spatial variability of dry deposition of GOM.

The solution-phase synthesis of hollow micro- and nanostructures by using suitable templates such as hard templates, soft templates and reactive templates has attracted considerable attention in recent years. This paper is focused on the template synthesis of inorganic hollow structures with tailored size, morphology, and architecture, with emphasis on the templating strategies recently developed in our lab for the facile solution-phase synthesis of novel inorganic hollow structures. The formation mechanisms of the hollow structures via different kinds of templates are discussed in depth to show the general concepts for the preparation processes. The properties and applications of hollow structures are briefly described, demonstrating the promising and broad application fields of hollow materials.

The reaction of aqueous Fe(II) with Fe(III) oxides is a complex process, comprising sorption, electron transfer, and in some cases, reductive dissolution and transformation to secondary minerals. To better understand the dynamics of these reactions, we measured the extent and rate of Fe isotope exchange between aqueous Fe(II) and goethite using a 57Fe isotope tracer approach. We observed near-complete exchange of Fe atoms between the aqueous phase and goethite nanorods over a 30-day time period. Despite direct isotopic evidence for extensive mixing between the aqueous and goethite Fe, no phase transformation was observed, nor did the size or shape of the goethite rods change appreciably. High-resolution transmission electron microscopy images, however, appear to indicate that some recrystallization of the goethite particles may have occurred. Near-complete exchange of Fe between aqueous Fe(II) and goethite, coupled with negligible change in the goethite mineralogy and morphology, suggests a mechanism of coupled growth (via sorption and electron transfer) and dissolution at separate crystallographic goethite sites. We propose that sorption and dissolution sites are linked via conduction through the bulk crystal, as was recently demonstrated for hematite. Extensive mixing between aqueous Fe(II) and goethite, a relatively stable iron oxide, has significant implications for heavy metal sequestration and release (e.g., arsenic and uranium), as well as reduction of soil and groundwater contaminants.

Until about a decade ago, black carbon (BC) was thought to be the only light absorbing substance in the atmospheric aerosol except for soil or desert dust In more recent years, light absorbing polymeric carbonaceous material was found in atmospheric aerosols. Absorption increases appreciably toward short wavelengths, so this fraction was called brown carbon. Because brown carbon is thermally rather refractory, it influences the split between organic carbon (OC) and elemental carbon (EC) in thermal methods and, through its light absorption characteristics, leads to overestimations of BC concentrations. The goal of the present study was to extend the integrating sphere method to correct the BC signal for the contribution of brown carbon and to obtain an estimate of brown carbon concentrations. Humic acid sodium salt was used as proxy for brown carbon. The extended method is first tested on mixtures of test substances and then applied to atmospheric samples collected during biomass smoke episodes (Easter bonfires) in Austria. The resulting concentrations of black and brown carbon are compared to EC obtained with a widely used thermal method, the Cachier method (Cachier et al. Tellus 1989, 41B, 379-390) and a thermal-optical method (Schmid et al. Atmos. Environ. 2001, 35, 2111-2121), as well as to concentrations of humic like substances (HULIS) and to biomass smoke POM (particulate organic matter). Both the thermal methods were found to overestimate BC on days with large contributions of woodsmoke, which agrees with the findings of the method intercomparison study by Reisinger et at. (Environ. Sci. Technol. 2008, 42, 884-889). During the days of the bonfires, the Cachier method gave EC concentrations that were higher by a factor of 3.8 than the BC concentrations, while the concentrations obtained with the thermal-optical method were higher by a factor of 2.6.

A multifactorial experimental design was employed to quantify and rank the effects of a series of ligands on the rate of Fe(II) (18 microM) oxidation in a system containing chloride, sulfate, carbonate/bicarbonate, fluoride, and natural organic matter (NOM) at pH 8.34 +/- 0.13. Several factors and combinations thereof correlated with the rate of Fe(II) oxidation at the 95% level of confidence. Presented in decreasing order of significance, those factors were carbonate/bicarbonate, NOM, sulfate, chloride, the sulfate/fluoride interaction, and fluoride. The center point of the experimental design was repeated with different organic matters substituted, including Nordic Reservoir NOM, fulvic and humic acids; Suwannee River NOM, fulvic and humic acids; and Pony Lake fulvic acid. Despite the widely differing geographical origins of these organic materials, their overall impact on the oxidation rate of Fe(II) was consistent with the observed rate varying no more than a factor of 2 as a function of different organic matters (on a milligrams of carbon per liter basis). The utility of the pentafactorial response surface model (based on Nordic Lake NOM) to predict Fe(II) oxidation rates was evaluated for different natural water samples, including two seawater and one freshwater.

We reported the deposition and structural characterization of zinc sulfide (ZnS) thin films by chemical bath deposition (CBD) from a bath containing thiourea, ZnSO4 and ammonia in aqueous solution on common glass substrates. The solution concentration and annealing condition played a very important role on transmissivity, homogeneity, crystal and transmissivity of ZnS thin films. Spectrophotometer, X-ray diffraction (XRD), Scanning electron microscopy (SEM), Energy dispersive spectroscopy (EDS), digital four-point probe resistance measurement were used to characterize their properties and composition. As a result, transmissivity for the samples were more than 80%. Then it would be stable above 600 nm. The surface morphology of the thin films were homogeneous. However, there were some white spots in the SEM patterns that might be colloidal particles sedimentation mixed with ZnS. These particles could be amorphous or no crystal. According to the detection, ZnS films' resistance were changed with the ZnSO4 solutions' concentration.

Investigations into the structuring by two-photon polymerization of a nonshrinking, photosensitive, zirconium sol-gel material are presented. This hybrid material can be photostructured even when it contains up to 30 mol % of zirconium propoxide (ZPO); by varying the material's inorganic content, it is possible to modify and tune its refractive index. The introduction of ZPO significantly increases the photosensitivity of the resulting photopolymer. The fabricated three-dimensional photonic crystal structures demonstrate high resolution and a clear band-stop in the near-IR region. In contrast to common practice, no additional effort is required to precompensate for shrinkage or to improve the structural stability of the fabricated photonic crystals; this, combined with the possibility of tuning this material's optical, mechanical, and chemical properties, makes it suitable for a variety of applications by two-photon polymerization manufacturing.

In this study, estimation capacities of response surface methodology (RSM) and artificial neural network (ANN) in a heterogeneous photo-Fenton process were investigated. The zeolite Fe-ZSM5 was used as heterogeneous catalyst of the process for degradation of C.I. Acid Red 14 azo dye. The efficiency of the process was studied as a function of four independent variables, concentration of the catalyst, molar ratio of initial concentration of H2O2 to that of the dye (H value), initial concentration of the dye and initial pH of the solution. First, a central composite design (CCD) and response surface methodology were used to evaluate simple and combined effects of these parameters and to optimize process efficiency. Satisfactory prediction second-order regression was derived by RSM. Then, the independent parameters were fed as inputs to an artificial neural network while the output of the network was the degradation efficiency of the process. The multilayer feed-forward networks were trained by the sets of input-output patterns using a backpropagation algorithm. Comparable results were achieved for data fitting by using ANN and RSM. In both methods, the dye mineralization process was mainly influenced by pH and the initial concentration of the dye, whereas the other factors showed lower effects.

A hydrogen reduction and activated sintering process was proposed to prepare chromic oxide green pigment. Through ICP, XRD, SEM, FT-IR, UV, and CIE-L*a*b* colorimetric analysis, key factors and mechanism that influenced preparation of chromic oxide green pigment were studied. The results revealed that lower hydrogen reduction temperature, suitable addition of Al and Ba, were beneficial to obtaining the high quality chromic oxide green pigment. Typically, when the hydrogen reduction temperature was kept at 450-500 degrees C, physicochemical properties and color performance of the prepared chromic oxide green pigment doped with about 0.1-0.2 wt % Al and 0.2-0.5 wt % Ba conformed to commercial pigment standards. Additionally, characteristics of the green process were discussed. About 90 wt % KOH was reused directly and about 90 wt % Cr(VI) was conversed to Cr(III) directly from potassium chromate to chromic oxide green pigment. Integrating the proprietary green metallurgical process from chromite ore to potassium chromate of this laboratory, more than 99 wt % Cr(VI) could be conversed to Cr(III) compounds and about 99 wt % KOH could be recycled to use. The whole green process, ranging from chromite ore to chromic oxide green pigment, eventually not only provided the possibility for producing the high quality chromic oxide green pigment, but could reach comprehensive utilization of resources, inner recycle of KOH, and zero emission of Cr(VI).

The interaction of 20 wt% 12-tungstophosphoric acid with Ce(x)Zr(1-x)O(2) solid solutions has been studied by PXRD, FTIR, FT-Raman, H(2)-TPR, NH(3)-TPD, diffuse reflectance UV-vis-NIR, and (31)P MAS NMR techniques. The study indicates that the Keggin anions are attached to Lewis metal ion centres and anion vacancies on Ce(x)Zr(1-x)O(2) supports through WO terminal bonds. The Keggin units at the interface are chemically perturbed as indicated by non-intrinsic IR bands observed at 958 cm(-1) (WO(ter) bond), and 1052, 1102 cm(-1) (PO bond). NH(3)-TPD shows that the Keggin anions fixed to Lewis sites and/or oxygen ion vacancies decrease the ammonia uptake on Ce(x)Zr(1-x)O(2) solid solutions. H(2)-TPR shows modified redox behaviour of Ce(x)Zr(1-x)O(2) solid solutions due to the simultaneous reduction of ceria, decomposition of Keggin anions and the reduction of WO(3). The broadening of (31)P MAS NMR and DR-UV-vis-NIR spectra demonstrate the existence of chemical interactions between the Keggin anions and Ce(x)Zr(1-x)O(2) supports.

Both low-dimensional bar-coded metal oxide layers, which exhibit molecular hinging, and free-standing organic nanostructures can be obtained from unique nanofibers of vanadium oxide (VO(x)). The nanofibers are successfully synthesized by a simple chemical route using an ethanolic solution of vanadium pentoxide xerogel and dodecanethiol resulting in a double bilayered laminar turbostratic structure. The formation of vanadium oxide nanofibers is observed after hydrothermal treatment of the thiol-intercalated xerogel, resulting in typical lengths in the range 2-6 microm and widths of about 50-500 nm. We observe concomitant hinging of the flexible nanofiber lamina at periodic hinge points in the final product on both the nanoscale and molecular level. Bar-coded nanofibers comprise alternating segments of organic-inorganic (thiols-VO(x)) material and are amenable to segmented, localized metal nanoparticle docking. Under certain conditions free-standing bilayered organic nanostructures are realized.

The carrier transport properties in nanocrystalline semiconductors and organic materials play a key role for modern organic/inorganic devices such as dye-sensitized (DSC) and organic solar cells, organic and hybrid light-emitting diodes (OLEDs), organic field-effect transistors, and electrochemical sensors and displays. Carrier transport in these materials usually occurs by transitions in a broad distribution of localized states. As a result the transport is dominated by thermal activation to a band of extended states (multiple trapping), or if these do not exist, by hopping via localized states. We provide a general view of the physical interpretation of the variations of carrier transport coefficients (diffusion coefficient and mobility) with respect to the carrier concentration, or Fermi level, examining in detail models for carrier transport in nanocrystalline semiconductors and organic materials with the following distributions: single and two-level systems, exponential and Gaussian density of states. We treat both the multiple trapping models and the hopping model in the transport energy approximation. The analysis is simplified by thermodynamic properties: the chemical capacitance, C(mu), and the thermodynamic factor, chi(n), that allow us to derive many properties of the chemical diffusion coefficient, D(n), used in Fick's law. The formulation of the generalized Einstein relation for the mobility to diffusion ratio shows that the carrier mobility is proportional to the jump diffusion coefficient, D(J), that is derived from single particle random walk. Characteristic experimental data for nanocrystalline TiO(2) in DSC and electrochemically doped conducting polymers are discussed in the light of these models.

Using organic molecules to direct inorganic crystal growth has opened up new avenues for controlled synthesis on surfaces. Combined with soft lithography to form patterned templates, self-assembled monolayers (SAMs) have been shown to be a powerful approach for the assembly of inorganic nanostructures. In this work, we show that the surface free energy of SAM-modified silver, which depends on end groups and deposition method of SAMs, has a dramatic effect on the nucleation and growth of crystalline ZnO, a technologically important material, from supersaturated solutions. For SAMs with inert methyl end groups, ZnO nucleation is inhibited. For SAMs with chemically active (carboxylic or thiol) end groups, the ZnO morphology is found to be three-dimensional nanorods on low-surface-energy surfaces and two-dimensional thin films on high-energy surfaces.

Photoreduction of Cr(VI) involving Fe is strongly affected by the presence of organic or inorganic compounds in an acidic environment. In this study, we have found a new pathway of Cr(VI) photoreduction in the presence of Fe-(III) that is influenced by two inorganic electrolytes (i.e., NO3- and Cl-) and the pH. In NO3- and Cl- systems without Fe(III), Cr(VI) photoreduction could occur and was independent of the Cr(VI) concentration. The zero-order rate constant of the photoreduction reaction increased when the solution pH was decreased from 2 to 1; the reaction rate was higher in the NO3- system than in the Cl- system. The higher reaction rate in the NO3- system was attributed to the photolysis of NO3-, which resulted in the formation of NO2- for reduction of Cr(VI). Conversely, the effect of Fe-(III) addition on the increase in Cr(VI) photoreduction rate in the Cl- system was more significant than that in the NO3- system. The addition of Fe(III) to the Cl- system caused the formation of [Fe(OH2)5Cl]2+, the photolysis of which subsequently resulted in the formation of Fe(II) for reduction of the Cr(VI). This study suggests that the photolysis of NO3- and Fe-Cl complex may contribute significantly to Cr(VI) reduction in surface water that receives electroplating wastewater containing high levels of NO3-, Cl-, and Fe-(III). Therefore, under the acidic conditions that are favorable for Fe-Cl complex formation or in the presence of NO3-, the effects of inorganic components on Cr(VI) photoreduction cannot be ignored for the precise evaluation of the transformation of Cr in the environment.