A new low temperature synthesis route of fraipontite (Zn,Al)3(Si,Al)2O5(OH)4

A low temperature synthesis method based on the decomposition of urea at 90°C in water has been developed to synthesise fraipontite. This material is characterised by a basal reflection 001 at 7.44 Å. The trioctahedral nature of the fraipontite is shown by the presence of a 06l band around 1.54 Å, while a minor band around 1.51 Å indicates some cation ordering between Zn and Al resulting in Al-rich areas with a more dioctahedral nature. TEM and IR indicate that no separate kaolinite phase is present. An increase in the Al content however, did result in the formation of some SiO2 in the form of quartz. Minor impurities of carbonate salts were observed during the synthesis caused by to the formation of CO32- during the decomposition of urea.

Influence of synthesis route on the catalytic properties of La1−xSrxMnO3

Lanthanum Strontium Manganate (LSM) powders were synthesized by six different routes, namely solid state reaction, drip pyrolysis, citrate, sol-gel, carbonate and oxalate co-precipitation. The LSM samples, produced by firing to 1000 °C for 5 h were then characterized by way of XRD, TPD's of oxygen, TPR and catalytic activity for a simple oxidation reaction, that of carbon monoxide to carbon dioxide. It was found that although the six samples had similar compositions and surface areas they performed quite differently during catalytic characterization. These observed differences correlated more closely to the mode of synthesis, than to the physical properties of the powders, or their impurity levels, indicating that the surface structures created by the different syntheses perform very differently under catalysis conditions. Co-precipitation and drip pyrolysis produced structures that were most efficient at facilitating oxidation type reactions.

Mechanical alloying—a novel synthesis route for amorphous phases

Mechanical alloying (MA) pioneered by Benjamin is a technique for the extension of solid solubility in systems where the equilibrium solid solubility is limited. This technique has, in recent years, emerged as a novel alternate route for rapid solidification processing (RSP) for the production of metastable crystalline, quasicrystalline, amorphous phases and nanocrystalline materials. The glass-forming composition range (GFR), in general, is found to be much wider in case of MA in comparison with RSP. The amorphous powders produced by MA can be compacted to bulk shapes and sizes and can be used as precursors to obtain high strength materials. This paper reports the work done on solid state amorphization by MA in Ti-Ni-Cu and Al-Ti systems where a wide GFR has been obtained. Al-Ti is a classic case where no glass formation has been observed by RSP, while a GFR of 25–90 at.% Ti has been obtained in this system, thus demonstrating the superiority of MA over RSP. The free energy calculations made to explain GFR are also presented.

Influence of synthesis route on structural phase transition in YBa2−xLaxCu3Oy (0

The compounds YBa2−xLaxCu3Oy, with compositions (0synthesised by nitrate decomposition method and solid-state reaction and characterised. Structural transition from orthorhombic to tetragonal phase occurred at (0.15synthesised by nitrate decomposition method, whereas no transition was observed in compounds synthesised by solid-state reaction for x values up to 0.20. The ternary phase formation temperature is influenced by the starting materials used and ionic size considerations. These factors are shown to determine the composition at which the changeover from orthorhombic (superconducting) to tetragonal (non-superconducting) phase transition (O–T transition) occurs.

Relaxor behaviour in BaBi4Ti4O15 ceramics fabricated using the powders obtained by mechanochemically assisted synthesis route

Mechanochemically activated reactants were found to facilitate the synthesis of fine powders comprising 200-400 nm range crystallites of BaBi4Ti4O15 at a significantly lower temperature (700 A degrees C) than that of solid-state reaction route. Reactants (CaCO3, Bi2O3 and TiO2) in stoichiometric ratio were ball milled for 48 h to obtain homogeneous mixture. The evolution of the BaBi4Ti4O15 phase was systematically followed using X-ray powder diffraction (XRD) technique. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were employed to probe its structural and microstructural details. The electron diffraction studies established the presence of correlated octahedral rotations and associated long-range polar ordering. High-resolution TEM imaging nevertheless revealed structural inhomogeneities leading to intergrowth defects. Dense BaBi4Ti4O15 ceramics with an average grain size of 0.9 mu m were fabricated using mechanochemically assisted synthesized powders at relatively low temperature (1000 A degrees C). The effect of grain size on the dielectric and relaxor behaviour of BaBi4Ti4O15 ceramics was investigated. Fine-grained ceramics (average grain size similar to 0.9 mu m) showed higher diffusion in phase transition, lower temperature of phase transition, lower Vogel-Fulcher freezing temperature and higher activation energy for the polarization reversal than those for coarse-grained ceramics (average grain size similar to 7 mu m) fabricated via the conventional solid-state reaction route.

The influence of the synthesis route on the final properties of SnO2-based varistors

A comparative study of two customary routes of ceramics processing applied to the synthesis of SnO2-based varistors is reported in this paper. Devices of equivalent composition were prepared through the Pechini method and through directly mixing the oxides without the addition of anti-agglomerants or binders. The microstructures of the sintered samples were characterised with X-ray diffraction and scanning and transmission electron microscopies. The electrical behaviour of the devices was studied on the basis of the current density versus electric field (J-E) characteristics and impedance spectroscopy measurements. The Pechini method ensures the homogeneity in the distribution of the additives in the tin oxide matrix but the formation of secondary phases seems to be independent of the synthesis route. Devices with similar non-linear coefficients of 18 and 21 were obtained through the mixed oxides route and the Pechini method, respectively. (C) 2007 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Effect of the Synthesis Route on the Microstructure and the Dielectric Behavior of CaCu3Ti4O12 Ceramics

CaCu3Ti4O12 (CCTO) was prepared by a conventional synthesis (CS) and through reaction sintering, in which synthesis and sintering of the material take place in one single step. The microstructure and the dielectric properties of CCTO have been studied by XRD, FE-SEM, EDS, AFM, and impedance spectroscopy to correlate structure, microstructure, and electrical properties. Samples prepared by reactive sintering show very similar dielectric behavior to those prepared by CS. Therefore, it is possible to prepare CCTO by means of a single-step processing method.

A new synthesis route for bone chars using CO2 atmosphere and their application as fluoride adsorbents

This study describes a new synthesis route for bone chars using a CO2 atmosphere and their behavior as adsorbent for fluoride removal from water. Specifically, we have performed a detailed analysis of the adsorption properties of bone char samples obtained at different carbonization conditions and a comparative study with samples of bone char obtained via pyrolysis under nitrogen. Experimental results show that the nature of the gas atmosphere (CO2 versus N2) and the carbonization temperature play a major role to achieve an effective bone char for water defluoridation. In particular, the best adsorption properties of bone char for fluoride removal are obtained with those samples synthesized at 700 °C. Carbonization temperatures above 700 °C under CO2 atmosphere cause the dehydroxylation of the hydroxyapatite in the bone char, thus reducing its fluoride adsorption capacity. The maximum fluoride adsorption capacity for the bone char obtained in this study under CO2 atmosphere (i.e., 5.92 mg/g) is higher than those reported for commercial bone chars.

Synthesis, Reactivity and Biological Activity of 17β-HSD1 Inhibitors Based on a Thieno[2,3-d]pryrimidin-4(3H)-one Core

Breast cancer is the most common cancer in women in Western countries. In the early stages of development most breast cancers are hormone-dependent, and estrogens, especially estradiol, have a pivotal role in their development and progression. One approach to the treatment of hormone-dependent breast cancers is to block the formation of the active estrogens by inhibiting the action of the steroid metabolising enzymes. 17beta-Hydroxysteroid dehydrogenase type 1 (17beta-HSD1) is a key enzyme in the biosynthesis of estradiol, the most potent female sex hormone. The 17beta-HSD1 enzyme catalyses the final step and converts estrone into the biologically active estradiol. Blocking 17beta-HSD1 activity with a specific enzyme inhibitor could provide a means to reduce circulating and tumour estradiol levels and thus promote tumour regression. In recent years 17beta-HSD1 has been recognised as an important drug target. Some inhibitors of 17beta-HSD1 have been reported, however, there are no inhibitors on the market nor have clinical trials been announced. The majority of known 17beta-HSD1 inhibitors are based on steroidal structures, while relatively little has been reported on non-steroidal inhibitors. As compared with 17beta-HSD1 inhibitors based on steroidal structures, non-steroidal compounds could have advantages of synthetic accessibility, drug-likeness, selectivity and non-estrogenicity. This study describes the synthesis of large group of novel 17beta-HSD1 inhibitors based on a non-steroidal thieno[2,3-d]pyrimidin-4(3H)-one core. An efficient synthesis route was developed for the lead compound and subsequently employed in the synthesis of thieno[2,3-d]pyrimidin-4(3H)-one based molecule library. The biological activities and binding of these inhibitors to 17beta-HSD1 and, finally, the quantitative structure activity relationship (QSAR) model are also reported. In this study, several potent and selective 17beta-HSD1 inhibitors without estrogenic activity were identified. This establishment of a novel class of inhibitors is a progressive achievement in 17beta-HSD1 inhibitor development. Furthermore, the 3D-QSAR model, constructed on the basis of this study, offers a powerful tool for future 17beta-HSD1 inhibitor development. As part of the fundamental science underpinning this research, the chemical reactivity of fused (di)cycloalkeno thieno[2,3-d]pyrimidin-4(3H)-ones with electrophilic reagents, i.e. Vilsmeier reagent and dimethylformamide dimethylacetal, was investigated. These findings resulted in a revision of the reaction mechanism of Vilsmeier haloformylation and further contributed to understanding the chemical reactivity of this compound class. This study revealed that the reactivity is dependent upon a stereoelectronic effect arising from different ring conformations.

Microwave-Assisted Synthesis of NiO Nanoparticles

NiO has been synthesized by microwave-induced chemical synthesis route using metalorganic complex of nickel in a domestic-type microwave oven (2.45 GHz). A novel metalorganic complex of nickel, viz., a beta-ketoester of nickel, synthesized and characterized as apart of this work, was employed as the precursor material. We varied the experimental parameters, such as the choice of solvent and microwave power, to obtain nanoparticles of NiO. The NiO nanoparticles were characterized by XRD, SEM, and TEM. The particle size of the NiO was found to vary from 7-40 nm. The magnetic behavior of the nanoparticles of NiO was examined with a vibrating sample magnetometer, revealing that as the particle size diminishes, the magnetic ordering in NiO changes, leading to a small, measurable coercivity.

On the mechanism of metal nanoparticle synthesis in the brust-schiffrin method

Brust-Schiffrin synthesis (BSS) of metal nanoparticles has emerged as a major breakthrough in the field for its ability to produce highly stable thiol functionalized nanoparticles. In this work, we use a detailed population balance model to conclude that particle formation in BSS is controlled by a new synthesis route: continuous nucleation, growth, and capping of particles throughout the synthesis process. The new mechanism, quite different from the others known in the literature (classical LaMer mechanism, sequential nucleation-growth-capping, and thermodynamic mechanism), successfully explains key features of BSS, including size tuning by varying the amount of capping agent instead of the widely used approach of varying the amount of reducing agent. The new mechanism captures a large body of experimental observations quantitatively, including size tuning and only a marginal effect of the parameters otherwise known to affect particle synthesis sensitively. The new mechanism predicts that, in a constant synthesis environment, continuous nucleation-growth-capping mechanism leads to complete capping of particles (no more growth) at the same size, while the new ones are born continuously, in principle leading to synthesis of more monodisperse particles. This prediction is validated through new experimental measurements.

Particle size, morphology and color tunable ZnO:Eu3+ nanophosphors via plant latex mediated green combustion synthesis

Efficient ZnO:Eu3+ (1-11 mol%) nanophosphors were prepared for the first time by green synthesis route using Euphorbia tirucalli plant latex. The final products were well characterized by powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV-visible spectroscopy (UV-Vis), Fourier transform infrared spectroscopy (FTIR), etc. The average particle size of ZnO:Eu3+ (7 mol%) was found to be in the range 27-47 nm. With increase of plant latex, the particle size was reduced and porous structure was converted to spherical shaped particles. Photoluminescence (PL) spectra indicated that the peaks situated at similar to 590, 615, 648 and 702 nm were attributed to the D-5(0) -> F-7(j(j=1,2,3,4)) transitions of Eu3+ ions. The highest PL intensity was recorded for 7 mol% with Eu3+ ions and 26 ml plant latex concentration. The PL intensity increases with increase of plant latex concentration up to 30 ml and there after it decreases. The phosphor prepared by this method show spherical shaped particles, excellent chromaticity co-ordinates in the white light region which was highly useful for WLED's. Further, present method was reliable, environmentally friendly and alternative to economical routes. (c) 2013 Elsevier B.V. All rights reserved.

Synthesis and Characterization of Au@Pt Nanoparticles with Ultrathin Platinum Overlayers

Gold-core platinum-shell (Au@Pt) nanoparticles with ultrathin platinum overlayers, ranging from submonolayer to two monolayers of platinum atoms, were prepared at room-temperature using a scalable, wet-chemical synthesis route. The synthesis involved the reduction of chloroauric acid with tannic acid to form 5 nm (nominal dia.) gold nanoparticles followed by addition of desired amount of chloroplatinic acid and hydrazine to form platinum overlayers with bulk Pt/Au atomic ratios (Pt surface coverages) corresponding to 0.19 (half monolayer), 0.39 (monolayer), 0.58 (1.5 monolayer) and 0.88 (2 monolayers). The colloidal particles were coated with octadecanethiol and phase-transferred into chlroform-hexane mixture to facilitate sample preparation for structural characterization. The structure of the resultant nanoparticles were determined to be Au@Pt using HRTEM, SAED, XPS, UV-vis and confirmed by cyclic voltammetry (CV) studies. Monolayers of octadecanethiol coated Au@Pt nanoparticles were self-assembled at an air-water interface and transfer printed twice onto a gold substrate to form bilayer films for electrochemical characterization. Electrochemical activity on such films was observed only after the removal of the octadecanethiol ligand coating the nanoparticles, using a RF plasma etching process. The electrochemical activity (HOR, MOR studies) of Au@Pt nanoparticles was found to be highest for particles having a two atom thick platinum overlayer. These nanoparticles can significantly enhance platinum utilization in electrocatalytic applications as their platinum content based activity was three times higher than pure platinum nanoparticles.

Type I collagen-mediated synthesis of noble metallic nanoparticles networks and the applications in Surface-Enhanced Raman Scattering and electrochemistry

In this paper, we demonstrated an effective enviromentally friendly synthesis route to prepare noble metallic (Au, Ag, Pt and Pd) nanoparticles (NPs) networks mediated by type I collagen in the absence of any seeds or surfactants. In the reactions, type I collagen served as stabilizing agent and assembly template for the synthesized metallic NPs. The hydrophobic interaction between collagen and mica interface as well as the hydrogen bonds between inter- and intra-collagen molecules play important roles in the formation of collagen-metallic NPs networks. The noble metallic NPs networks have many advantages in the applications of Surface-Enhanced Raman Scattering (SERS) and electrochemistry detection. Typically, the as-prepared Ag NPs networks reveal great Raman enhancement activity for 4-ATP, and can even be used to detect low concentration of DNA base, adenine.