Solvothermal Preparation of Drug Crystals: Didanosine

For the first time, crystals of suitable size for X-ray diffractometry structure determination (Dian important anti-HI V drug were prepared under solvothermal conditions. In this study, the crystal structure of didanosine (2`,3`-dideoxyinosine, ddI) in the form of a hydrate was determined using single-crystal X-ray diffractometry. Powder X-ray diffraction analysis revealed that the solid-state phase of the drug incorporated into pharmaceutical solid dosage forms is isostructural to the solvothermally prepared ddI material, even though they do not exhibit an identical chemical composition due to different water fractions occupying hydrophobic channels formed within the crystal lattice. Two ddI conformers are present in the structure, in agreement with a previous structure elucidation attempt. Concerning the keto enol equilibrium of ddI, our crystal data and vibrational characterizations by Fourier transform infrared (FTIR) and FT-Raman spectroscopy techniques were conclusive to state that both conformers exist in the keto form, contrary to solid-state NMR spectroscopic assignments that suggested ddI molecules occur as enol tautomers. In addition, characterizations by thermal (differential scanning calorimetry) and spectroscopic techniques allowed us to understand the structural similarities and the differences related to the hydration pattern of the nonstoichiometric hydrates.

Low temperature solvothermal synthesis of ZnO quantum dots

ZnO quantum dots were synthesized via a low-temperature solvothermal process without using surfactants. Heat treatment of ZnCl2 and NaOH solutions in tetra-ethylene glycol at 140°C led to the formation of spherical ZnO nanoparticles consisting of the aggregates of uniform-sized quantum dots. The particle size and morphology were characterized using transmission electron microscopy, dynamic light scattering, X-ray diffraction, and Brunauer–Emmett–Teller gas absorption measurements. It was found that the quantum dots in the particles were single crystals of ZnO of ∼5 nm in diameter having the wurtzite structure. The quantum dots showed quantum size effects even in the agglomerated form. The growth mechanism of this new type of ZnO nanoparticles is proposed.

Controlled synthesis of TiO2 hierarchical nanofibre structures via electrospinning and solvothermal processes : photocatalytic activity for degradation of methylene blue

The present article describes a new titanium oxide‐based (TiO2) photocatalyst that shows promise for acceleration of dye degradation. A hierarchical TiO2 nanostructure comprising nanorods on‐nanofibres has been prepared using a sol–gel route and electrospinning. Calcination of electrospun nanobre mats was performed in air at 500 °C. The TiO2 nanofibre surface was then exploited as a ‘seeding ground’ to grow TiO2 nanorods by a solvothermal process in NaOH. The nanofibres had a diameter of approximately 100 nm while the nanorods were evenly distributed on the nanofibre surface with a mean diameter of around 50–80 nm. The hierarchical nanostructure showed enhanced photocatalytic activity when compared to pure TiO2 nanofibres. This improved efficiency in degrading methylene blue through the photocatalytic process was attributed to the larger specific surface area of the TiO2 nanostructures, as well as high surface‐to‐volume ratio and higher reactive surface resulting in enhanced surface adsorption and interfacial redox reaction.

Solvothermal method to obtain europium-doped yttrium oxide

Pure yttrium oxide or mixed with europium oxide (3 at%) were treated in supercritical isopropanolic suspension at 500degreesC for 20 It and filling degree of 50%. Products were supercritically dried and characterized by scanning electron microscopy (SEM), X-ray powder diffraction (XRD), infrared spectroscopy (IR) and luminescence spectroscopy (LS). Particle shape is irregular with an equivalent diameter of ca. 5 mum. Cubic crystalline phase is mainly obtained and hydroxide ion in low concentration is detected by IR vibrational spectrum. Europium in this concentration does not extensively change such observed characteristics from the pure yttrium oxide. Luminescence spectra show that the doped product is a mixture of the two oxides added by oxyhydroxide impurities. Nevertheless, this precursor sample, after being heated at 900degreesC during 1 h, has all characteristics, especially luminescent ones, of the P22 commercial phosphor. (C) 2003 Elsevier B.V. (USA). All rights reserved.

Synthesis of wurtzite ZnS nanoparticles using the microwave assisted solvothermal method

In this article, we report the development of an efficient and rapid microwave assisted solvothermal (MAS) method to prepare wurtzite ZnS nanoparticles at 413 K using different precursors. The materials obtained were analyzed by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (MET) ultraviolet-visible (UV-vis) and photoluminescence (PL) measurements. The structure, surface chemical composition and optical properties were investigated as a function of the precursor. In addition, effects as well as merits of microwave heating on the processing and characteristics of ZnS nanoparticles obtained are reported. The possible formation mechanism and optical properties of these nanoparticles were also reported. © 2012 Elsevier B.V. All rights reserved.

TiO2 synthesized by microwave assisted solvothermal method: Experimental and theoretical evaluation

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Experimental and theoretical studies of photoluminescence in Zns obtained by microwave-assisted solvothermal method

A shift of the photoluminescence (PL) emission was observed in ZnS prepared by microwave assisted solvothermal method with the increase of the time in microwave. In this work we reported a study of the optical behavior linking with the structural disorder according to XRD and FEG-TEM results. The reduction of intrinsic defects in the lattice is responsible for the decrease of electronic levels in the band gap changing the PL profile. This effect was confirmed by electronic structure calculations.

Pigments based on Cr and Sb doped TiO2 prepared by microemulsion-mediated solvothermal synthesis for inkjet printing on ceramics

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

The modification of structural and optical properties of nano- and submicron ZnO powders by variation of solvothermal syntheses conditions

Nano- (30-60 nm) and submicron (100-350 nm) ZnO particles were synthesized using solvothermal method at 200 degrees C from an ethanolic solution of zinc acetate dihydrate, applying different reaction conditions, i.e., pH value of precursor and time of the reaction. The X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), UV-vis diffuse reflectance (DR), Raman spectroscopy, and photoluminescence (PL) spectroscopy have been employed for characterization of synthesized ZnO powders. It was shown that the structural, morphological, and optical properties are largely determined by reaction conditions during solvothermal synthesis. The particle crystallinity improves with the decrease of pH value and/or the increase of time of the reaction. The Raman and PL spectra analyses indicate that the oxygen interstitials are dominant intrinsic defects in solvothermally synthesized ZnO powders. It was observed that concentration of defects in wurtzite ZnO crystal lattices slightly changes with the variation of pH value of the precursor and time of the solvothermal reaction. The correlation between structural ordering and defect structure of particles and corresponding growth processes was discussed.

Phonon confinement model to measure the average sizes of anatase nanoparticles synthesized by a solvothermal method using H2O2

In this work, crystalline titanium dioxide (TiO2) nanoparticles with variable average crystallite sizes (e.g., 8 nm) and surface areas (e.g., 192 m² g-1) were synthesized in pure anatase phase using H2O2 to reduce the hydrolysis rate of the titanium ions. An isopropanol (IP) solution was employed as the reaction medium. The TiO2 nanoparticles were characterized by powder X-ray diffraction analysis (XRD), Raman spectroscopy and transmission electron microscopy (TEM). By changing the synthesis parameters it was possible to control nanoparticle size and avoid the coalescence process. A dependence of the Raman wavenumber on the nanocrystal sizes was determined, which is quite useful for a quick check of the size of TiO2 nanocrystals.

Solvothermal Synthesis, Structure and Optical Property of Nanosized CoSb3 Skutterudite

Binary skutterudite CoSb3 nanoparticles were synthesized by solvothermal method. The nanostructuring of CoSb3 material was achieved by the inclusion of various kinds of additives. X-ray diffraction examination indicated the formation of the cubic phase of CoSb3. Structural analysis by transmission electron microscopy analysis further confirmed the formation of crystalline CoSb3 nanoparticles with high purity. With the assistance of additives, CoSb3nanoparticles with size as small as 10 nm were obtained. The effect of the nanostructure of CoSb3on the UV–visible absorption and luminescence was studied. The nanosized CoSb3 skutterudite may find application in developing thermoelectric devices with better efficiency. K

Comparative study of photocatalytic performance of titanium oxide spheres assembled by nanorods, nanoplates and nanosheets

TiO2 spheres assembled by nanorods, nanoplates and nanosheets were fabricated by facile hydrothermal/solvothermal methods. The three samples were thoroughly characterised by scanning electron microscopy, X-ray diffraction, the Brunauer–Emmett–Teller method and UV spectroscopy. The surface area of spheres assembled by nanosheets was 83.9 m2g–1, which is larger than that obtained for nanorods (10.8 m2g–1) and nanoplates (6.31 m2g–1). Their photocatalytic performance was evaluated in terms of the decomposition rate of methyl orange in these three samples under UV irradiation. The best photoactivity was observed in the samples constructed from nanosheets.

Ultrathin hematite films deposited layer-by-layer on TiO2 underlayer for efficient water splitting under visible light

Ultrathin hematite (α-Fe2O3) film deposited on a TiO2 underlayer as a photoanode for photoelectrochemical water splitting was described. The TiO2 underlayer was coated on conductive fluorine-doped tin oxide (FTO) glass by spin coating. The hematite films were formed layer-by-layer by repeating the separated two-phase hydrolysis-solvothermal reaction of iron(III) acetylacetonate and aqueous ammonia. A photocurrent density of 0.683 mA cm−2 at +1.5 V vs. RHE (reversible hydrogen electrode) was obtained under visible light (>420 nm, 100 mW cm−2) illumination. The TiO2 underlayer plays an important role in the formation of hematite film, acting as an intermediary to alleviate the dead layer effect and as a support of large surface areas to coat greater amounts of Fe2O3. The as-prepared photoanodes are notably stable and highly efficient for photoelectrochemical water splitting under visible light. This study provides a facile synthesis process for the controlled production of highly active ultrathin hematite film and a simple route for photocurrent enhancement using several photoanodes in tandem.

Pre-lithiation of onion-like carbon/MoS2 nano-urchin anodes for high-performance rechargeable lithium ion batteries

Hybrid urchin-like nanostructures composed of a spherical onion-like carbon (OLC) core and MoS2 nanoleaves were synthesized by a simple solvothermal method followed by thermal annealing treatment. Compared to commercial MoS2 powder, MoS2/OLC nanocomposites exhibit enhanced electrochemical performance as anode materials of lithium-ion batteries (LIBs) with a specific capacity of 853 mA h g−1 at a current density of 50 mA g−1 after 60 cycles, and a moderate initial coulombic efficiency of 71.1%. Furthermore, a simple pre-lithiation method based on direct contact of lithium foil with MoS2/OLC nano-urchins was used to achieve a very high coulombic efficiency of 97.6% in the first discharge/charge cycle, which is at least 26% higher compared to that of pristine MoS2/OLC nano-urchins. This pre-lithiation method can be generalized to develop other carbon-metal sulfide nanohybrids for LIB anode materials. These results may open up a new avenue for the development of the next-generation high-performance LIBs.

Co(II) and Cr(III) complexes of formate-formamide mixed ligands: synthesis, structures, single crystal-to-single crystal transformation and magnetic behaviour

Solvothermal treatment of an equimolar mixture of Co(NO3)(2)center dot 6H(2)O, HCONH2 and NaN3 in MeOH at 100 degrees C yielded a three-dimensional NaCl type network Co(HCOO)(2)(HCONH2)(2) center dot HCONH2 (1a) containing formamides in the pores of the structure. Solvated pink 1a undergoes single crystal-to-single crystal (SCSC) transformation at 215 degrees C to form the desolvated dark brown product Co(HCOO)(2)-( HCONH2)(2) (1b) with the retention of the original framework. Reversible single crystal-to-single crystal transformation of 1b (brown) to 1a (pink) in the presence of excess formamide was also established at room temperature. The coordination environment around Co(II) in both 1a and 1b is octahedral with a CoN2O4 coordination composition. A similar reaction replacing Co(II) by Cr(III) produced a heterometallic 3D extended network Na[Cr(HCOO)(4)(HCONH2)(2)]center dot 2H(2)O (2a) at 100 degrees C. An increase in reaction temperature to 150 degrees C produced a simple mononuclear complex Cr(HCOO)(3)(HCONH2)(3) center dot 3H(2)O (2b). Variable temperature magnetic studies revealed the presence of a canting phenomena in both 1a and 1b, and hysteresis loop in the field dependent magnetisation plot at 2 K whereas complex 2a is simply paramagnetic in nature.