Kinetics study on the dissolution of UO_2 particles by microwave and conventional heating in 4 mol/L nitric acid

The dissolution of UO2 particles in 4 mol·L-1 nitric acid medium at temperatures of 90-110℃ by mi- crowave heating and conventional heating has been investigated, respectively. It is found that the dissolution ratios of UO2 particles by microwave heating were 10%-40% higher than that by conven- tional heating. Kinetics research shows that the dissolution of UO2 particles in 4 mol·L-1 nitric acid is controlled by the diffusion control model for microwave heating and by the surface reaction control model for conventional heating. The diffusion control model for the dissolution of UO2 particles by mi- crowave heating could be explained by the diffuseness on the surface of UO2 particles.     

Silica nanoparticles obtained by microwave assisted sol–gel process: multivariate analysis of the size and conversion dependence

Silica nanoparticles were synthesized by the sol–gel method in alcoholic solution under microwave irradiation in the presence of an ammonium catalyst. The effect of the reaction time, the reaction temperature, water and ammonium concentrations on particle size and conversion (measured by light scattering and FTIR respectively) were analyzed using multivariate analysis. The results showed that water and ammonium concentrations are the main factors that control the particle size and the conversion. Both properties increase with water and ammonium concentration. Moreover, comparing with the results obtained using traditional heating, the microwave heating gave rise to higher reaction rate and narrower dispersion of the particle size.     

Preparation and characterization of zein/chitosan complex for encapsulation of α-tocopherol, and its in vitro controlled release study

Chitosan (CS) nanoparticles coated with zein has been newly demonstrated as a promising encapsulation and delivery system for hydrophilic nutrient with enhanced bioactivities in our previous study. In this study, a hydrophobic nutrient, α-tocopherol (TOC), was successfully encapsulated into zein/CS complex. The fabrication parameters, including zein concentration, zein/CS weight ratio, and TOC loading percentage, were systematically investigated. The physicochemical and structural analysis showed that the electrostatic interactions and hydrogen bonds were major forces responsible for complex formation. The scanning electron microscopy study revealed the spherical nature with smooth surface of complex. TOC encapsulation was also evidenced by differential scanning calorimetry. The particle size and zeta potential of the complex varied from 200 to 800 nm and +22.8 to +40.9 mV, respectively. The kinetic release profile of the TOC showed burst effect followed by slow release. Compared with zein nanoparticles, zein/CS complex provided better protection of TOC release against gastrointestinal conditions, due to CS coatings. Zein/CS complex is believed to be a promising delivery system for supplementation or treatment of hydrophobic nutrients or drugs.     

Synthesis and electrochemical characterization of LiMn2−xAlxO4 powders prepared by mechanical alloying and rotary heating

LiMn_2−xAl_xO₄ (0.0⩽x⩽0.10) intercalation powders have been synthesized by mechanical alloying followed by rotary heating. The precursor of LiMn_2−xAl_xO₄ has been prepared using LiOH · H₂O, MnO₂, and Al₂O₃ by mechanical alloying, which ensured a high level of homogeneity in the chemical composition of the precursor and resulted in a reduction in the synthesis temperature and heating time. Highly crystallized LiMn_2−xAl_xO₄ powders were obtained by subsequent rotary heating of the precursor at 600 °C for 3 h. Rotary heating enhanced the experimental control in particle size distribution of the final products. The synthesized LiMn_2−xAl_xO₄ powder has a narrow particle size distribution, high discharge capacities and good cycleability. Compared with the conventional solid-state reaction process, the present method of mechanical alloying combined with rotary heating should be a suitable technique of decreasing synthesis temperature and shortening heating time, and enhancing the uniformity of particle size of the product.     

A comparative study of inclusion complexes of flunarizine with alpha (α-CD) and beta-cyclodextrin (β-CD)

A detailed NMR (¹H, COSY, and ROESY) spectroscopic study of complexation of Flunarazine (FL) with α- and β-CD was carried out. ¹H NMR titration studies confirmed the formation of FL/α-CD and FL/β-CD complexes as evidenced by chemical shift variations of the proton resonances of both the CDs and FL. The stoichiometry of the complexes was determined to be 1:2 (FL/α-CD) and 1:1 (FL/β-CD) and overall binding constants were also calculated. It was confirmed with the help of ROESY spectral data that only one of the F-substituted aromatic ring and phenyl ring penetrate the α-CD cavity while both F-substituted aromatic rings as well as phenyl ring penetrates the β-CD cavity during complexation. The binding modes of FL/CD cavity interactions derived from ROESY experimental data show that the resulting complex of FL with β-CD possesses better induced fit interaction as compared to α-CD, which is responsible for the enhanced molecular stability with β-CD in comparison to α-CD. The mode of penetration of guest into the CD cavity and structures of the complexes has been established.     

Preparation of titanium carbide powders by sol–gel and microwave carbothermal reduction methods at low temperature

Titanium carbide ultrafine powders were prepared from tetrabutyl titanate and sucrose by sol–gel and microwave carbothermal reduction. The influences of reaction temperature and molar ratio of Ti to C on the synthesis of titanium carbide were studied. The results show that excess amount of carbon plays a positive effect on the carbothermal reduction of TiO₂ at low temperature. The inceptive carbothermal reduction temperature of TiO₂ and formation of titanium oxycarbide was below 900 °C, and pure TiC can be prepared at 1,200 °C, which was considerably lower compared to that by conventional carbothermal reduction using a mixture of TiO₂ and carbon powders as raw materials. The morphology and particle size of synthesized TiC powder were examined by field emission-scanning electron microscopy (FE-SEM) and the quantities of the phases of the powders were analyzed by Rietveld refinement method, the particle sizes of the TiC powders synthesized at 1,300 °C distribute over 0.1–0.5 μm.     

Microwave-assisted reactions： Three-component process for the synthesis of 2-amino-2-chromenes under microwave heating

2-Amino-2-chromenes are class of heterocycles that posses considerable interest as pigments,cosmetics,potential agrochemicals and being the main constituents of many natural products.Although,they are generally prepared either under conventional heating,benign reagents or very recently,a three component condensation in poly-ethylene glycol-water in the presence of nanosized magnesium oxide,most of these methods require prolonged reaction time,reagents in stoichiometric amounts and generate moderate yield...     

Preparation of superhydrophobic silica nanoparticles by microwave assisted sol–gel process

Hydrophobic silica nanoparticles were obtained by microwave assisted sol–gel method using a two-step procedure. In the first step different size silica particles were generated from tetraethyl orthosilicate and in the second one the silica particles were hydrophobized using hexadecyl trimethoxysilane (HDTMOS). Under microwave irradiation, high conversion degrees were obtained at relatively short reaction times. The HDTMOS added in the second step instead of coating the silica nanoparticles generated new ones and therefore the final product showed a bimodal size distribution. All the synthesized nanoparticles gave rise to high water contact angles (≈150°) and low hysteresis values.     

Conformational investigation of α-methylthio and α-phenylthio derivatives of acetone and cyclohexanone by molecular mechanics. An x-ray study of α-phenylthioacetone

A conformational investigation of -methylthioacetone, -methylthiocyclohexanone, -phenylthioacetone, and -phenylthiocyclohexanone was undertaken in the MM2(87) force field. In all cases theac-G rotamers with unidirectional orientation of the C=O and S-R bonds are preferred in accordance with the experimental investigations. In all cases the energy of dipole-dipole interaction makes a contribution to the stabilization of these forms. For the eclipsedsp conformers the relatively high calculated values of the energies contradict the data of the experimental investigations, which take account of their participation in the equilibrium. X-ray crystallographic analysis of -phenylthioacetone (3) showed that thesp-T structure with a planar orientation of the thioanisole fragment is realized in the solid phase.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan' Scientific Center, Russian Academy of Sciences, 420083 Kazan'. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 6, pp. 1364–1371, June, 1992.     

Selective synthesis of α-fluoro-β-keto- and α-fluoro-β-aminophosphonates via electrophilic fluorination by selectfluor

A series of α-mono- and α,α-difluoro-β-ketophosphonates were synthesized in moderate to good yields with excellent selectivities via electrophilic fluorination by Selectfluor. Subsequently, synthetic potential of the obtained α-monofluoro-β-ketophosphonates was demonstrated by their application in synthesis of α-monofluoro-β-aminophosphonates, useful building blocks in the preparation of phosphapeptides.     

Complex formation of cinnamaldehyde-methyl-β-cyclodextrin and muscone-methyl-β-cyclodextrin by supercritical carbon dioxide processing and sealed heating method

Firstly, the interaction between cinnamaldehyde (CIN) and methyl-β- cyclodextrin (MBCD) was studied in aqueous solution. 1:1 inclusion complex was formed and the association constant was 187 ± 9 M^?1. Then the complex of CIN–MBCD and muscone–MBCD was prepared both by sealed heating method and by supercritical carbon dioxide (sc CO₂) approach. Complete complex was obtained by both methods for CIN–MBCD. Some CIN molecules was weakly associated with MBCD molecules in products by sealed heating method, all CIN molecules was strongly associated with MBCD molecules in products by sc CO₂ processing. Complete complex between muscone and MBCD was not obtained. The choice for the size of guest molecule still existed for MBCD cavity in sealed heating method and sc CO₂ processing.     

Conductivity studies of the molecular encapsulation of sodium perfluoroctanoate byβ-cyclodextrin derivatives

The molecular encapsulation of sodium perfluoroctanoate (SPFO) by hydroxypropyl--cyclodextrin (HP--CD) or 2,6-di-O-methyl--cyclodextrin (DM--CD) has been analyzed by measuring the conductivity in solution of the ternary systems formed by CD + SPFO + H₂O. The studies were carried out at 25 °C using a fully computerized electrical conductivity technique. The measurements were made as a function of CD concentration at various non-micellar concentrations of SPFO, and as a function of CD and SPFO concentrations with [CD]/[SPFO] constant at stoichiometric ratio. The inclusion complexes, HP--CD-SPFO and DM--CD-SPFO, were characterized through the stoichiometry, which has been found to be 1 : 1 in both cases, and the binding constants, which have been evaluated from the conductivity data with a model proposed by us considering the variation of the ionic molar conductivities with the concentration and the association of the surfactant counterion to the inclusion complex. The resultingK values indicate that the interaction between the CD cavity and the monomeric SPFO is strong and similar in both cases.     

Rapid, one-pot synthesis of α,α-disubstituted primary amines by the addition of Grignard reagents to nitriles under microwave heating conditions

A series of α,α-disubstituted amines have been prepared in a simple and efficient one-pot procedure by the addition of Grignard reagents to a series of aliphatic, aromatic, and heteroaromatic nitriles. Key to this reported procedure is the unprecedented addition of the Grignard reagent to the nitrile under heating by microwave irradiation which both significantly improves reaction yields and reduces reaction times. In general, the Grignard addition reaction is complete within 5-10 min at 100 °C followed by rapid reduction with sodium borohydride to give the target amines.     

Synthesis,Stability and Reactivity of α-Fluorinated Azidoalkanes

Organic α-fluorinated azidoalkanes appeared in the literature for the first time half a century ago. However, for a long time they remained undeveloped and were regarded as chemical curiosities. Recent advances in the preparation of α-fluorinated azidoalkanes as well as studies on their stability and reactivity opened up their broader synthetic potential for the preparation of valuable fluorinated and non-fluorinated compounds.     

The analysis of “power window” induced by thermal effect during the microwave heating

The “windows” are often considered as the evidence of microwave non-thermal effect. Here, enzyme catalysis acrylonitrile reaction was carried out and the coupled multiphysics field equations were solved by finite difference time domain (FDTD) method. The temperature curves can be obtained under the different power. Then, the results calculated by chemical reaction kinetic show that the power window of product concentration can be induced by thermal effect. The power window cannot be a criterion of microwave non-thermal effects.     

Thermal Stability and Decomposition Kinetics of the β-CD Cinnamic Aldehyde Inclusion Complex

The stability of the -CD cinnamic aldehyde inclusion complex wasinvestigated by TG and DSC. The weight loss takes place in three stages:dehydration occurs at 50–120 °C; the dissociationof -CDC₉H₈O occurs at 200–260 °C;and the decomposition of -CD begins at 280 °C. Thekinetics of the dissociation of cinnamic aldehyde from the -CD cavitywere studied by means of thermogravimetry both at constant temperatureand linear increasing temperature. The results show that the dissociationof -CDC9H8O is dominated by a one-dimensional diffusionprocess. The activation energy, E, is 160 kJmol-1. Thepre-exponential factor A is 5.8 × 1014 min-1.     

Synthesis and characterization of silica xerogels obtained via fast sol–gel process

The synthesis and physical properties of high surface area silica xerogels obtained by a two-step sol–gel process in the absence of supercritical conditions are reported. The hydrolysis and condensation reactions were followed by infrared spectroscopy. The increment in the bands corresponding to silanol and hydroxyl groups suggests that the hydrolysis reaction was complete during the first 30 min. The effect on surface area and global reaction time under various reaction conditions, such as type of alkaline catalyst and solvents, water–monomer and solvent–monomer molar ratios, was also studied. The obtained results suggest that surface area was increased using 3-aminopropyltriethoxysilane as catalyst. The use of isopropyl alcohol as solvent promotes the reduction of the capillary stress, giving a well-structured xerogel. As a conclusion, with H₂O/i-PrOH/TEOS in a molar ratio of 10:4:1, it was possible to obtain silica xerogels with surface areas about 1,240 m²/g. Such surface areas are comparable with those obtained under supercritical conditions (aerogels), and higher than those xerogels conventionally obtained under normal condition (500–800 m²/g).     

Magnetic molecularly imprinted polymer beads prepared by microwave heating for selective enrichment of β-agonists in pork and pig liver samples

Novel magnetic molecularly imprinted polymer (MIP) beads using ractopamine as template for use in extraction was developed by microwave heating initiated suspension polymerization. Microwave heating, as an alternative heating source, significantly accelerate the polymerization process. By incorporating magnetic iron oxide, superparamagnetic composite MIP beads with average diameter of 80 μm were obtained. The imprinted beads were then characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis and vibrating sample magnetometer. Highly cross-linked porous surface and good magnetic property were observed. The adsorption isotherm modeling was performed by fitting the data to Freundlich isotherm model. The binding sites measured were 3.24 μmol g⁻¹ and 1.17 μmol g⁻¹ for the magnetic MIP beads and the corresponding non-imprinted magnetic beads, respectively. Cross-selectivity experiments showed the recognition ability of the magnetic MIP beads to analytes is relative to degree of molecular analogy to the template. Finally, this magnetic MIP bead was successfully used for enrichment of ractopamine, isoxsuprine and fenoterol from ultrasonically extracted solution of pork and pig liver followed by high performance chromatography with fluorescence detection. The proposed method presented good linearity and the detection limits was 0.52-1.04 ng mL⁻¹.The recoveries were from 82.0% to 90.0% and from 80.4% to 86.8% for the spiked pork and pig liver, respectively, with the RSDs of 5.8-10.0%. Combination of the specific adsorption property of the MIP material and the magnetic separation provided a powerful analytical tool of simplicity, flexibility, and selectivity.