Solvent effects on infrared spectra of 2-methyl-4,5-dimethoxy-3-oxo-2H-pyridizine： Part 1. Single solvent systems

Infrared spectroscopy studies of 2-methyl-4,5-dirnethoxy-3-oxo-2H-pyridlzine (MDOP) in 12 pure organic solvents were undertaken to investigate the solvent-solute interactions. The frequencies of the carbonyl (C = O) of MDOP were correlated with solvent properties such as solvent acceptor number (AN) and the linear solvation energy relationships (LSER). These frequencies showed a good correlation with the solvent acceptor number (AN) and the LSER.     

Effect of bromization on the propertises of a series of substituted 1,8,15,22—tetra（2,4—ditertbutylphenoxy） phthalocyanines

A series of 1,8,15,22-tetra(2,4-ditertbutylphen-oxy) phthalocyanines [α-（oAr）4PcM,M1=(H)2,M2=Pd,M3=Cu,M4=Zn,M5=Pb] were synthesized in this study.Each compound was bromized in two kinds of solvent.One is the solvent mixture of 1,1,2-trichloroethane and water,the other is 1,1,2-trichloroethane alone.The effects of solvent,bromine excess added and reaction duration on the bromization reaction were studied.The shift of maximum absorbance wave-length both is solution and in solid thin film was investigated comparatively,discovering that both were bathochromism but the former was more.TG data showed that the temperature of thermal decomposition decreased continuously with the increase of numbers of bromine.Finally,the fragments produced during the bromization of (OAr)4PcPb in 1,1,2-trichloroethane were characterized by GC/MS.Based on the electronic structure,the possible mechanism of decomposition of these compounds was presented and discussed.     

The Effect of Casting Solvent on the Electrical Property of Polyaniline/ Polyacrylonitrile

Blends of dodecylbenzene sulfonic acid doped polyaniline （PANI-DBSA） and polyacryionitrile （PAN） dissolved in either CHCh/DMF or CHCl3/DMSO mixture were solution cast. The conductivity of the blends with various compositions was measured and the doped ：xtent of PANI- DBSA in different casting solvent systems was studied. Solution blends prepared from CHCh/DMSO displayed higher conductivity than those obtained via CHCh/DMF. The dedoping reaction of PANI-DBSA in CHCl3/DMF identified by UV-Vis and FTIR analysis contributed to the lower conductivity of PANI-DBSA/PAN blend.     

4-Formyl-2-（2H-benzotriazol-2-yl）-phenol： an ESIPT chromophore

In the present work, excited state intramolecular proton transfer （ESIPT） emission properties of a new benzotriazole derivative 4-formyl-2-（2H-benzotriazol-2-yl）- phenol （C1） were studied. 4-Formyl-2-（2H-benzotriazol-2- yl）-methoxy-benzene （C2）, 4-formyl-2-（2H-benzotriazol-2- yl）-phenyl acetate （C3） and 4-methyl-2-（2H-benzotriazol- 2-yl）-phenol （C4） were used as the reference molecules. ^1H NMR chemical shift of hydroxy group in C1 was located at more down field than that of C4 or p-hydroxy-benzaldehyde （C5）, respectively. C1 showed two absorption bands in the range of 260-400 nm zones in various solvents, while C2 and C3 exhibited single absorption band. The equal molar mixtures of C2/C5 or C3/C5 showed single absorption band. C2 and C3 displayed single fluorescence emission band in various solvents, while C1 exhibited dual emission bands in some strong polar solvents. Furthermore, the second emission band in these strong polar solvents showed the large Stokes shift. The results show that the second emission band of C1 was produced by ESIPT. C2 and C3 could not undergo ESIPT due to no hydroxy group. The geometry optimization calculation of enol and keto forms in the ground and excited states of C1 provided tough theoretical evidences of ESIPT.     

Polymerization of acrylonitrile catalyzed by lanthanide-sodium alkoxide clusters Lne（OCH2CH2NMe2）12（OH）eNas [Ln=Yb （1）, Nd （2） and Sm （3）]

Polymerization of acrylonitrile was carried out using,for the first time,the lanthanide-sodium alkoxide clusters Ln2(OCH2CH2NMe2)12(OH)2Na8 [Ln=Yb (1),Nd (2) and Sm (3)] as single component catalysts.These heterobimetallic complexes exhibit high activity and give atactic polyacrylonitriles with high molecular weight.The polymerization temperature can be varied over the range ?78 to 50°C.The solvent has a substantial effect on the polymerization activity.The order of activity for solvents is DMF>DME≈toluene≈...     

Controlled assembly of gold and rare-earth upconversion nanoparticles for ratiometric sensing applications

In this paper, the Au nanoparticles and rare-earth (RE) upconversion nanoparticles (NPs) were respectively synthesized by using polyelectrolyte as the capping agents. Since the synthesized Au NPs and RE NPs had the similar size and surface conditions, Their mixture were employed in a pH sensing application. Benefited from the good spectral overlap between the RE upconversion emission bands and pH-tunable surface plasmon bands of the Au NPs, the pH-induced manipulation of green-to-red emission intensity ratio of the upconversion fluorescence was achieved in the Au-RE mixture. The results demonstrate a rapid ratiometric approach for pH sensing, which is more efficient than traditional sensing methods that depend on single intensity-based responses to analytes.     

Low-temperature densification sintering and properties of CaAl_2Si_2O_8 ceramics with MeO·2B_2O_3(Me=Ca,Sr,Ba)

Dense CaAl2Si2O8 ceramics were prepared via a two-step sintering process at temperatures below 1000°C. First, pre-sintered Ca Al2Si2O8 powders containing small amounts of other crystal phases were obtained by sintering a mixture of calcium hydroxide and kaolin powders at 950°C for 6 h. Subsequently, the combination of the pre-sintered ceramic powders with Me O·2B2O3(Me = Ca, Sr, Ba) flux agents enabled the low-temperature densification sintering of the CaAl2Si2O8 ceramics at 950°C. The sintering behavior and phase formation of the CaAl2Si2O8 ceramics were investigated in terms of the addition of the three MeO·2B2O3 flux agents. Furthermore, alumina and quartz were introduced into the three flux agents to investigate the sintering behaviors, phase evolvements, microstructures, and physical properties of the resulting CaAl2Si2O8 ceramics. The results showed that, because of their low-melting characteristics, the MeO·2B2O3(Me = Ca, Sr, Ba) flux agents facilitated the formation of the CaAl2Si2O8 ceramics with a dense microstructure via liquid-phase sintering. The addition of alumina and quartz to the flux agents also strongly affected the microstructures, phase formation, and physical properties of the CaAl2Si2O8 ceramics.     

Addition of IrO2 to RuO2+TiO2 coated anodes and its effect on electrochemical performance of anodes in acid media

Ternary mixed metal oxide coatings with the nominal composition IrxRu(0.6-x)Ti0.4O2(x=0, 0.1, 0.2, 0.3) on the titanium substrate were prepared by thermal decomposition of a chloride precursor mixture. Surface morphology and microstructure of the coatings were investigated by Scanning electron microscopy(SEM), Field emission scanning electron microscopy(FE-SEM) and X-ray diffraction(XRD) analysis. Systematic study of electrochemical properties of these coatings was performed by cyclic voltammetry(CV) and polarization measurements. The corrosion behavior of the coatings was evaluated under accelerated conditions(j=2 A cm-2) in acidic electrolyte. The role of iridium oxide admixture in the change of electrocatalytic activity and stability of Ru0.6Ti0.4O2coating was discussed. Small addition of IrO2can improve the stability of the RuO2+TiO2mixed oxide, while the electrocatalytic activity for oxygen evolution reaction(OER) is decreased. The shift of redox potentials for Ru0.6Ti0.4O2electrode that is slightly activated with IrO2and improvement in the stability can be attributed to the synergetic effect of mixed oxide formation.     

Controlling PCBM aggregation in P3HT/PCBM film by a selective solvent vapor annealing

A selective solvent vapor, i.e., cyclohexanone or isopropyl benzene, which is a poor solvent for poly(3-hexylthiophene-2,5-diyl) (P3HT) and a good solvent for fullerene derivative [6,6]-phenyl-C61-butyric acid methyl ester (PCBM), was employed to reduce the size of PCBM aggregates and prolong the formation time of big PCBM aggregates in P3HT/PCBM film. PCBM nucleates and aggregates of 10-20 nm scale form in the first few minutes annealing. Then the size of PCBM aggregates kept unchanged until annealing for 60 min. Finally, larger PCBM aggregates of micron-size formed hours later. On the contrary, the growth rate of PCBM aggregates was faster and their size was larger when treated with a good solvent vapor for both components. The P3HT crystallinity was the same with different types of annealing solvents, although the rate of P3HT self-organization was decreased after a selective solvent vapor annealing. Because of the smaller size of phase separation, the device annealed in a selective solvent vapor for 30 min had a higher PCE than that annealed in a good solvent vapor.     

A Convenient Method for the Oxidation of Alcohols with KMnO_4 to Their Corresponding Carbonyl Compounds in Ionic Liquid Media

1 Results Carbonyl compounds constitute an important group of molecules in organic chemistry,which appears in pharmaceuticals,dyes and industrially important chemicals[1-2].The oxidation of alcohols to the corresponding carbonyl groups is a fundamental transformation in organic chemistry and industrially important[3].There is considerable interest in the use of room temperature ionic liquids as promising substitutes for volatile organic solvents.The ambient-temperature ionic liquids,especially those based on 1,3-dialkylimidazolium cations,have been emerged as promising green solvents in recent decades[4].Some of the advantages of using ionic liquids in catalytic reactions are connected with the lack of a measurable vapor pressure.Products can be easily distilled out of the reaction mixture and the impact on the environment and operating personnel is dramatically reduced.In addition,due to the great choice of different ionic liquids,the solvent properties may be tuned to suit a particular application.In order to investigate such oxidation reactions in ionic liquids; the selective oxidation of alcohols to aldehydes was selected as a model reaction.     

Preparation of high selectivity silicalite-1 membranes by two-step <Emphasis Type="Italic">in situ</Emphasis> hydrothermal synthesis

High selectivity silicalite-1 membranes were synthesized on silica tubes by in situ hydrothermal synthesis. Using a two-step synthesis, a membrane with a separation factor of 99 was prepared for separating an ethanol/water mixture at 60°C. The average (n = 4) flux and separation factor of the membranes were 0.47 kg m-2 h-1 and 89, respectively. The membranes exhibited high reproducibility, and the relative standard deviation of the average (n = 4) flux and separation factor were only 5.3% and 9.2%, respectively. These results suggest that silica is a suitable support for synthesis of high-performance silicalite-1 membranes.     

Low-temperature densification sintering and properties of CaAl2Si2O8 ceramics with MeO·2B2O3 (Me=Ca,Sr, Ba)

Dense CaAl2Si2O8 ceramics were prepared via a two-step sintering process at temperatures below 1000°C. First, pre-sintered CaAl2Si2O8 powders containing small amounts of other crystal phases were obtained by sintering a mixture of calcium hydroxide and kaolin powders at 950°C for 6 h. Subsequently, the combination of the pre-sintered ceramic powders with MeO·2B2O3 (Me=Ca, Sr, Ba) flux agents enabled the low-temperature densification sintering of the CaAl2Si2O8 ceramics at 950°C. The sintering behavior and phase formation of the CaAl2Si2O8 ceramics were investigated in terms of the addition of the three MeO·2B2O3 flux agents. Furthermore, alumina and quartz were introduced into the three flux agents to investigate the sintering behaviors, phase evolvements, microstructures, and physical properties of the resulting CaAl2Si2O8 ceramics. The results showed that, because of their low-melting characteristics, the MeO·2B2O3 (Me=Ca, Sr, Ba) flux agents facilitated the formation of the CaAl2Si2O8 ceramics with a dense microstructure via liquid-phase sintering. The addition of alu-mina and quartz to the flux agents also strongly affected the microstructures, phase formation, and physical properties of the CaAl2Si2O8 ce-ramics.     

Extraction of Zr(IV) from hydrochloric acid with tri-octyl amine and Cyanex 921 in kerosene

This article reports the extraction of zirconium (IV) from aqueous HCl solution by tri-octyl amine (TOA), Cyanex 921, and their binary mixture using kerosene as the diluent. The effect of some parameters on the extraction of Zr(IV) was investigated such as equilibration time, aqueous phase acidity, extractant molarity, chloride ion concentration, nature of diluents, and temperature. The extraction of Zr(IV) was found to be 99% from 7.5 M HCl using the mixture of extractants containing 0.1 M TOA and 0.02 M Cyanex 921 in kerosene. Kerosene was found to be the effective diluent for the extraction of Zr(IV) with the binary mixture of TOA and Cyanex 921. The positive enthalpy change and positive entropy change in the binary extraction system show the endothermic process with an increase in entropy. Stripping of Zr(IV) from the loaded organic phase containing the mixture of TOA (0.1 M) and Cyanex 921 (0.02 M) indicates that HNO₃ and Na₂CO₃ are the best stripping agents.     

Resonance-enhanced multiphoton ionization spectroscopy on the B''''~2Σ~+ and B~2Π states of NS

Resonance-enhanced multiphoton ionization (REMPI) spectra of N32S and N34S have been recorded in the range of 35700―40200 cm?1. The radical was generated by a pulsed dc discharge of a mixture of SF6 and N2 under a supersonic free jet condition. All the 16 observed bands of N32S radicals have been as-signed, among which 12 bands belong to three transition progressions (v'=0-4, 0), (v'=1-4, 1) and (v'=2-4, 2) from the X2Π ground state to the B'2Σ upper state and the rest correspond to (9, 0), (10, 0), (11, 0) and (12, 0) bands of B2Π-X2Π transition, respectively. Analysis of the rotationally resolved spectra yields exhaustive spectroscopic constants of both the X2Π ground state and the B'2Σ excited state. The electronic transition bands of the isotopic molecule N34S have been rotationally analyzed for the first time and the rotational constants of the ground and upper states have been determined simultaneously.     

Storage Characteristics of LiNi_(0.8)Co_(0.1 X)Mn_(0.1-X)O_2 (X=0,0.03,0.06) Cathode Materials for Lithium Batteries

1 Results LiNi0.8Co0.1 xMn0.1-xO2 cathodes with x=0,0.03 and 0.06 were prepared by firing a mixture of stoichiometric amounts of LiOH·H2O and coprecipitated Ni0.8Co0.1 xMn0.1-x(OH)2 at 800 ℃ for 15 h.Using these powders,their storage characteristics upon exposure to air and electrolytes at 90 ℃ were compared before charging and after charging to 4.3 V with a variation of the storage time.As the Co content (x) increased in the cathode,both the Ni2 content in the lithium 3a sites,and the contents of the LiOH and Li2CO3 impurity phases decreased.In particular,changes in the oxidation state of the Ni and Mn ions after 4.3 V charging upon storage at 90 ℃ were monitored using X-ray absorption near edge spectra (XANES),and Ni4 was found to reduce to Ni3 while the oxidation state of the predominant Mn4 did not change.However,residual Mn3 ions in the cathodes dissolved into the electrolytes.Moreover,the cathodes stored at 90 ℃ for 7 days were transformed into a spinel phase (Fd3m),regardless of the Co content.In an effort to resolve this dissolution problem,Al2O3 and Co3(PO4)2 nanoparticles were coated onto the cathode (LiNi0.8Co0.1Mn0.1O2) with the highest amounts of metal dissolution at 90 ℃.The results showed that the Co3(PO4)2-coated cathode exhibited greatly decreased metal dissolution and decreased its irreversible capacity by 5%,compared with a bare and Al2O3-coated cathodes.     

Microstructural study and numerical simulation of phase decomposition of heat treated Co–Cu alloys

The influence of heat treatment on the phase decomposition and the grain size of Co–10 at% Cu alloy were studied. Few samples were aged in a furnace for either 3 or 5 h and then quenched in iced water. The materials and phase compositions were investigated using energy dispersive spectrometry and X-ray diffraction techniques. X-ray diffraction analysis showed that the samples contained Co, Cu, Cu O, Co Cu2O3, Co Cu O2 phases in different proportions depending on the heat treatment regimes. The formation of dendrite Co phase rendered the spinodal decomposition while the oxidations prevent the initiation of the spinodal decomposition even for a deep long aging inside the miscibility gap.Since the Bragg reflections from different phases of Co–Cu alloy significantly overlap, the crystal structural parameters were refined with FULLPROF program. The shifts in the refined lattice constants(a, b and c), the space group and the grain size were found to be phase- and heat treatment-dependant. Two-dimensional computer simulations were conducted to study the phase decomposition of Co–Cu binary alloy systems.The excess free energy as well as the strain energy, without a priori knowledge of the shape or the position of the new phase, was precisely evaluated. The results indicate that the morphology and the shape of the microstructure agree with SEM observation.     

Gas chromatographic method for the determination of hexaconazole residues in black tea

A highly reliable, quantitative and sensitive analytical method for determining the residues of the fungicide, hexaconazole in black tea is described. The proposed method is based on liquid-liquid extraction followed by gas chromatographic determination, using nitrogen phosphorus detector （GC-NPD） for the identification and quantitation of hexaconazole. The most appropriate solvent mixture for extracting hexaconazole residues from black tea was n-hexane：acetone at 1 ：1 （v/v）. The extract was cleaned up by adsorption column chromatography using activated florisil. Performance of the method was assessed by evaluating quality parameters such as recovery value, repeatability, reproducibility, linearity and limits of detection and quantitation. When the method was assessed for repeatability, the percentage of recovery ranged between 86% and 96% while the relative standard deviation was between 0.30% and 2.35%. In studies on reproducibility the recovery ranged from 81% to 85% and relative standard deviation from 1.68% to 5.13%, implying that the method was reliable. A field trial was conducted to verify the application of this method with real samples. Results prove that the validated method was suitable for extracting hexaconazole residues.     

Synthesis of WC powder through microwave heating of WO_3–C mixture

A simple,easy,and low-cost process for the fabrication of tungsten carbide(WC) powder through microwave heating of WO_3–C mixtures was developed. Thermodynamic calculations and experimental investigations were carried out for WO_3–C and W–C systems,and a formation mechanism was proposed. In the results,for the synthesis of WC,the use of over stoichiometric amount of C together with a specially assembled experimental setup(which effectively retains heat in the system) is necessary. The WC powder is successfully obtained by heating WO_3:5C mixture for 900 s in a domestic microwave oven.     

Morphology-controllable solvothermal synthesis of nanoscale LiFePO4 in a binary solvent

LiFePO4(LFP) nanobars,microplates and nanorods have been selectively synthesized via a solvothermal method in a water-ethylene glycol(EG) binary solvent with H3PO4,LiOH·H2O,and FeSO4·7H2O as starting materials.The morphology and size of the as-obtained LFP products can be deliberately controlled by varying the volume ratio of EG to water.The formation mechanism and electrochemical properties of different LFP morphologies have been investigated.With carbon coating,the Li-ion diffusion coefficients of LFP nanorods,nanobars and micro-plates are 2.58×10-9,2.91×10-10,and 7.22×10-10 cm2 s-1,respectively.For the carbon-coated nanorods,excellent rate capability and cyclability were attained.At 5 C,the capacity was 141 mAh g-1 for the first cycle and maintained 120 mAh g-1 after 100 cycles;at 10 C,the capacity was still as high as 132 mAh g-1.     

Isothermal section of ternary Sn ? Zn?Ni phase equilibria at 250 °C

Ternary Sn ?Zn? Ni alloys were prepared and equilibrated at 250 °C for 4? 15 weeks. The phases formed in these equilibrated alloys were determined experimentally. The isothermal section of Sn ?Zn? Ni system was constructed, based on the phase diagrams of the three constituent binary sy stems and the ternary phase equilibria data, determined in this study and referenced in literatures. 12 single-phase regions were identified in the Sn? Zn?Ni ternary system at 250 °C, including the three ternary compounds, δ , τ1 and τ2. There were 13 ternary phase regions and 23 binary phase regions in the 250 °C Sn ? Zn? Ni isothermal section. The solubility of Zn in the binary Sn ?Ni compounds is significant, and is 15.1% (mole fraction) in the Ni3Sn phase.