Study of Synthesis of Copoly （lactic acid／glycolic acid） by Direct Melt Polycondensation

A two steps direct copolymerisation process was developed. The first step is to produce oligomer and then the oligomer of lactic acid/glycolic acid (90/10) is polymerized with binary catalyst tin chloride dihydrate/ptoluenesulfonic acid. In this way, the direct synthesis of copoly (lactic acid/glycolic acid) without any organic solvent was investigated. The properties and structures of products were characterized by nuclear magnetic resonance (NMR), differential scanning calorimetry (DSC), X-ray diffraction and so on. The results show that comparatively high molecular weight copolymer of lactic acid and glycolic acid can be prepared by direct processing under appropriate technological conditions.     

Organic solvent- and phase transfer catalyst-free oxida-tion of cyclohexanol to cyclo-hexanone with dilute H2O2

The oxidation of cyclohexanol to cyclohexanone with 30% aqueous hydrogen peroxide by using peroxotungstate complexes formed in situ from sodium tungstate dihydrate and various bidentate organic ligands as the catalysts, without organic solvents, halide and phase transfer catalyst has been carried out. The influence of 13 ligands on the oxidation is investigated. The maximum yield of cyclohexanone is obtained when using 1,10-phenanthroline (96%) and oxalic acid (95%) as the ligand. Very high yields (around 90%) have also been obtained for the instances of using salicylic acid, 3,5-dibromosalicylic acid, and 8-hydro- xylquinoline as ligands. A research to improve the reaction condition using cheap oxalic acid as the ligand indicates that the optimum condition is that the reaction mixture with a molar ratio of cycohexanol︰tungstate dihydrate︰oxalic acid︰30% H2O2=100︰2︰2︰120 was stirred at 85-90℃ for 12 h.     

Organic solvent- and phase transfer catalyst-free oxidation of cyclohexanol to cyclohexanone with dilute H2O2

The oxidation of cyclohexanol to cyclohexanone with 30% aqueous hydrogen peroxide by using peroxotungstate complexes formed in situ from sodium tungstate dihydrate and various bidentate organic ligands as the catalysts, without organic solvents, halide and phase transfer catalyst has been carried out. The influence of 13 ligands on the oxidation is investigated. The maximum yield of cyclohexanone is obtained when using 1,10-phenanthroline (96%) and oxalic acid (95%) as the ligand. Very high yields (around 90%) have also been obtained for the instances of using salicylic acid, 3,5-dibromosalicylic acid, and 8-hydro- xylquinoline as ligands. A research to improve the reaction condition using cheap oxalic acid as the ligand indicates that the optimum condition is that the reaction mixture with a molar ratio of cycohexanol︰tungstate dihydrate︰oxalic acid︰30% H₂O₂=100︰2︰2︰120 was stirred at 85—90℃ for 12 h. :     

Decomposition mechanism of chromite in sulfuric acid-dichromic acid solution

The sulfuric acid leaching process is regarded as a promising, cleaner method to prepare trivalent chromium products from chromite; however, the decomposition mechanism of the ore is poorly understood. In this work, binary spinels of Mg-Al, Mg-Fe, and Mg-Cr in the powdered and lump states were synthesized and used as raw materials to investigate the decomposition mechanism of chromite in sulfuric acid-dichromic acid solution. The leaching yields of metallic elements and the changes in morphology of the spinel were studied. The experimental results showed that the three spinels were stable in sulfuric acid solution and that dichromic acid had little influence on the decomposition behavior of the Mg-Al spinel and Mg-Fe spinel because Mg2+, Al3+, and Fe3+ in spinels cannot be oxidized by Cr6+. However, in the case of the Mg-Cr spinel, dichromic acid substantially promoted the decomposition efficiency and functioned as a catalyst. The decomposition mechanism of chromite in sulfuric acid-dichromic acid solution was illustrated on the basis of the findings of this study.     

Synthesis of high molecular weight polylactic acid from aqueous lactic acid co-catalyzed by tin(II)chloride dihydrate and succinic anhydride

Poly(lactic acid) (PLA) is widely used as biodegradable plastic and biomedical materials due to its excellent me- chanical properties and biodegradable characterization. The price of poly(lactic acid) has gradually become com- petitive to the average alkene polymers since the method for the preparation of lactic acid from starch fermentation has been developed. With the decline of petroleum re- serves, much attention is devoted to polylactic acid due to its environmentally benignancy and its …     

Corrosion-wear behavior of nanocrystalline Fe88Si12 alloy in acid and alkaline solutions

The corrosion-wear behavior of a nanocrystalline Fe₈₈Si₁₂ alloy disc coupled with a Si₃N₄ ball was investigated in acid (pH 3) and alkaline (pH 9) aqueous solutions. The dry wear was also measured for reference. The average friction coefficient of Fe₈₈Si₁₂ alloy in the pH 9 solution was approximately 0.2, which was lower than those observed for Fe₈₈Si₁₂ alloy in the pH 3 solution and in the case of dry wear. The fluctuation of the friction coefficient of samples subjected to the pH 9 solution also showed similar characteristics. The wear rate in the pH 9 solution slightly increased with increasing applied load. The wear rate was approximately one order of magnitude less than that in the pH 3 solution and was far lower than that in the case of dry wear, especially at high applied load. The wear traces of Fe₈₈Si₁₂ alloy under different wear conditions were examined and analyzed by scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy. The results indicated that the tribo-chemical reactions that involve oxidation of the worn surface and hydrolysis of the Si₃N₄ ball in the acid solution were restricted in the pH 9 aqueous solution. Thus, water lubrication can effectively improve the wear resistance of nanocrystalline Fe₈₈Si₁₂ alloy in the pH 9 aqueous solution.     

THE TRANSFER BEHAVIOUR OF SOME CATIONS AT WATER／NITROBENZENE INTERFACE BY SEMIDIFFERENTIAL CYCLIC VOLTAMMETRY

The transfer of Sr~(2+) and Ba~(2+) ion, facilitated by 18-Crown-6 present in the aqueous phase, and of succinylcholine ion at w/nb interface were investigated by semi-differential cyclic voltammetry. A good polarographic curve of succinylcholine ion dissolved in water was obtained in the system of 0.01 mol/l LiCl (w)——0.01 mol/l TBATPB (nb). The peak current is directly proportional to the concentration of SC~(2+) ion. It can be used for the determination of SC and the detection limit is 1.05×10~(-5) mol/l.The apparent D~w and D~(nb) have been estimated. The transfer of Sr~(2+) and of Ba~(2+) at the interface are facilitated by 18-Crown-6 present in the aqueous phase and the peak current is directly proportional to the concentration of 18-Crown-6 in water. This method can be used for the determination of the complexing agent and for the stability constant of the complex formed in the aqueous phase.All the experimental results are in keeping with the theoretical.     

Effects of L-lactic acid and D,L-lactic acid on viability and osteogenic differentiation of mesenchymal stem cells

Poly(lactic acid) (PLA) and other aliphatic polyesters containing the unit of lactic acid are very popular biodegradable materials. While the degradation products, lactic acids, have been worried to bring with negative influence on biocompatibility, the focused experimental studies are less reported. This study is aimed at an in vitro examination of cytotoxicity of both L-lactic acid and D,L-lactic acid. Mesenchymal stem cells (MSCs) derived from rat bone marrow are employed to test the cytotoxicity of the lactic acids. Considering that the addition of lactic acids not only introduces lactate groups but also alters medium pH and ion strength, these three candidate effects are examined in a decoupled way by setting different comparison groups. The results confirm that the change of medium pH is the predominant factor. It has also been found that D-lactate is more cytotoxic than L-lactate at high concentrations. Yet, either L-or D,L-lactic acids seem acceptable in most of medical applications, because the cytotoxicity is significant only when the concentrations are as high as 20 mmol/L for both of them.     

Microwave absorbing properties of polyaniline/montmorillonite doped with dodecylbenzensulfonic acid nanocomposite

In this paper, we reported a new type of high performance microwave-absorbing material, polyaniline/montmorillonite doped with dodecylbenzensulfonic acid (PAni-DBSA/MMT) nanocomposite. The microwave-absorbing properties of this nanocomposite were investigated for the frist time. The nanocomposites were synthesized from emulsion polymerization using dodecylbenzensulfonic acid (DBSA) as dopant and emulsifier. The structure of the nanocomposite was analyzed by X-ray diffraction(XRD) and FT-IR, and its results denoted that PAni-DBSA/MMT is a typical intercalative polymer/layered silicate(PLS) nanocomposite, and the interaction between MMT layers and PAni chains enhances the delocalization of free electrons in PAni chains. The complex permittivity, permeability and reflection loss (R.L.) of microwave of a 2.00 mm thick samples containing 50% by weight of PAni-DBSA/MMT nanocomposite and PANI?DBSA were measured, respectively, in 2?18 GHz range. The results showed that the PANI-DBSA/MMT nanocomposite is capable of absorbing 2.0?18 GHz microwaves, and the reflection loss was less than -10 dB in the frequency range of 9.1?12.5 GHz, while the minimum reflection loss was -15.8 dB at 11 GHz. The microwave absorbing mechanism of nanocomposite is disscused.     

Preparation of porous chitosan-poly（acrylic acid）- calcium phosphate hybrid nanoparticles via mineralization

In this work, the preparation of chitosan-poly（acrylic acid）-calcium phosphate hybrid nanoparticles （CS-PAA-CaP NP） based on the mineralization of calcium phosphate （CAP） on the surface of chitosan-poly （acrylic acid） nanoparticles （CS-PAA NPs） was reported. CS-PAA-CaP NPs were achieved by directly adding ammonia to the aqueous solution of CS-PAA nanoparticles or by thermal decomposition of urea in the aqueous solution of CS-PAA nanoparticles, resulting in the mineralization of CaP on the surface of CS-PAA NPs. Through these two routes, especially using urea as a pH-regulator, the precipitation of CS-PAA NPs, a common occurrence in basic environment, was avoided. The size, morphology and ingredient of CS-PAA-CaP hybrid nanoparticles were characterized by dynamic light scattering （DLS）, transmission electron microscope （TEM）, scanning electron microscope （SEM）, thermogravimetry analysis （TGA） and X-ray diffractometer （XRD）. When urea was used as the pH regulator to facilitate the mineralization during the thermal urea decomposition procedure, regular CS-PAA-CaP hybrid nanoparticles with a porosity-structural CaP shells and 400-600 nm size were obtained. TGA result revealed that the hybrid NPs contained approximately 23% inorganic component, which was consistent with the ratio of starting materials. The XRD spectra of hybrid nanoparticles in- dicated that dicalcium phosphate （DCP： CaHPO4） crystal was a dominant component of mineralization. The porous structure of the CS-PAA-CaP hybrid NPs might be greatly useful in pharmaceutical and other medical applications.     

白酒窖泥中乳酸菌分离鉴定及其发酵产挥发性风味物质比较

从白酒窖泥中分离得到11株乳酸菌,经16S rDNA基因序列同源性分析,鉴定为1株短乳杆菌、1株鼠李糖乳杆菌、2株干酪乳杆菌和7株铅黄肠球菌。 分析了11株菌MRS培养基发酵产乳酸性能,结果表明:乳酸产量与菌群生长呈正相关,鼠李糖乳杆菌L₉、干酪乳杆菌L₁₀与L₁₁发酵液乳酸含量较高,分别为15.74、15.58、14.74g/L。4株代表菌相同条件下发酵高粱培养液产挥发性风味组分,共有物质13种,包含了白酒中重要香气成分:乙酸、己酸、乙酸苯乙酯和苯乙醇,且乙酸、己酸相对含量较高。各菌产可挥发性组分差异明显,相对含量较高的化合物种类为:短乳杆菌L₅产烷烃类化合物(27.91%),铅黄肠球菌L₈产醇类化合物(43.14%),鼠李糖乳杆菌L₉产酯类(7.35%)、酮类(3.61%)和吡嗪类(3.3%)化合物,干酪乳杆菌L₁₁产酸类(27.98%)和芳香类(5.96%)化合物。仅有短乳杆菌L₅产四甲基吡嗪,短乳杆菌L₅和铅黄肠球菌L₈可明显产乙醇,鼠李糖乳杆菌L₉和干酪乳杆菌L₁₁产3-羟基-2-丁酮。这些物质对白酒风味和口感有重要影响。研究显示,窖泥中各种乳酸菌特征不一,对白酒酿造有不同影响。本研究旨在为进一步挖掘白酒酿造功能微生物、拓展乳酸菌的应用提供理论依据。     

Phase behavior and properties of salt-free cationic/anionic surfactant mixtures of oleic acid and stearic acid

Cationic base surfactant, tetradecyltrimethylammonium hydroxide （TTAOH）, can be obtained through anion exchange from tetradecyltrimethylammonium bromide （TTABr）. Salt-free cationic and anionic （catanionic） surfactant mixtures were studied by mixing TTAOH with oleic acid （OA） or stearic acid （SA） in water. The phase behavior of TTAOH/OA/H2O is compared with that of TTAOH/SA/H2O. It was found that the phase behavior of TTAOH/OA/H2O and TTAOH/SA/H2O system differs from each other due to the existence of the unsaturated double carbon bond （C=C） in OA. At fixed total surfactant concentration （25 mg/mL） of TTAOH/ONH2O system at 25℃, one can observe an isotropic L1 phase, and a L1/Lα two-phase region with increasing OA content. The volume of top turbid Lα phase increases while the bottom phase changes gradually from transparently clear to a bit turbid until a single Lα-phase is reached. Finally at high OA concentration, excess OA is separated from the bulk aqueous solutions. TTAOH/SA/H2O system usually forms white precipitating at 25℃ due to the high chain melting temperature of SA. When heated to 60℃, however, the state of samples changes. At fixed total surfactant concentration of 25 mg/mL, an isotropic Lα phase and a milk-white or bluish Lα-phase are observed with increasing SA concentration. Transparent thin layers which are strongly birefringent form at the tops of some samples within the Lα-phase region. Finally, at high SA concentration, excess SA is separated from the bulk aqueous solutions. In addition to phase behavior study, we also measured the conductivity of TTAOH/OA/H2O system at 25℃ and TTAOH/SA/H2O system at 60℃, respectively. Surface tension and rheological measurements were also performed on typical samples.     

Syntheses and lyotropic liquid crystal properties of a series of sandwich-type tungstoarsenates heteropoly compounds with As/W ratio of 4/30

A series of sandwich-type tungstoarsenates heteropoly compounds with As/W ratio of 4/30, Na16[As4W30M4(H2O)2O112]·XH2O (M = Zn,Cu,Co,Ni,Mn and Cd), have been synthesized for the first time and structurally characterized by elemental analysis, IR and 183W NMR spectra. The crystal structure of Na16[As4W30Cu4(H2O)2O112]·63H2O was determined to be a triclinic system, of P1 symmetry, a = 1.2721(3) nm, b = 2.451 6(5) nm, c = 2.6450(5) nm, α= 89.90(3)°,β= 77.32(3)°, γ= 89.96(3)°, 2=2. Using tetrahepty lammonium bromide as a phase transfer reagent, [As4W30Cu4(H2O)2O112]16- was transferred from aqueous solution to organic phase (benzene), and the heteropolyanion lost the coordination water molecules to form the coordination-unsaturated ion. After lactic acid was added to the benzene solution, the coordination-saturation was recovered. By esterification reaction between lactic acid and cholesterin, the latter was attached to the heteropolyanion indirectly. Therefore, a new type of lyotropic liquid crystal was obtained, which was characterized by a polarimicroscope, DSC and variable temperature wide-angle X-ray diffraction.     

化学沉淀-溶剂沉淀法脱除湿法磷酸中氟的研究

 以乙醇为溶剂,RNH₂为沉淀剂,采用化学沉淀-溶剂沉淀法对湿法磷酸进行净化,在乙醇与预处理酸体积比为2.0、溶剂沉淀剂用量为3.5%、反应温度40℃、反应时间100min条件下,脱氟率可达到96%以上,磷收率为86%以上.     

Reductive leaching of manganese from low-grade pyrolusite ore in sulfuric acid using pyrolysis-pretreated sawdust as a reductant

Manganese (Mn) leaching and recovery from low-grade pyrolusite ore were studied using sulfuric acid (H₂SO₄) as a leachant and pyrolysis-pretreated sawdust as a reductant. The effects of the dosage of pyrolysis-pretreated sawdust to pyrolusite ore, the concentration of sulfuric acid, the liquid/solid ratio, the leaching temperature, and the leaching time on manganese and iron leaching efficiencies were investigated. Analysis of manganese and iron leaching efficiencies revealed that a high manganese leaching efficiency was achieved with low iron extraction. The optimal leaching efficiency was determined to be 20wt% pyrolysis-pretreated sawdust and 3.0 mol/L H₂SO₄ using a liquid/ solid ratio of 6.0 mL/g for 90 min at 90℃. Other low-grade pyrolusite ores were tested, and the results showed that they responded well with manganese leaching efficiencies greater than 98%.     

Extraction of Aluminum and Iron from Boiler Slag by Sulfuric Acid

This paper presents a new method of recycling aluminum and iron in boiler slag derived from plants that use coal as fuel. The new method integrates efficient extraction and reuse of the leached pellets together. An elemental analysis of aqueous solutions leached by sulfuric acid was determined by EDTA-Naz-ZnCl2 titration method. The components and microstructures of the samples were examined by means of XRF, XRD and SEM. An aluminum extraction efficiency of 86.50% was achieved when the sintered pellets were leached using 4 mol · L^- 1 H2SO4 at solid/ liquid [m（g）/V（mL）] ratio of 1 ： 5 at 80 ℃ for 24 h. An iron extraction efficiency of 94.60% was achieved in the same conditions for the maximum extraction efficiency of Al. The extraction efficiencies of Al and Fe increased with an increase in temperature, leaching time and acidity. The concentration of alumina and iron hydroxide in the final product was determined to be 99.12% and 92.20% respectively. This product of alumina would be used directly for the production of metallic aluminum.