Synthesis and Structure of a Novel Disulfide-Containing Aniline

A novel disulfide-containing aniline, 8-dihydro-1H,4H-2,3,6,7-tetrathia-anthracen-9-ylamine (5) was synthesized.The single-crystal X-ray analysis of 4 indicates that the molecular has a non-planar structure, with its four sulfur atoms out of the plane of benzene ting. The designed molecular has the advantage of high theoretic specific capacity and reversibility,[1,2] when it is to be polymerized and used as the cathode material of the secondary lithium batteries.     

A Novel Non-phosgene Process for the Synthesis of Methyl N-Phenyl Carbamate from Methanol and Phenylurea： Effect of Solvent and Catalyst

A novel environmentally benign process for the synthesis of methyl N-phenyl carbamate (MPC) from methanol and phenylurea was studied. Effect of solvent and catalyst on the reaction behavior was investigated. The IR spectra of methanol and phenylurea dissolved in different solvents were also recorded. Compared with use of methanol as both a reactant and a solvent, phenylurea conversion and selectivity to MPC increased by using toluene, benzene or anisole as a solvent, while phenylurea conversion decreased slightly by using n-octane as a solvent. The phenylurea conversion declined nearly 50% when dimethyl sulfoxide (DMSO) was used as a reaction media, and MPC selectivity decreased as well. The catalytic reaction tests showed that a basic catalyst enhanced the selectivity to MPC while an acidic catalyst promoted the formation of methyl carbamate and aniline. Moderate degree of basicity showed the best catalytic performance in the cases studied.     

Synthesis of a New Cobalt （Ⅱ） Complex and its Interaction with DNA

A new complex of bis(N-benzyl benzotriazole-N^3) dichloro Co(Ⅱ) (Co(Ⅱ)L2Cl2) was synthesized and its crystal was characterized. The interaction of this new complex with fs-DNA was studied by electrochemical and UV spectrophotometric method. In 0.01 mol/L pH 4.2 Tris-HCl buffer solution Co(Ⅱ)L2Cl2 has two reductive peaks with peak potentials at 0.38 V and 0.27 V, respectively, and an oxidative peak at 1.05 V. After the addition of DNA, the peak currents decrease and the peak potential at 0.27 V shifts negatively. The UV spectrophotometric experiment indicates that the maximum absorbance of Co(Ⅱ)L2Cl2 at 204 nm decreases and exhibits bathochromic shift after the addition of DNA. All the results reveal that Co(Ⅱ)L2Cl2binds with DNA by intercalation as well as electrostatic interaction.     

Synthesis of α-Bromine- Terminated Polystyrene Macroinitiator and Its Initiation of MMA Polymerization by ATRP

In the present paper the synthesis of block copolymers via the transformation from living anionic polymerization (LAP) to atom transfer radical polymerization (ATRP) was described. Α-Bromine-terminated polystyrenes(PStBr) in the LAP step was prepared by using n-BuLi as initiator, tetrahydrofuran (THF) as the activator, α-methylstyrene (α-MeSt) as the capping group and liquid bromine (Br2) as the bromating agent. The effects of reaction conditions such as the amounts of α-MeSt, THF, and Br2 as well as molecular weight of polystyrene on the bromating efficiency (BE) and coupling extent (CE) were examined. The present results show that the yield of PStBr obtained was more than 93.8% and the coupling reaction was substantially absent. PStBr was further used as the macroinitiator in the polymerization of methyl-methacrylate(MMA) in the presence of copper(Ⅰ) halogen and 2,2-bipyridine(bpy) complexes. It was found that the molecular weight of the resulted PSt-b-PMMA increased linearly with the increase of the conversion of MMA and the polydispersity was 1.2-1.6. The structures of PStBr and P(St-b-MMA) were characterized by 1H NMR spectra.     

Synthesis and Expression in Escherichia coli of a Human Neutrophil Activating Protein-1/Interleukin-8 Gene

The complete gene coding for human neutrophilactivating protein-1/interleukin-8 was synthesized using a semi-chemical semi-enzymatic method. The synthetic gene was then overexpressed in Escherichia coli under the temperature-regulated control of the P_RP_L tandem promoters. As determined by SDS-PAGE and densitometry, the overexpressed protein comprised up to 18.5% and 10.9% of the total soluble protein in E. coli cells grown in shake flasks and in batch fermentation, respectively. The recombinant NAP-1/IL-8 was then purified to>95% homogeneity by gel filtration and cation exchange chromatography. The purified protein appeared as a single band on the SDS-PAGE gel and possessed potent chemotactic activity in the concentration of <10 ng/ml, as assayed by the agarose plate method. An early skin reactivity was also observed when the pure NAP-1/IL-8 was injected subcutaneously into the rabbits. The N-terminal 36 amino acid sequence of the recombinant NAP1/IL-8 was determined using the Edman method and was sho     

Efficient Fixation of Carbon Dioxide by Electrolysis Facile Synthesis of Useful Carboxylic Acids

Electrochemical fixation of atmospheric pressure of carbon dioxide to organic compounds is a useful and attractive method for synthesizing of various carboxylic acids. Electrochemical fixation of carbon dioxide, electrochemical carboxylation, organic halides, organic triflates, alkenes, aromatic compounds, and carbonyl compounds can readily occur in the presence of an atmospheric pressure of carbon dioxide to form the corresponding carboxylic acids with high yields, when a sacrificial anode such as magnesium or aluminum is used in the electrolysis. The electrochemical carboxylation of vinyl bromides was successfully applied for the synthesis of the precursor of nonsteroidal anti-inflammatory agents such as ibuprofen and naproxen. On the other hand, supercritical carbon dioxide （scCO2） has significant potential as an environmentally benign solvent in organic synthesis and it could be used both as a solvent and as a reagent in these electrochemical carboxylations by using a small amount of cosolvent.     

Effect of La2O3／γ—Al2O3 Catalyst on the Activation of CH4 and CO2 to C2 Hydrocarbons under Non—equilibrium Plasma

In the reaction of methane and carbon dioxide to C2 hydrocabons under non-equilibrium plasma, methane conversion was decreased,but selectivity of C2 hydroxarbons was increased when using La2O3/γ-Al2O3 as catalyst. So the yield of C2 hydrocarbons was higher than using plasma alone. The synergism of La2O3/γ-Al2O3 and plasma gave methane conversion of 24.9% and C2 yield of 18.1%. The distribution of C2 hydrocarbons changed when Pd-La2O3/γ-Al2O3 was used as catalyst,the major C2 product was ethylene.     

Catalytic Systems Containing p-Toluenesulfonic Acid for the Coupling Reaction of Formaldehyde and Methyl Formate

The coupling reaction of formaldehyde(FA)and methyl formate(MF)to form methyl glycolate(MG)and methyl methoxy acetate(MMAc),catalyzed by p-toluenesulfonic acid(p-TsOH)as well as assisted by different kinds of solvents or Ni-containing compounds,had been investigated.The results showed that when the reaction was carried out at 140℃,with a molar ratio of FA to MF of 0.65:1, molar fraction of p-TsOH to total feedstock of 11.0%,and reaction time of 3 h,the yield of MG and MMAc was 31.1% and 17.1%,respectively,p-TsOH catalyzed the coupling reaction by means of the synergistic catalysis of protonic acidity and soft basicity.Adding extra solvents to the reaction system was unfavorable for the reaction.The composite catalytic system consisting of p-TsOH and NiX_2(X=Cl,Br,I)exhibited a high catalytic performance for the coupling reaction,and NiX_2 acted as a promoter in the reaction,whose promotion for the catalysis increased in the following order:NiCl_2相似文献   

Effect of Dimethyl Ether Co-feed on Catalytic Performance of Methane Dehydroaromatization over Mo／HZSM-5 Catalyst

The effect of dimethyl ether (DME) co-feed on the catalytic performance of methane dehydroaxomatization (MDA) over 6Mo/HZSM-5 catalyst was investigated as a function of DME concentration under reaction conditions of T=1023 K, p=101 kPa and SV=1500 ml/(g.h). A high benzene yield wasobtained and the stability of the catalyst was improved by adding 1.5%DME to the CH4 feed. The C6H6 yield was as high as ca. 10% even after reaction for 6 h. The stability of the catalyst was further improved when DME concentration in the co-feed gas was increased to an appropriate value. TGA and TPO results of the used 6Mo/HZSM-5 catalyst showed that the amount of coke on the used catalyst was reduced and the chemical nature of the coke was changed. When 1.5%DME was added to the CH4 feed, the coke formed on the catalyst could be burned off more easily than that when only CH4 was used as reactant. It is supposed that the oxygen in DME may play a role in preventing the coke burnt off at lower temperature from transforming into the coke burnt off at higher temperature, which results in the improvement of the stability of the catalyst.     

Study on the alkylation reaction of guanine and N-acetylguanine and the synthesis of 1''''-C alkylated carba-DHPG analogues

The alkylation reaction of guanine and N-acetylguanine with model compounds such as isopropyl bromide or 4-heptyl tosylate were studied. The reaction conditions such as temperature, solvent, base, and catalyst were examined for their effects on the reaction rate, and the yield and regioselectivity of the coupling reaction. The highest yield was obtained by using DMSO as the solvent. The reaction proceeded in a homogenous manner to give higher yield of 9-N and 7-N substituted product in a mole ratio of 1:1. The ratio could be raised to 2:1 if dibenzo-18-crown-6 was used as a catalyst. Using the above procedure, three carba-DHPG analogues bearing different 1'-C alkyl side chains were synthesized.     

Synthesis of ITQ-2 zeolite under static conditions and its properties

Zeolite ITQ-2 can be synthesized by swelling the layers of MCM-22 precursor. It has a single delami-nated structure of MWW with thickness of 2.5 nm. It shows disordered properties in long range and ordered in short range, which is a promising catalytic ma…     

2-十二烷基二硫代-4-苯基-1,3,4-噻二唑-5-硫酮的合成及其对铜的缓蚀性能

合成了2-十二烷基二硫代-4-苯基-1,3,4-噻二唑-5-硫酮(DPTT),用元素分析、IR1、H NMR等技术对化合物进行了结构表征.采用动态旋转挂片法考察了DPTT和苯并三唑(BTA)复配时对铜的缓蚀作用.结果表明,单一DPTT在浓度为3.0 mg/L时缓蚀效果最佳;DPTT与BTA复配使用时显示出较好的协同效应,1.0 mg/L DPTT和1.0 mg/L BTA复配时缓蚀效果最好.     

Synthesis of new amidophosphite ligand and its application in Ir-catalyzed asymmetric hydrogenation of heterocyclic compounds

A new chiral amidophosphite ligand was synthesized and tested in the iridium-catalyzed hydrogenation of heterocyclic compounds. The enantioselectivity of hydrogenation of 2-methylquinoline considerably increases when piperidine hydrochloride is used as an additive. The hydrogenation reaction of 8-methyl-2,4,5,6-tetrahydro-1H-pyrazino[3,2,1-jk]carbazole by metal complex was conducted for the first time to prepare enantiomerically enriched antidepressant Pyrazidol.     

歧化松香胺-壳聚糖缀合物的合成、表征及药控缓释行为

以天然可再生资源壳聚糖和歧化松香胺为原料,经由苯甲醛保护氨基的Schiff碱壳聚糖,通过环氧氯丙烷搭桥生成具有环氧活性基的壳聚糖,再与歧化松香胺发生接枝反应,首次合成了一种新型壳聚糖衍生物--歧化松香胺-壳聚糖缀合物(DRACC),通过FT-IR、UV、1H-NMR、XRD、SEM和TG-DTA等测试手段对产物进行了分析和表征.由元素分析法测得DRACC的取代度为0.506.并分别以壳聚糖和DRACC作为药物非诺洛芬钙缓释制剂的载体,研究了其在人工肠液和人工胃液中的缓释性能.结果表明,DRACC载体在人工肠液和人工胃液中均具有良好的缓释作用.     

Synthesis of a novel fluorescent probe and investigation on its interaction with nucleic acid and analytical application

A novel fluorescent probe N-(N-(2-(4-morpholinyl)ethyl)-4-acridinecarboxamide)-alpha-alanine (N-(N-(ME)-4-ACA)-alpha-ALA) was synthesized. The structure was characterized by 1H NMR, MS, elemental analysis, fluorescent and ultraviolet spectra. This new compound exhibited high binding affinity to DNA, intense fluorescence and high water solubility. Experiment indicated that the fluorescent intensity was quenched when DNA was added. A method for DNA determination based on the quenching fluorescence (lambda(ex)=258nm, lambda(em)=451nm) of N-(N-(ME)-4-ACA)-alpha-ALA was established. Under optimal conditions (pH 7.2, CN-(N-(ME)-4-ACA)-alpha-ALA)=3 x 10(-6) mol L(-1)), the linear range is 0.1-4.0 microg mL(-1) for both fish semen (fsDNA) and calf thymus DNA (ct-DNA). The corresponding determination limits are 4.6 ng mL(-1) for fsDNA and 5.1 ng mL(-1) for ct-DNA, respectively. The relative standard deviation is 1.0%. Thus this compound can be used as a DNA fluorescent probe. The experiments proved that the interaction mode between N-(N-(ME)-4-ACA)-alpha-ALA and DNA was groove binding. The modified Rosenthal's graphical method gave the binding constant of 1.0 x 10(6) L mol(-1) and a binding size of 0.31 base pairs per bound drug molecule.     

Synthesis of water-soluble hyperbranched polymer and its application in acrylic latex

A water-soluble hyperbranched polymer (WHBP), obtained from a second generation of hyperbranched polyester and maleic anhydride, was studied. Its effects on the properties of acrylic latexes, which were based on emulsion polymerization of butyl acrylate (BA), methyl methacrylate (MMA), acrylic acid (AA) and WHBP, and latex film were discussed. The characteristics of WHBP were determined by nuclear magnetic resonance spectroscopy (NMR), Fourier transform infrared (FTIR) and gel permeation chromatography (GPC). Particle size and morphology of latex particles were confirmed by dynamic light scattering (DLS) and transmission electron microscope (TEM). The investigation showed that WHBP could be used in emulsion polymerization, and that latex of poly(BA-MMA-WHBP) was more stable than that of poly(BA-MMA-AA). The hardness of latex film increased from 2B to HB when WHBP was used.     

有机化合物PDBP的合成及其在催人反应中的应用

用量子化学AM1方法优化了1－苯基二苯并膦（PDBP）和三苯基膦（TPP）的几何构型,比较了两种化合物的电子结构和空间结构,发现PDBP作为羧基合成铑膦催化剂的配体要优于三苯基膦（TPP）;系统研究了PDBP的合成方法,其最佳合成条件为：在无水无氧的条件下,采用二乙胺锂与溴化四苯基膦摩尔比为3,反应温度为22℃,反应5h,反应后酸化,pH值为1－2,产物收率可达到85％－88％,采用元素分析、红外、核磁等方法,对其结果进行了表征,并将PDBP用于丙烯氢甲酰化反应的催化剂配体。实验证明,在相同的反应条件下,以其为配体的催化剂活性约是目前工业上使用的以三苯基膦为配体的催化剂的1．2倍,选择性约为其1．7倍。     

AAPBA@KCC-1的合成及其对血清中唾液酸和神经节苷脂的分析应用

将3-丙烯酰胺基苯硼酸(AAPBA)修饰在介孔二氧化硅KCC-1的表面,合成AAPBA@KCC-1材料,并通过扫描电子显微镜、透射电子显微镜、N_2吸附解吸附测试和X射线光电子能谱对其进行表征;将AAPBA@KCC-1材料作为分散固相萃取(dSPE)的吸附剂,对血清样品中的唾液酸和神经节苷脂(GLS)进行提取和富集;采用傅里叶变换离子回旋共振质谱法和超高效液相色谱-离子淌度-四极杆飞行时间质谱法分别对AAPBA@KCC-1材料吸附得到的唾液酸和神经节苷脂进行分析。结果表明,AAPBA@KCC-1材料能够有效吸附唾液酸和神经节苷脂,简化了样品前处理的操作,可以进一步应用于生物样品中唾液酸和神经节苷脂的研究。     

Synthesis of cardanol-based photo-active SET-LRP initiator and its application to preparation of UV-cured resin

A benzophenone-containing SET-LRP initiator based on renewable and abundant cardanol was synthesised in 71 % yield using the selective etherification reaction. Next, methyl methacrylate (MMA) as a monomer was polymerised under SET-LRP conditions using the newly prepared initiator to prepare cardanol-end poly(methyl methacrylate) (PMMA). The kinetic results of the polymerisation indicated that the reaction was controllable when the monomer conversion was lower than approximately 50 %, and the molecular masses of PMMA measured by GPC were higher than the theoretical values while the monomer conversion was more than 50 %. In addition, most of the carbon-carbon double bonds of the side hydrocarbon chain of the end-cardanol group in the PMMA were kept intact from ¹H NMR spectrum characterisation. Accordingly, when the cardanol-end PMMA together with a tertiary amine-containing cardanol derivative was irradiated by UV light, the corresponding UV-cured resin was obtained. The chemical resistance and hardness of the UV-cured film were enhanced with the increasing irradiation time.     

有机硅氧烷预聚体的合成及其在化学固沙中的应用

以甲基三乙氧基硅烷为反应物,在盐酸催化下水解缩合,合成无色透明粘稠的液体有机硅氧烷预聚体,IR和1H NMR表征证实其为目的产物;当有机硅氧烷预聚体与工业乙醇的体积比为1∶1,以质量分数0.60%的NaOH-CH3OH溶液为固化剂,加入该溶液0.05 mL,在30 ℃,预聚体交联固化时间为9 min;在50 ℃,预聚体交联固化时间为4 min;首次将有机硅氧烷预聚体,或它与聚乙烯醇（PVA20-88）的混合物用作化学固沙剂,形成的固结层具有较好的耐水性和较高的抗剪强度;当PVA20-88与有机硅氧烷预聚体的质量比为1∶4时,粘聚力达到483.7 kPa,内摩擦角为68.39°,在160 h的紫外光照射下,具有很好的耐老化性。