三组分反应合成多官能团化α-氰基噻吩的简便方法

本文报道了一种利用多组分反应合成α-氰基噻吩的新方法. 在碱存在条件下, β-二羰基化合物、二硫化碳和溴乙腈经过连续的多步反应, “一锅”合成多官能团化的α-氰基噻吩. 该方法简洁, 条件温和, 产率高.     

Synthesis of double-hydrophilic double-grafted copolymers PMA-g-PEG/PDMA and their protein-resistant properties

A series of double-hydrophilic double-grafted PMA-g-PEG/PDMA copolymers, which contained poly(methacrylate) (PMA) as backbone, poly(ethylene glycol) (PEG) and poly(N,N-dimethylacrylamide) (PDMA) as side chains synthesized successfully by using reversible addition-fragmentation chain transfer (RAFT) polymerization and atom transfer radical polymerization (ATRP), were used as physical coatings for the evaluation of protein-resistant properties by capillary electrophoresis (CE). Electroosmotic flow (EOF) measurement results showed that the PMA-g-PEG/PDMA copolymer coated capillaries could suppress electroosmotic mobility in a wide pH range (pH = 2.8–9.8) and EOF mobility decreased with the increase of copolymer molecular mass and PDMA content. At the same time, protein recovery, theoretical plate number of separation and repeatability of migration time demonstrated that antifouling efficiency was improved with the increase of molecular mass and PEG content.     

S-亚硝基-N-乙酰基-D,L-青霉胺二肽分子中S-NO键断裂能的测定

利用滴定量热技术并结合适当的热力学循环测定了乙腈溶液中7个S-亚硝基-N-乙酰基-D,L-青霉胺二肽化合物中S—NO键的异裂能和均裂能, 其能量范围分别为234.5—246.2 kJ/mol和101.6—122.1 kJ/mol. 结果表明, 所研究的亚硝基硫醇化合物更容易通过S—NO键的均裂释放NO自由基(NO·). 通过热力学循环对7个亚硝基硫醇化合物自由基负离子中S—NO键的异裂能和均裂能进行估算, 能量范围分别为19.2—35.5 kJ/mol和-4.2—22.6 kJ/mol, 表明这些自由基负离子在室温下不稳定, 容易通过S—NO键的异裂释放出NO-.     

Preparation and characterization of white bamboo charcoal PET fiber

<正>Bamboo charcoal polyester fiber(BC-PET) has been widely applied in home textiles,functional clothing and hydra-balance material,due to their strong adsorptivity,good resolvability,anti-statics,deodorization,antibacterial,anion releasing and far infrared emitting.But BC-PET is black and difficult to be dyed,and its application is limited.In this article,nitric acid was used to treat the surface of bamboo charcoal(BC) powder,and BC powder was modified by titanium dioxide sol to prepare white bamboo charcoal(white-BC) particle.White bamboo charcoal polyester fiber(white-BC-PET) was obtained by mixing white-BC and polyester(PET) resin in double screw extruder.Performance of fiber was tested referring to national standard GB/T14464-2008 of common PET fiber and most of its indicators have already exceeded GB the level of excellent product.SEM photographs showed that the white-BC was uniformly distributed inside or on the surface of fiber.The white-BC-PET could absorb some aniline and had at least 90%anti-bacterial rate.The anti-bacterial rate could have almost been kept after it was washed 50 times.It was hopeful to be applied in various fields as functional fiber.     

Stable and good color purity white light‐emitting devices based on random fluorene/spirofluorene copolymers doped with iridium complex

Conjugated polymers PSNFP and PSNFF based on naphthalene‐containing spirofluorene structure and 9,9‐dioctylfluorene, 2,5‐dioctylbezene were designed and synthesized for light emitting applications. These two polymers show good blue emission both in solution and thin film. Thermal gravimetric analysis reveals they have good thermal stability with the decomposition temperature higher than 400 °C. Electrochemistry characterization shows that both of these polymers have a large band gap and deep highest occupied molecular orbital, which are important features for phosphorescent host materials. White light‐emitting diodes were fabricated by using PSNFF as the host material, containing two typical phosphorescent Ir complex dopants: green emitter Ir(mppy)₃ and red emitter Ir(piq)₂. The color coordinate CIE stayed nearly constant, changed from (0.32, 0.31) to (0.28, 0.31) when the current density varied from 2 to 20 mA cm^?2. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Blue-light emitting diodes and flat display based on poly (p-phenylenevinylene) copolymers

Copolymers containing alternating flexible aliphatic blocks and rigid poly (p-phenylenevinylene) (PPV) blocks were synthesized and characterized. It was found that the fluorescent intensity increases with increasing length of the flexible blocks. Bright blue-light emitting diodes were fabricated using PPV copolymers as electroluminescent layers. The devices show 190 cd/m² light-emitting brightness at 460 nm and 15 V turn-on voltage. The effects of oxadiawle derivative PBD and tris(8-hydroxyquinoline) aluminum Alq₃ electron-transporting layers on the luminance and stability of the devices are discussed. Project supported by the National Natural Science Foundation of China, PCLCC, the State Comission of Science and Technology of China (863-715-002-0130) and the Chinese Acadeny of Sciences (KJ951-A1-501-01)     

(1S,2S)-DPEN修饰的Ir/Al2O3催化苯乙酮及其衍生物的不对称加氢反应$

在碱性条件下制备了三氧化二铝负载的铱(Ir/γ-Al2O3)催化剂,并用于苯乙酮及其衍生物的不对称催化加氢反应.考察了不同的碱、碱浓度、手性二胺(1S,2S)-1,2-二苯基乙二胺[(1S,2S)-DPEN]浓度、反应温度和反应压力对催化剂及反应的影响.结果显示,在优化反应条件下,该催化剂表现出较高的催化活性和良好的对映选择性,其中异丁酰苯不对称催化加氢反应的对映选择性达到了80.3%.该催化剂不需要使用任何稳定剂,制备方法简单,催化性能稳定,通过简单的离心分离即可循环使用.     

乙酰鸟氨酸脱乙酰酶固定化细胞拆分D,L-缬氨酸

报道了一种利用具有乙酰鸟氨酸脱乙酰酶活性的固定化细胞拆分D,L-缬氨酸的新方法. 该酶促反应最适条件: pH=6, 反应温度50 ℃, 底物N-乙酰-D,L-缬氨酸浓度200 mmol/L, 固定化细胞用量0.2 g/mL(或100 U/mL). 0.1 mmol/L CoCl₂条件对该酶促反应有显著的激活作用. 在以上条件下反应2～3 h, 测得产物L-缬氨酸浓度95 mmol/L. 该固定化细胞连续10次使用, 平均转化率为90.8%(以N-乙酰-L-缬氨酸计), 显示出了良好的工业化应用前景.     

Cu7.2S4量子点玻璃的制备及三阶非线性光学性质

利用溶胶-凝胶法结合气氛控制合成了含Cu7.2S4量子点的玻璃. 通过热重-差热分析仪对干凝胶样品的热分解机制进行了分析, 并利用X射线粉末衍射仪、 X射线光电子能谱、 透射电子显微镜、 X射线能量色散谱)、 高分辨透射电子显微镜及选区电子衍射对 Cu7.2S4量子点在玻璃中的微结构进行了表征, 利用飞秒Z扫描技术研究了材料在800 nm的三阶非线性光学性质. 结果表明, 尺寸在9~21 nm之间的Cu7.2S4纳米晶已经在玻璃中形成, 该玻璃展示出了优异的三阶非线性光学性能, 其三阶非线性光学折射率(γ)、 三阶非线性吸收系数(β)和三阶非线性极化率[X(3)]分别为1.11×10-15 m2/W, 8.91×10-9 m/W和9.56×10-18 m2/V2.     

超支化聚(β-环糊精)的合成与表征

通过硅氢加成反应, 以ABx型功能化β-环糊精大单体为原料, 采用一步法合成出新型超支化聚(β-环糊精)高分子. ABx大单体由单取代对甲苯磺酰化β-CD依次与烯丙基胺、1,1,3,3-四甲基二硅氧烷(含氢双封头)及丙烯酰氯反应得到. 采用1H NMR, 13C NMR, 29Si NMR和飞行时间质谱对ABx大单体及其聚合物的结构进行了表征. 利用凝胶渗透色谱/多角度激光光散射(SEC/MALLS)联用仪得到了超支化聚(β-环糊精)的分子量、分子量分布及本体黏度.     

带有酰胺侧基的中空手性高分子微球的合成及其分离性能

合成了带有手性基团的多孔高分子微球, 并将其作为高效液相色谱手性固定相用于分离制备盐酸贝那普利的一个重要中间体(R)-α-羟基苯丁酸乙酯.     

α,β-聚[N-(丁二酸基)- L-天冬酰胺]的合成及其顺铂大分子药物的细胞毒性

L-天冬氨酸在H2O/三乙胺混合溶剂中直接均相开环聚(L-天冬酰亚胺)(PSI), 合成α,β-聚[N-(丁二酸基)-L-天冬酰胺](PSAA). 研究了H2O和三乙胺的混合体积比对反应物溶解性能的影响, 并用FTIR和1H NMR表征了PSAA的结构. 以PSAA和α,β-聚(L-天冬氨酸)(PAsp)为载体, 与顺式二氯二氨合铂(Ⅱ)(CDDP)络合, 合成了PSAA-CDDP和PAsp-CDDP大分子药物. 结果表明, 载体PSAA和PAsp对Bel7402细胞的毒性均低于同浓度的聚赖氨酸; PSAA-CDDP的水溶性良好, 载药量较高, 达到了14.6%, 其药物控制释放性能较好; PSAA-CDDP和PAsp-CDDP的细胞毒性随着其浓度的增大而增大, 且细胞毒性PAsp-CDDP相似文献   

双酚A葡萄糖醛酸苷的高效制备

采用鼠肝微粒体(RLM)生物转化法,利用正交实验在体外实现了双酚A(BPA)向双酚A葡萄糖醛酸苷(BPA-G)的高效转化,同时借助新型色谱分离材料C18WAX及固相萃取技术实现了BPA-G的高效富集与纯化,并对产物进行了结构表征.     

Design, synthesis and preliminary biological evaluation of brain targeting L-ascorbic acid prodrugs of ibuprofen

L-Ascorbic acid（AA,vitamin C） exhibits a high concentration in the brain.The transportation of AA in brain is mainly mediated by the glucose transporter 1（GLUT₁） and the Na⁺-dependent vitamin C transporter SVCT₂.While L-ascorbic acid C6-O conjugation has been investigated as a tool to enhance brain drug delivery,C5-O conjugation and C5-O & C6-O conjugation as brain targeting tools have not been reported.In this letter,ibuprofen was linked directly to C5-O,C6-O and C5-O & C6-O positions of L-ascorbic acid with eater bonds,providing prodrug 1,2 and 3,respectively,to improve their targeting abilities in the brain.Prodrug 1,2 and 3 were synthesized in facile ways with good yields.And the preliminary evaluation in vivo illustrated that prodrug 2 had a better targeting ability than prodrug 1. Moreover,prodrug 3,whose C5-O & C6-O positions were both modified,had good targeting ability for brain which will provide an important evidence for our further study on C5-0- & C6-0- di-derivatives of L-ascorbic acid.     

OPTIMIZATION OF THE SYNTHESIS OF ACRYLAMIDE HYDROGEL BY γ-RAY IRRADIATION

Hydrogels have been synthesized from 10%, 20%, 30%, 40%, 50% and 60% aqueous solutions of acrylamide monomer by gamma radiation employing doses in the range of 0.2-30 kGy from a Co-60 source. The effect of solution concentration, y-ray dose, pH and time was studied in order to observe the optimizing conditions in the characterization of hydrogels. Gel fraction increases with dose for all concentrations indicating hundred-percentage conversion of gel at doses ≥5 kGy for homogenous solutions in the range of 20%-50% concentration. On the other hand, 10% solution provides conversion less than 86% even at 30 kGy, whereas 60% monomer makes an inhomogeneous solution which stile gives about 100% gel fraction. Swelling of hydrogels under water with respect to time varies with both the doses and concentrations due to the change of crosslinking density in the gels. The maximum volume change of hydrogels during swelling and water desorption mainly occurs within 24 h. Swelling is also enhanced with the rise of pH due to change of ionic content of the solvent. Considering the amount of gel fraction and the properties of hydrogel, the samples prepared from 20% solution at 5 kGy show better results. Moreover, the effect of bacteria on hydrogel was found to be nil, suggesting a prohibition of growth of microorganism in it.     

PREPARATION AND STRUCTURE OFFIVE DERIVATIVES OFβ-(1→3)-D-GLUCAN ISOLATED FROM PORIA COCOS SCLEROTIUM*

A new solvent of cellulose (1.5 mol/L NaOH/0.5 mol/L urea aqueous solution) was used as one of the homogeneous reaction media of polysaccharides for methylation, hydroxyethylation and hydroxypropylation. A water insoluble β-(1→3)-D-glucan, sample PCS3-Ⅱ, isolated from fresh sclerotium of Poria cocos was sulfated in dimethyl sulfoxide (Me2SO), carboxymethylated in NaOH, isopropanol solution, as well as methylated, hydroxyethylated and hydroxypropylated in the new solvent system, respectively, to obtain five water-soluble derivatives coded as S-PCS3-Ⅱ, C-PCS3-Ⅱ, M-PCS3-Ⅱ, HE-PCS3-Ⅱand HP-PCS3-Ⅱ. Their chemical structure and distribution of substitution were characterized by infrared spectroscopy (IR), elementary analysis (EA), ^1H-NMR, ^13C-NMR, 2D-COSY, 2D-TOCSY and 2D-^1H-detected ^1H ^13C HMQC spectra. The results reveal that the relative reactivity of hydroxyl groups of the β(1→3)-D-glucan is in the order C-6 ＞ C-4 ＞ C-2 on the whole. The substitution of the samples S-PCS3-Ⅱ, C-PCS3-Ⅱ and M-PCS3-Ⅱ occurred mainly at C-6 position and secondly at C-4 and C-2 positions, and that of HE-PCS3-Ⅱ occurred at C-6 and C-4 positions and of HP-PCS3-Ⅱ almost completely occurred at C-6 position. The degrees of substitution (DS) obtained from ^13C-NMR range from 0.23 to 1.27. The water solubility of the derivatives is in the order S-PCS3-Ⅱ ＞ C-PCS3-Ⅱ ＞ M-PCS3-Ⅱ ＞ HE-PCS3-Ⅱ ＞ HP-PCS3-Ⅱ. This work provides a novel and nonpolluting process for the methylation, hydroxyethylation and hydroxypropylation of β-(1→3)-D-glucan.     

Sn和Pb单掺杂Al4小团簇的理论研究

在CCSD(T)/aug-cc-pVTZ&;CEP-121G//B3LYP/6-311+G(d)&;LANL2DZ水平上, 研究了由更高周期的Sn和Pb单掺杂Al4团簇形成的五原子含铝体系XAl4(X=Sn, Pb), 确定了体系的低能异构体, 分析了关键异构体的结构和稳定性. 研究结果表明, 与SiAl4及GeAl4的基态平面四配位Si/Ge结构所不同, 等价电子的SnAl4和PbAl4体系的基态结构不是平面四配位Sn/Pb, 而是平面四配位Al, 其中杂原子Sn/Pb采取二配位方式, 此外, Sn/Pb采取三配位方式的非平面结构的稳定性也要优于平面四配位Sn/Pb结构.     

新型薄膜扩散梯度装置定量测量水环境中重金属形态

采用以纤维素透析膜为扩散相, 0.05 mol/L羧甲基纤维素钠(CMC)溶液为结合相的薄膜扩散梯度(DGT)装置(CMC-DGT)定量累积和测量水溶液中Cu²⁺, Cd²⁺和Pb²⁺的有效态; 考察了pH值和离子强度对CMC-DGT累积Cu²⁺, Cd²⁺和Pb²⁺的影响以及不同配体(乙二胺四乙酸二钠、 单宁酸和黄腐酸)对重金属有效态的影响; 测量了外加标的天然水和工业废水中重金属的有效态浓度; 并比较了不同结合相DGT装置对同一水体中重金属的有效态浓度. 实验结果表明, 0.05 mol/L CMC溶液对Cu²⁺, Cd²⁺和Pb²⁺累积容量分别为0.24, 0.11和0.45 mg/mL; 定量累积的最佳pH值范围分别为3.7～8.0, 4.7～9.0和4.7～8.0; 随着离子强度的增大, CMC-DGT对Cu²⁺, Cd²⁺和Pb²⁺的累积容量下降; CMC-DGT能够定量地累积配制水中的游离Cu²⁺, Cd²⁺和Pb²⁺, 回收率分别为92.1%, 100.6%和96.4%; 当有配体存在时, 随着配体浓度的增大, CMC-DGT测量的Cu²⁺, Cd²⁺和Pb²⁺有效态的浓度随之下降; 在过滤工业废水、 河水和湖水中, 不同结合相DGT装置对重金属有效态的测量值不同. 结果表明, CMC可作为DGT技术新的液态结合相.     

二乙氧基硫代磷酸酯类有机磷农药单链抗体的制备及广谱特异性

从分泌抗二乙氧基硫代磷酸酯类有机磷农药(DPPs)单克隆抗体(MAb)的杂交瘤细胞系(12C2)中提取了总RNA, 经RT-PCR反转录成cDNA, 设计带linker引物, 采用重叠延伸PCR制备单链抗体(scFv)基因, 将其克隆到噬菌体载体p3MH中, 构建成噬菌体单链抗体表达载体, 转化大肠杆菌表达出噬菌体表面展示scFv, 对经过Phage-ELISA鉴定的阳性克隆进行噬菌体外壳蛋白基因geneⅢ的去除, 用IPTG诱导其可溶性表达, 对表达产物进行SDS-PAGE, Western-Blot及ELISA鉴定, 并与亲本MAb进行性能对比. 结果表明, 可溶性表达的scFv分子量为27000; scFv与DPPs的交叉反应率比其亲本MAb提高了1.3~3.5倍, 表明其广谱特异性有所提高. 由于scFv与MAb相比具有诸多优点, 因此本研究为有机磷农药多残留检测方法的建立提供了一种更广谱、 更灵敏的新型识别分子.     

NONLINEAR J-E CHARACTERISTICS IN THE ELECTRIC-THERMAL EQUILIBRIUM STATE FOR HIGH DENSITY POLYETHYLENE CONDUCTIVE COMPOSITES*

 The nonlinear J-E characteristics under self-heating equilibrium for conductive composites based on high density polyethylene were studied. The results show that there are identical conduction mechanisms under self-heating equilibrium for the composites with various initial resistivities determined by filler content or ambient temperature. The nonlinear conduction behavior was involved in the limited microstructure transformations of the conducting network induced by electrical field applied and the corresponding self-heating effect. A reversible thermal fuse (RTF) model was suggested to interpret the physical origin of the nonlinear J-E characteristics.