Synthesis of homochiral spiro[4.4] nonane-1,6-diols

Homochiral cis,cis-; cis,trans- and trans,trans-spiro[4.4]nonane-1,6-diols were prepared via diastereoselective reduction of enantiomerically pure spiro[4.4]nonane-1,6-dione (1) with the corresponding reducing agents: lithium n-butyldiisobutylaluminium hydride for cis,cis-diol (2) with 88% yield; BH3·THF for cis, trans-diol (3) with 91% yield; LiAlH4 for trans,trans-diol (4) with 15% yield.     

利用目标试验因子分析法确定化学反应的级数及速率常数

利用目标试验因子分析(TTFA)结合数值遗传算法(NGA).解析反应过程中在线测得的动力学谱-光谱数据矩阵,可在未知各组分纯光谱及动力学模型情况下同时求解出各组分的纯光谱、反应级数及速率常数。提出用近似计算法计算各组分的动力学谱,使该方法能适用于任意反应级数的体系。针对两步连续反应模型,对反应物、中间体和最终产物均有吸收及某一种组分没有吸收的体系的模拟实验数据矩阵进行了处理,表明该方法均能适用。利用该方法对邻苯二甲酸二甲酯在碱性介质中的水解反应及日落黄水溶液的电解降解反应过程中测得的数据矩阵进行解析,均获得了可靠结果。     

聚乙二醇接枝聚乳酸的自组装纳米微球的制备及性能

对制备的新型聚乙二醇(PEG)接枝聚乳酸(PLA)在水中的自组装性能进行研究, 探讨其作为纳米药物载体的可行性和稳定性. 目测法得到其溶解度为(2.16～4.32)×10^－2 mg•mL^－1; 荧光法得到聚合物的临界胶束浓度为1.12×10^－3 mg•mL^－1; 透射电子显微镜观察显示该聚合物在水中的自组装聚集体为纳米级球形; 动态激光光散射测试微球的粒径和Zeta电位发现, 在微球的制备过程中, 聚合物的亲/疏水性比例、水相介质及水溶液的pH值对它影响显著; 而制备后, 稀释和冷冻对它无显著影响, 改变微球的环境pH值至酸性, 出现聚集, 至碱性无影响. 研究结果显示, 该聚合物在水和磷酸钠盐缓冲液中可形成稳定的纳米微球, 通过微球的制备条件和存在环境可控制其粒径和Zeta电位, 因此根据应用需要, 通过控制其粒径和Zeta电位, 可能提高微球的在体血液循环时间并实现靶向缓释.     

Diels-Alder Addition of Dicyclopentadiene with Cyclopentadiene in Polar Solvents

Diels-Alder addition of dicyclopentadiene and cyclopentadiene in polar solvents has been studied to produce tricyclopentadiene（TCPD） that is a potential high-density fuel precursor. GC and MS analysis shows that the adducts contain two isomers, namely exo- and endo-TCPD. Theoretical simulation shows that although the transition state of endo-TCPD has a lower activation energy, exo-TCPD is thermodynamically preferred. Polar solvents can accelerate the reaction rate and improve the exo/endo ratio of TCPD because the transition state of exo-TCPD has a higher polarity than that of endo-TCPD. The solvent effect follows the order of polarity： benzyl methanol〉cyclohexanone〉toluene. The conversion rises when the temperature ranges from 120 to 150 ℃, but the selectivity of TCPD slightly decreases. Increasing the pressure can improve the conversion but the exo/endo ratio of TCPD is unchanged. The apparent kinetics in different solvents was determined via nonlinear regression. The activation energies are 99.47, 101.15, and 107.32 kJ/mol for benzyl methanol, cyclohexanone, and toluene, respectively. The optimal reaction conditions are as follows： benzyl methanol as solvent, temperature 150 ℃, and pressure 900 kPa. After an 11-hour reaction, a conversion of 58.0%, a TCPD selectivity of 95.7%, and an exo/endo ratio of 1/5.3 has been obtained.     

5-羟基-5-甲基-3,4-二苯基异唑的合成

以苯乙氰和苯甲酸甲酯为起始原料,经Claisen缩合、羟胺化、环合制得伐地考昔的关键中间体--5-羟基-5-甲基-3,4-二苯基异唑,总产率54.68%.其结构经1H NMR,IR和MS确证.     

PbS纳米棒的水热合成与表征

以乙酸铅和硫脲为主要原料,十二烷基磺酸钠和十六烷基三甲基溴化铵为表面活性剂,在120℃反应12h,水热法制备了PbS纳米棒.并利用X射线粉末衍射(XRD)、透射电子显微镜(TEM)和高分辨电子显微镜(HRTEM)等手段对产物进行了表征,实验结果表明：产物为纯相立方结构的PbS单晶纳米棒.考察了乙酸铅和硫脲间的摩尔比以及反应温度对合成产物的影响,并初步探讨其形成机理.     

Liquid–liquid extraction of neodymium (III) and europium (III) using synergic mixture of furosemide and tribenzylamine in benzyl alcohol

The extraction behavior of Nd(III) and Eu(III) with 0.05 mol dm⁻³ furosemide in benzyl alcohol as single acidic extractant and then with equimolar (0.05 mol dm⁻³) synergic mixture of furosemide as acidic extractant and tribenzylamine as neutral donor in benzyl alcohol has been studied from aqueous solutions of pH 1 to 6. The effect of various parameters and of various cations and anions on the extraction of these metal ions was investigated. The composition of the extracted adducts was determined by slope analysis method that came out to be [(M(FS)₂)⁺ (CH₃COO)⁻] and [M(FS)₃·3TBA] where M = Nd(III) and Eu(III).

     

电喷雾-差分电迁移率-粒子计数法绝对定量分析牛血清白蛋白

建立了基于电喷雾-差分电迁移率-粒子计数的蛋白定量分析方法,通过优化电喷雾电压、液体溶液流速以及气体流速等参数,对牛血清白蛋白标准物质进行了定量分析。结果表明,在泰勒锥状态下,样品溶液流速300 nL/min,空气流速1.0 L/min,二氧化碳流速0.1 L/min的条件下,可以实现牛血清白蛋白标准物质和溶液标准物质的准确定量分析,测定结果为分别为20.05 g/L和69.52 g/L,与标准物质定量值的相对误差在±5%以内。该方法快速准确、灵敏度高、耗样量少,且不需要内标和外标,为蛋白质绝对定量分析提供了一种新的方法。     

两步电泳沉积制备TiO2光阳极用于高效染料敏化太阳能电池

采用不同沉积电压制备TiO₂光阳极,研究电压对薄膜沉积速率、厚度和形貌的影响。通过台阶仪、光学照片、扫描电子显微镜（SEM）、电化学交流阻抗谱、开路电压衰减曲线对光阳极和电池进行系统表征,并测试了染料敏化太阳能电池器件的电流密度-电压（J-V）曲线,计算其光电转换效率。结果表明,提高沉积电压时,光阳极薄膜的沉积速率加快,膜厚也增加,但是电压过高时,薄膜会有裂缝和覆盖不全的问题,这会对电池的效率造成负面影响。综合考虑低沉积电压条件下薄膜均匀无裂缝和高沉积电压条件下沉积速率快的优点,采用先30 V电压、后60 V电压的电泳沉积方式来制备光阳极,结果呈现协同效果,既降低了制备时间又得到高质量的薄膜,在无其他修饰的情况下,电池的光电转换效率可以达到7.29%。     

NEW HETEROCYCLIC SYSTEM SYNTHESIS I REACTION OF DIHYDRO-1,5-BENZO-DIAZEPINES AND THIAZEPINES WITH (ETHOXYCARBONYL)CARBENES

Dihydro-1-benzoyl-1,5-benzodiazepines react with (ethoxycarbonyl)carbenes to give 4H-azirino-[1,2-a][1,5]-benzodiazepines and unexpected new tin9 system 1H-pyrrolo-[1,2-a][1,5]-benzodiazepines. Dihydro-1,5-benzothiazepines react with (ethoxycarbonyl)carbenes in cyclohexane to gire unexpected rin9 cleavage products ethyl (2E, 4E)-3-aryl-2-arylthiohexadienoates.