氧化酶及烷烃氧化

记述了氧化酶在生物催化中的应用. 较之传统的化学反应, 氧化还原生物催化反应有较好的选择性、可控性和经济性, 人们正在积极地寻找这类催化剂. 自然界中被高度还原的烃类品种丰富, 因此催化烷烃末端或近末端氧合反应的酶也相对容易找到. 很多这一类的酶生化特性已作了详细的描述, 烷烃加氧酶催化高附加值反应的潜力已得到了广泛地认可.     

亚烷基卡宾与甲醛环加成反应机理的理论研究

用二阶微扰理论研究了单重态亚烷基卡宾与甲醛发生的三种环加成反应的机理 ，采用MP2/6－31G~*方法计算了势能面上各驻点的构型参数、振动频率和能量。根 据能量数据可以预言环加成反应（1）的a途径将是单重态亚烷基卡宾与甲醛环加成 反应的主要反应通道，该反应由两步组成：（I）亚烷基卡宾与甲醛生成了一富能 中间体（INT1a），是一无势垒的放热反应，（II）中间体异构化为产物亚烷基环 乙烷，其势垒为24.1 kJ·mol~(-1)(MP2/6-31G~*)。     

单氨基取代3∶1不对称酞菁锌的合成及其在有机溶剂中聚集状态的研究

Monoamino substituted asymmetrical phthalocyanine zinc(Ⅱ), 2-amino-9,10,16,17,23,24-hexapentyloxy phthalocyanine zinc(Ⅱ), was synthesized by statistical condensation and characterized by elemental analysis, UV-Vis, IR and TOF-MS. The aggregative behavior was studied in DMF, THF and CH₂Cl₂. The results show that it is not aggregateve in DMF and THF, whereas form dimer in CH₂Cl₂ at 8 × 10^-7～8 × 10^-6 mol·L^-1. The equilibrium constant for the dimer was calculated at the same time, indicating that the less polar solvent is unfavorable for the presence of the monomer.     

QuEChERS/超高效液相色谱-串联质谱法同时测定水产品中四溴双酚A与六溴环十二烷

建立了同时测定水产品中四溴双酚A(TBBPA)和六溴环十二烷(HBCD)的超高效液相色谱-串联质谱方法。样品前处理采用QuEChERS方法,均质生物样品用水分散后加乙腈提取,经C_(18)分散固相萃取净化。采用CORTECS~?C_(18)色谱柱(4.6 mm×100 mm×2.7μm)分离,以甲醇-水为流动相进行梯度洗脱,流速为0.7 mL/min。采用电喷雾离子源,在负离子模式下以多反应监测(MRM)方式检测。结果表明,TBBPA和3种HBCD单体在0.5～500μg/L范围内线性良好,相关系数(r)大于0.998,检出限(LOD,S/N=3)和定量下限(LOQ,S/N=10)分别为0.04～0.16μg/kg和0.12～0.55μg/kg。在5、20、50μg/kg加标水平下的平均回收率为74.0%～121%,相对标准偏差(RSD)为0.20%～23%。该方法操作简单、快速、重现性好,适用于水产品中TBBPA和HBCD的快速检测。     

Copper phosphonates with dinuclear and layer structures: a structural and magnetic study

Hydrothermal reactions of copper (II) nitrate with 1-hydroxycyclohexanephosphonic acid [C₆H₁₀(OH)PO₃H₂] or Δ¹-cyclohexenephosphonic acid [C₆H₉PO₃H₂] have resulted in three new copper phosphonates, namely, Cu(C₆H₁₀(OH)PO₃)(H₂O)₂ (1), Cu(C₆H₁₀(OH)PO₃) (2) and Cu(C₆H₉PO₃)(H₂O) (3). Compound 1 has a dinuclear structure in which two {CuO₅} square pyramids are bridged by two {CPO₃} tetrahedra through corner sharing. The dimers are connected through intermolecular hydrogen bonds, forming supramolecular layers. Both compounds 2 and 3 show layer structures typical for metal mono-phosphonates, in which the inorganic metal-containing layers are separated by cyclohexane or cyclohexene groups. The magnetic studies show that ferromagnetic interactions are mediated between copper centers in compound 1. In compounds 2 and 3, antiferromagnetic interactions are dominant.     

聚丙烯酰胺凝胶结构非均匀性的动态光散射研究

利用动态光散射技术研究了聚丙烯酰胺 (PAAm)凝胶结构的非均匀性 ,分析了PAAm凝胶结构非均匀性的形成原因及凝胶动态光散射的数据处理方法和分析结果的物理意义 .研究结果表明 ,PAAm凝胶中含有动态相关长度 (LC)不同的两相 ,其中 ,LC 为 10～ 2 0nm的区域是聚合物稀疏相 ,LC 为 85nm左右的区域是聚合物密集相 ,两相的不均匀分布形成了PAAm凝胶结构的非均匀性 .分析表明 ,PAAm凝胶存在两相主要是由于单体和交联剂的溶解度存在差异所致 .随交联度增大 ,PAAm凝胶结构的非均匀性显著增强     

Mixed-valent diruthenium diphosphonate with kagomé structure

This paper reports the first example of diruthenium phosphonate with kagomé structure, namely, [NH3(CH2)4NH3][Ru2(hedpH(0.5))2].2H2O (hedp = 1-hydroxyethylidenediphosphonate). The compound contains kagomé layers that are linked by very strong hydrogen bonds into a nanoscale kagomé structure. Ferromagnetic interactions are mediated between the paramagnetic diruthenium units.     

冻干保护剂溶液低温退火特性的研究

利用差示扫描量热仪(DSC)研究了10%叔丁醇/10%蔗糖/水溶液的冻结特性, 退火温度及退火时间, 分析了溶液的退火行为. 实验结果表明, 溶液降温时, 蔗糖的存在阻碍了叔丁醇析出, 最大冻结浓缩溶液玻璃化转变温度Tg′由－32.5 ℃降低到－42.0 ℃, 升温时在－30 ℃叔丁醇发生反玻璃化. 在反玻璃化峰附近的温度进行退火可使叔丁醇充分析出, Tg′由－42.0 ℃上升到－34.9 ℃. 所需的退火时间与退火温度有关, 退火温度越接近Tg′, 所需的退火时间越长. 在－37 ℃时, 退火20 min可完全消除反玻璃化.     

Using Toad Oocytes as an Ultrasensitive System for Estimating the Biological Activity of Trichosanthin

A sensitive bioassay for estimating the activity of Trichosanthin was developed by using intraoocyte microinjection as the technique and germinal vescicle breakdown as a marker. The GVBD inhibitory activity assay was million-fold more sensitive than the routinely used abortifacient activity assay. The detectable amount of Trichosanthin ranged from 0.5 to 100 pg. Since the least detectable dose was 0.5 pg, it made the assay suitable to analyse the microquantity of pure Trichosanthin used for studying the structure and function of the drug.     

激光光散射研究丙烯酰胺-二甲基二烯丙基氯化铵共聚物的溶液行为

用激光光散射技术表征了阳离子含量受控的丙烯酰胺 二甲基二烯丙基氯化铵共聚物 (简称P(AM DMDAAC) )在 0 1mol LNaCl溶液中的基本参数和溶液行为 .表观基本参数 : Mw ,app =5 0 4× 10 5g·mol- 1 、app =39 9nm和A2 ,APP =1 5× 10 - 4cm3·mol·g- 2 .动态光散射研究结果表明 ,扩散系数Dt 与角度、浓度皆呈非线性依赖关系 ,当C >C 或在较大的散射角域 ,Dt 偏离线性关系所预示的理论值而向减小的方向发展 ,表明存在缔合物 ;流体力学半径Rh 分布有大、小两个范围 ,并随温度升高向小尺寸方向发展 ,证明了体系中存在缔合行为以及升温的解缔合作用 .在一定条件下 ,“亚稳定性”的存在有力地旁证了体系的缔合行为