丙烷在无机膜反应器中的芳构化

研究了在固定床反应器和膜反应器中的丙烷芳构化，考察了ＨＺＳＭ－５担载的Ｇａ和Ｐｔ－Ｇａ催化剂对反应的影响。结果表明，采用无机膜反应器可以提高丙烷芳构化选择性，从而提高芳烃收率达１０％以上。在膜反应器中，低碳烷烃选择性降低，烯烃选择性增强。固定床相比，膜反应器在低温时对芳构化反应的促进作用最为显著，但是随着温度升高，其促进作用减弱。     

Nd（naph）_3－Al（i－Bu）_3催化马来酸酐和环氧丙烷交替共聚合

研究了马来酸酐和环氧丙烷的交替共聚，发现Ｎｄ（ｎａｐｈ）＿３－Ａｌ（ｉ－Ｂｕ）＿３是马来酸酐（ＭＡｎ）和环氧丙烷（ＰＯ）交替共聚的良好催化剂．用红外光谱、核磁共振研究了共聚物的结构．共聚反应动力学研究表明共聚反应与单体和催化剂浓度均呈一级关系．表观活化能为１１３ｋＪ／ｍｏｌ．     

分子筛负载席夫碱钴配合物的制备及其催化氧气氧化环己烷

采用柔性配位法将双水杨醛叉乙二胺合钴(Cosalen)封装到了NaY分子筛的超笼中,采用FT-IR,UV-Vis,XRD,TG/DTA 和 BET比表面积及孔容分析对负载型配合物(Cosalen-NaY)进行了表征.在催化氧气氧化环己烷的反应过程中,Cosalen-NaY能有效地促进环己基过氧化物的分解,在0.85 MPa的氧压下,150 ℃反应3 h,环己烷的转化率达到13.4%,在反应体系中加入乙腈作溶剂,130 ℃下进行反应,环己烷的转化率提高到{28.3%.产物中环己醇、环己酮、己二酸的选择性明显高于Cosalen为催化剂的反应.催化剂回收实验表明Cosalen-NaY经过三次重复使用后,没有显著的活性组分流失,可以重复使用.     

Electron paramagnetic resonance study of amphiphiles partitioning behavior in desiccation-tolerant moss during dehydration

Desiccation tolerance is a crucial characteristic for desert moss surviving in arid regions. Desiccation procedure always induces amphiphiles transferring from the polar cytoplasm into lipid bodies. The behavior of amphiphiles transferring can contribute to the enhancement of desiccation tolerance and the reduction of plasma membrane integrity simultaneously. The effects of amphiphiles partitioning into the lipid phase during water loss has been studied for pollen and seeds using electron paramagnetic resonance (EPR) spectroscopy. However, desiccation-tolerant high plants occur among mosses, several angiosperms and higher plants seeds or pollens. They have different strategies for survival in dehydration and rehydration. A desiccation-tolerant moss Tortula desertorum was used to investigate the behaviors of amphiphilic molecules during drying by spin label technology. There are small amount of amphiphilic probes partitioning into membrane during moss leaves dehydration, comparing with that in higher plants. Cytoplasm viscosity changed from 1.14 into glass state only dehydration less than 60 min. Moss leaves lost plasma membrane integrity slightly, from 0.115 to 0.237, occurred simultaneously with amphiphiles partition. The results showed the more advantages of mosses than higher plants in adapting fast dehydration. We propose that EPR spin label is feasible for studying the amphiphiles partitioning mechanisms in membrane protection and damage for desiccation-tolerant mosses.     

Quantum chemical study on the abstraction reaction of alkylidenegermylene with oxirane and thiirane

The mechanisms of theion reaction of alkylidenegermylene with oxirane and thiirane have been characterized detail in using density functional theory, as well as ab initio method, including geometry optimization and vibrational analysis for the involved stationary points on the potential energy surface. Energies were calculated by CCSD(T)/6-311G(d)//B3LYP/6-311G(d,p) method for the involved conformations. The results show that the reaction pathways for both reactions consist of two ways: (1) the reactants can yield bent products (P1; P4) by syn-isomers; (2) the reactants can also yield three-membered products (P2; P5) by anti-isomers, which then further react with oxirane and thiirane to form the ultimate products (P3-1, P3-2; P6). Furthermore, a comparison with alkylidenecarbene, oxirane, and thiirane was done.     

Partial Oxidation of Methane to Synthesis Gas over Hexaaluminates LaMAl11O19-δ catalysts

A series of M-substituted hexaaluminates LaMAl11O19-δ (M=Fe, Co, Ni, Mn, and Cu)were prepared and characterized by XRD, XPS, TPR and TGA techniques, respectively. They exhibited different reducibility and catalytic activity for partial oxidation of methane (POM) to synthesis gas. Among the LaMAl11O19-δ samples, LaNiAl11O19-δ showed the best catalytic activity for the topic reaction and selectivity for synthesis gas at 780 ℃ for 2 h. The conversion of CH4 was over 99.2%, and the product selectivity for both CO and H2 was above 90.3%.     

用动态光散射跟踪钙-海藻酸水溶液凝胶化

海藻酸(alginate)是一种天然多糖,是直链键合的β-D-甘露糖醛酸(M)和α-L-古洛糖醛酸(G)的无规嵌段共聚物[1].在海藻酸水溶液中加入钙、铜、锌、铅等二价正离子,能够形成凝胶;其中钙-海藻酸凝胶在细胞输送、组织工程等领域受到人们的关注[2,3].影响海藻酸凝胶化的因素包括海藻酸的分子量和分子量分布、M/G值和序列分布、溶液浓度、正离子种类与浓度等[4,5].     

气相色谱-质谱法同时筛检人血液中26种常见毒药物

建立了气相色谱-质谱法(GC-MS)同时快速筛检人血液中26种常见毒药物的新方法.通过对样品前处理方法的摸索及GC-MS分析条件的优化,采用磷酸盐缓冲液(pH 3.5)稀释血样后,乙醚萃取,分段选择离子监测(SIM)法鉴定,并用提取离子进一步验证,可以同时检测甲胺磷、毒鼠强、地西泮、尼可刹米、利多卡因、苯巴比妥、阿托品等7大类共26种常见毒药物,回收率大部分达80%～90%,检测限为0.01 mg/L.本法用色谱保留时间、质谱特征离子同时定性,消除了血液中复杂基体的干扰,适用于中毒患者血液的应急检测.     

一种耐高温憎水聚芳醚的合成与性能初步研究

以双酚芴单体和全氟联苯为原料,通过亲核取代反应,在较低温度(120℃)下直接聚合,得到了一种高分子量的含芴部分含氟的聚芳醚,并用1H-NMR进行表征.合成的聚合物具有好的热稳定性,玻璃化温度达到271℃,5%的热失重为420℃.这些聚合物能溶于四氢呋喃、二氯甲烷、氯仿和DMAC等常见的有机溶剂,通过溶液浇注的方法制备出光滑、柔韧的膜,并利用表面接触角(CA)对膜材料的表面性能进行了表征.用氯仿制备膜的接触角为102°,而用四氢呋喃制备膜的接触角为107°,接触角接近聚四氟乙烯(112°),具有较好的憎水性.     

溶胶凝胶固定化酶流动注射化学发光法测定人体血清中的胆固醇

采用溶胶凝胶技术分别固定了胆固醇脂酶和胆固醇氧化酶,制成固定化酶柱;人体血清中胆固醇脂在胆固醇脂酶的催化作用下生成胆固醇,胆固醇在胆固醇氧化酶的催化作用下被氧化产生H2O2,将其与鲁米诺发生耦合的化学发光反应,在模拟酶血红蛋白的催化作用下产生较强的化学发光。结合流动注射技术,建立了溶胶凝胶固定化酶流动注射化学发光法测定胆固醇的新方法。实验发现,发光强度与胆固醇的浓度在一定范围内呈良好的线性关系,总胆固醇的线性范围为1.01×10-6～2.02×10-4mol/L(r=0.9975);检出限为7.5×10-7mol/L;游离胆固醇的线性范围为5.0×10-8～2.18×10-5mol/L(r=0.9991);检出限为5.0×10-9mol/L。用生化分析仪(东芝TBA-120FR)与本方法进行对照,两种方法无显著性差异。本方法已应用于临床血清样品中胆固醇的检测。