新工科项目“地方(行业)高校化学类专业应对产业变化的升级改造研究与实践”的实施

This "emerging engineering education (3E)" project "Upgrade and Practice of Chemistry-related Majors of Local and/or Specialized University Responding to the Industry Changes" was supported by the Ministry of Education. To aim at the issue of how to upgrade the chemistry-related majors of a local and/or specialized university responding to industry changes, an investigation on local regional economy and industry changes was carried out, the capability requirements of 3E for talents were analyzed, and the training objectives, graduation requirements as well as the new teaching models were also studied for the major to meet the future requirements. The practical experience for 3E construction of chemistry-related majors by selected universities was suggested.     

含长丙烯序列无规乙丙共聚物的合成与表征

用δ-TiCl₃-Et₂AlCl催化剂,以庚烷作溶剂,在单体C₃含量>60mol%的情况下,乙丙常压共聚可得到含长丙烯序列无规乙丙共聚物(LP-EPR)。其特性粘数〔η〕在2—3dl/g之间。影响〔η〕的主要因素是〔Al〕/〔Ti〕比、聚合温度和时间。共聚物的组成主要依赖单体C₃含量。通过庚烷萃取、红外、扭摆、x-射线衍射及相差显微镜等方法证明,在共聚物的无规乙丙分子链中含有全同聚丙烯(PP)序列,序列含量直接影响共聚物的结晶度、强度和硬度。     

Cr/MCM-41催化剂上的乙烯聚合行为

以纯硅ＭＣＭ４１为载体，负载Ｐｈｉｌｉｐｓ烯烃聚合催化剂活性组分Ｃｒ．ＸＲＤ及ＴＥＭ表征结果表明，所得到的Ｃｒ／ＭＣＭ４１催化剂具有良好的晶体结构和较理想的长程有序一维孔道．ＦＴＩＲ和Ｒａｍａｎ光谱表征结果表明，Ｃｒ／ＭＣＭ４１上不仅可发生乙烯聚合过程，而且形成的聚乙烯以结晶和无定形两种形态存在．乙烯聚合活性不仅与反应参数有关，而且与Ｃｒ的负载量密切相关．用于乙烯聚合后，Ｃｒ／ＭＣＭ４１催化剂仍保持其特征的晶体结构和一维孔道结构．     

小角X射线散射法研究CH2Cl2,CHCl3和CCl4对PE液晶结构的影响

采用小角X射线散射法研究了CH_2Cl_2、CHCl_3和CCl_4对磷脂酰乙醇胺(PE)液晶结构影响的机理.CH_3Cl_2、CHCl_3和CCl_4对PE液晶结构影响的差别主要是其空间旋转电子云密度分布形状不同所致.空间旋转电子云密度分布呈椭球状的物质有使PE液晶形成六角形H_1相的趋向;呈圆锥状的物质有诱发PE液晶形成立方六角相的趋向;呈球状的物质有使PE液晶形成片层立方相的趋向.     

AN ATOMIC FORCE MICROSCOPY STUDY ON THE AGGREGATION OF ISOTACTIC POLY（METHYL METHACRYLATE）

Aggregation process of isotactic poly(methyl methacrylate) (i-PMMA) has been studied extensively for many years, and considerable progress has been made in both experimental and theoretical studies. They are, however, seldom sustained by real-space observations of the underlying morphology. In this paper, the aggregation process of i-PMMA in concentrated acetone solutions and the fractal structure of the resulting three-dimensional clusters were characterized on the basis of real-space AFM observations of their two-dimensional projection. It was found that spherical multiple-chain particles formed upon collapse and aggregation of the involving chains as a whole during quenching the solution to room temperature. By keeping the solution at room temperature, the initially formed particles stick together upon contact to form larger particles through reassembling very slowly. The succeeding collision of the enlarged spherical particles leads to the formation of small clusters. These newly formed small clusters grow when they meet with other clusters or single Brownian particles. This leads to the formation of large clusters with fractal dimension of 1.95$±0.05, which suggest a reaction-limited cluster aggregation of i-PMMA in a concentrated acetone solution. This is in accordance with the conclusion obtained by light scattering measurements.     

液相色谱串联质谱法同时测定垃圾渗滤液中的邻苯二甲酸酯和烷基酚

利用反相液相色谱-电喷雾-串联质谱法同时分析了水体中的6种邻苯二甲酸酯(DMP、DEP、DBP、DEHP、DOP和DNP)以及OP、NP和BPA。用Waters XTerraTMMS C18色谱柱,乙腈和乙酸铵溶液作为梯度洗脱的流动相。结果表明,9种物质的分离效果良好,邻菲二甲酸酯采用亚离子模式检测,烷基酚采用负离子模式检测。通过多反应监测模式(MRM)对各目标物进行定量,检出限为0.1~1μg/L。该方法已用于北京某垃圾填埋场渗滤液中相关物质的检测,结果表明:原水中邻苯二甲酸酯和烷基酚的总浓度为218~291μg/L,其中主要是DEHP。垃圾渗滤液处理工艺对这些物质有明显的去除效果。     

Regiochemistry in radical cyclization of allenes

The cyclization of allenic radicals was systematically studied for the first time by computational methods. It was found that the theoretical results at the ONIOM(QCISD(T)/6-311+G(2df,2p):UB3LYP/6-311+G(2df,2p)) level were in good agreement with all the available experimental data. For the cyclization of penta-3,4-dien-1-yl radicals the major product was penta-1,2-diene from direct reduction whereas a small amount of vinylcyclopropane may also be produced. For the cyclization of hexa-4,5-dien-1-yl radicals the major product is 1-methyl-cyclopentene. Furthermore, for the cyclization of hepta-5,6-dien-1-yl radicals both vinylcyclopentane and 1-methyl-cyclohexene are produced. Marcus theory analysis indicated that the formation of an olefinic radical product always had a lower intrinsic energy barrier than the formation of an allylic radical product. On the other hand, the formation of an olefinic radical product was always much less favorable than the formation of an allylic radical product in the thermodynamic term. For the cyclization of substituted hexa-4,5-dien-1-yl radicals, substitution at the allene moiety does not affect the regioselectivity where the allylic radical product is always favored. For the cyclization of hepta-5,6-dien-1-yl radicals, substitution at the allene moiety dramatically affects the regioselectivity, where some radical-stabilizing groups such as -CN and -COMe may even completely reserve the regioselectivity.     

PSF/TiO2杂化超滤膜形成过程的热力学和动力学研究

采用溶胶-凝胶法制备了不同纳米TiO₂含量的聚砜(PSF)/TiO₂杂化超滤膜, 研究了TiO₂浓度对聚砜铸膜液流变学及热力学性质的影响, 构建了计算成膜过程中表观扩散系数(D_a)的新方法, 求出不同TiO₂浓度及温度下的D_a值, 进而剖析了铸膜液流变学和热力学性质的变化对成膜动力学的影响. 并通过扫描电镜观察、杂化膜孔隙率和超滤性能的测试考察了表观扩散系数与膜结构和性能的关系. 结果表明, 加入TiO₂溶胶的PSF铸膜液由牛顿流体转变为非牛顿流体, 其粘度随TiO₂浓度增大而增大. TiO₂的加入减小了铸膜液对非溶剂的容纳能力, 加速铸膜液的液-液相分离, 同时TiO₂引起的热力学促进作用和流变学阻碍作用相互竞争, 共同影响D_a的变化. 实验得出, D_a随温度升高而增大, 随TiO₂浓度的增大有先增大后减小的趋势. 表观扩散系数D_a与膜的结构和性能具有很好的相关性并能直观地描述整个成膜过程.     

超高效液相色谱法同时测定蜂胶中的12种活性成分

采用超高效液相色谱法同时测定了蜂胶中类黄酮、阿魏酸、咖啡酸苯乙酯等12种活性成分。蜂胶样品用甲醇稀释,超声波提取,样液过滤后以Acquity BEH C18柱(100 mm×2.1 mm,1.7 μm)为分离柱,0.4%磷酸水溶液和甲醇为流动相,梯度洗脱,采用二极管阵列检测器检测。整个分离过程在9.5 min内完成。以加标蜂胶样品做添加回收测定,12种化合物的回收率为90.1%～104.3%,相对标准偏差为2.12%～4.90%。该方法为评价蜂胶质量提供了一种新的检测方法,已应用于实际蜂胶样品的测定。     

固体酸催化合成4-羟基苯基-1''''-O-D-吡喃葡萄糖苷

报道了一种简便易行的绿色合成4-羟基苯基-1'-O-D-吡喃葡萄糖苷(即熊果苷及其端基异构体)新方法,采用固体酸蒙脱石K-10或4A分子筛为催化剂,将四苄基保护的葡萄糖(2)或α-三氯乙酰亚胺酯糖给体(3)与氢醌直接进行糖基化反应,最高以86%的产率获得4-羟基苯基12',3',4',6'-四-O-苄基-1'-O-D-吡喃葡萄糖苷(4),进而脱除苄基保护,定量获得熊果苷及其端基异构体(1).中间体(4)的结构经IR、MS、1H NMR及元素分析等测试技术进行了确认,化合物(1)的理化数据与文献值相同.