高校实验室安全教育在线资源调查研究*

对国内高校实验室安全教育在线资源现状进行调研。调查结果表明:在线资源主要有慕课、虚拟仿真实验及安全教育考试系统。因此,在安全教育过程中,可充分利用现有线上资源,弥补线下教学因时间有限、容量有限导致的不足,从而提高安全教育实效。线上、线下安全教育如何有机结合从而最大限度地发挥其在高校安全教育中的作用,仍需不断探索。     

End‐Functionalized Palladium SCS Pincer Polymers via Controlled Radical Polymerizations

A direct and facile route toward semitelechelic polymers, end‐functionalized with palladated sulfur–carbon–sulfur pincer (Pd^II‐pincer) complexes is reported that avoids any post‐polymerization step. Key to our methodology is the combination of reversible addition‐fragmentation chain‐transfer (RAFT) polymerization with functionalized chain‐transfer agents. This strategy yields Pd end‐group‐functionalized materials with monomodal molar mass dispersities (Đ ) of 1.18–1.44. The RAFT polymerization is investigated using a Pd^II‐pincer chain‐transfer agent for three classes of monomers: styrene, tert‐butyl acrylate, and N‐isopropylacrylamide. The ensuing Pd^II‐pincer end‐functionalized polymers are analyzed using ¹H NMR spectroscopy, gel‐permeation chromatography, and elemental analysis. The RAFT polymerization methodology provides a direct pathway for the fabrication of Pd^II‐pincer functionalized polymers with complete end‐group functionalization.

     

Metal‐Folded Single‐Chain Nanoparticle: Nanoclusters and Self‐Assembled Reduction‐Responsive Sub‐5‐nm Discrete Subdomains

Easy access to discrete nanoclusters in metal‐folded single‐chain nanoparticles (metal‐SCNPs) and independent ultrafine sudomains in the assemblies via coordination‐driven self‐assembly of hydrophilic copolymer containing 9% imidazole groups is reported herein. ¹H NMR, dynamic light scattering, and NMR diffusion‐ordered spectroscopy results demonstrate self‐assembly into metal‐SCNPs (>70% imidazole‐units folded) by neutralization in the presence of Cu(II) in water to pH 4.6. Further neutralization induces self‐assembly of metal‐SCNPs (pH 4.6–5.0) and shrinkage (pH 5.0–5.6), with concurrent restraining residual imidazole motifs and hydrophilic segment, which organized into constant nanoparticles over pH 5.6–7.5. Atomic force microscopy results evidence discrete 1.2 nm nanoclusters and sub‐5‐nm subdomains in metal‐SCNP and assembled nanoparticle. Reduction of metal center using sodium ascorbate induces structural rearrangement to one order lower than the precursor. Enzyme mimic catalysis required media‐tunable discrete ultrafine interiors in metal‐SCNPs and assemblies have hence been achieved.     

基于杂交链式反应辅助多重信号放大的端粒酶灵敏检测

端粒酶是真核细胞维持端粒长度的关键逆转录酶,其生物活性的高低可以为多种癌症的临床诊断和预后治疗提供有价值的信息.本研究以人宫颈癌细胞(HeLa细胞)裂解液中的端粒酶为研究对象,通过借助杂交链式反应辅助多重信号放大策略,提出了一种新颖、灵敏的检测端粒酶电化学方法.首先将端粒酶的延伸引物自组装在金电极表面,当端粒酶存在时,端粒酶能够催化引物的延伸,产生与发卡环探针H1部分互补的序列,进而引发杂交链式反应,形成由两个发卡环探针(H1和H2)交替杂交而形成的DNA长链.由于H1和H2末端均修饰有生物素,加入链霉亲和素修饰辣根过氧化物酶后,辣根过氧化物酶被被连接到电极表面,催化邻苯二胺氧化生成2,3-二氨基吩嗪,产生显著的电化学信号.实验结果表明,本研究建立的端粒酶电化学检测方法高效、可行,线性范围宽,灵敏度高,可以检测每毫升10个HeLa细胞裂解液中的端粒酶.本方法具有较好的选择性,能有效区分端粒酶和对照蛋白.     

Catalytic chain transfer polymerization of isobutylene: The role of nucleophilic impurities

Fast polymerization of isobutylene (IB) initiated by tert‐butyl chloride using ethylaluminum dichloride·bis(2‐chloroethyl) ether complex (T. Rajasekhar, J. Emert, R. Faust, Polym. Chem. 2017, 8, 2852) was drastically slowed down in the presence of impurities, such as propionic acid, acetone, methanol, and acetonitrile. The effect of impurities on the polymerization rate was neutralized by using two different approaches. First, addition of a small amount of iron trichloride (FeCl₃) scavenged the impurity and formed an insoluble · impurity complex in hexanes. The polymerization rate and exo‐olefin content were virtually identical to that obtained in the absence of impurities. Heterogeneous phase scavenger (FeCl₃) exhibited better performance than homogenous phase scavengers. In the second approach, conducting the polymerization in wet hexanes, the fast polymerization of IB was retained in the presence of impurities with a slight decrease in exo‐olefin content. ¹H NMR studies suggest that nucleophilic impurities are protonated in the presence of water, and thereby neutralized. Mechanistic studies suggest that the rate constant of activation (k_a), rate constant of propagation (k_p), and rate constant of β‐proton elimination (k_tr) are not affected by the presence of impurities. To account for the retardation of polymerization in the presence of impurities, delay of proton transfer to monomer in the chain transfer step is proposed. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3697–3704     

Effect of chain structure on the glass transition temperature and viscoelastic property of cis‐1,4‐polybutadiene via molecular simulation

In this work, by adopting the united atom model of cis‐1,4‐poly(butadiene) (PB), we systemically investigate the effect of the chain structure on the glass transition temperature (T_g) and the viscoelastic property of PB system. First, we analyze the atom translational mobility, bond reorientation dynamics, torsional dynamics, conformational transition rate, and dynamic heterogeneity of the PB chains with different chain structures in detail by determining the corresponding T_g. In addition, our results clearly indicate that with the decrease of the amount of the free end atoms of PB via the end‐linking method, the mobility of the PB chains quickly decreases. As a result, the T_g of the PB chains gradually increases. Depending on the chain structure and the calculation method, the T_g of the PB chains varies from 154 to 240 K. In addition, the temperature dependence of the dynamic properties has different Arrhenius behaviors above and below T_g. The calculated activation energy varies from 7.37 to 16.37 KJ/mol for different chain structures above T_g, which can be compared with those for other polymers. In addition, through the end‐linking approach the strong interaction between the PB chains improves the storage modulus G′ and the loss modulus . Meanwhile, the immobility of the free end atoms effectively reduces the friction loss of the chains under the shear field, which is reflected by the low loss factor . In summary, this work can further help to understand the effect of the chain structure on the dynamic properties of the PB chains. Meanwhile, it provides an effective approach to reduce the energy loss during the dynamic periodic deformation, which can cut the fuel consumption via the end‐linking method. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1005–1016     

浙江大学基础化学实验研究生助教的实践和探索

研究生助教是对研究生自身能力的培养和锻炼,同时也补充了本科教学教师资源。提高本科教学的质量,需要加强对研究生助教的培训、指导、管理和考评,也需要加强课程教学的统一规范管理,加强对学生学习的督促和引导。本文探讨了基础化学实验研究生助教的教学经验,并对今后实验教学管理以及研究生助教的培养等提出一些思考和建议。     

不确定需求与产出供应链回购契约决策

针对市场需求的不确定性和供应商产出产品合格率的不确定性,提出供应商产出量小于销售商订购量时需再生产满足销售商的订购,以及供应商生产过量和回购的产品通过折扣市场出售,建立以供应链期望利润为目标函数,以回购单价为决策变量的供应链回购契约决策模型.通过模型的分析,证明了模型存在最优的期望利润,给出了最优回购单价满足的方程;同时,也证明了最优订购量,最优生产量和销售商最优期望利润是回购单价的增函数.最后,通过算例验证了模型的有效性.     

基于严格α-双链对角占优矩阵的非奇H-矩阵的判定准则

研究了非奇H-矩阵的判定问题.先给出了几个判定严格α-双链对角占优矩阵的充要条件,进一步利用矩阵对角占优理论得到了判定非奇H-矩阵的一些充分条件,推广和改进了已有的相关结果,并用数值算例说明了这些判定方法的有效性.