酶促聚合与ATRP结合合成聚己内酯和聚N,N-二甲氨基甲基丙烯酸乙酯嵌段共聚物及其自组装

摘要：用化学酶法合成聚己内酯（PCL）和聚N,N-二甲氨基甲基丙烯酸乙酯（PDMAEMA）双亲嵌段聚合物（PCL-b-PDMAEMA）。通过核磁共振（1H NMR）,红外光谱仪(FTIR-IR),凝胶渗透色谱(GPC) 对其结构以及分子量与其分子量分布情况进行了表征。对聚合物的溶液性质进行了研究,结果表明：临界胶束浓度（CMC）嵌段聚合物中疏水链段增多有利于形成胶束,表现为CMC降低,并具有较高的热力学稳定性。PDMAEMA是PH和温度敏感材料,研究发现,在不同的温度和pH值条件下表现不同的聚集状态, 当聚合物的pH值降低时平均流体力学直径增加,温度升高平均流体力学直径降低。     

Electronic structure and acid–base properties of Kojic acid and its dimers. A DFT and quantum topology study

Kojic acid is a polyfunctional heterocyclic compound, with several important reaction centres; it has a wide range of applications in the cosmetic, medicine, food, agriculture and chemical industries. The present study aims at better insight into its electronic structure and bonding characteristics. Thus, density functional theory at the M06-2x /6-311++G^** level of theory is used to investigate its ground state electronic and acid–base properties. Protonation and deprotonation enthalpies are computed and analysed. The ability of Kojic acid to form both water complexes and dimers is explored. Several different complexes and dimer structures were examined. Natural bond order and quantum topology features of the charge density were analysed. The origin of the stability of the studied complexes and dimer structures can be traced to hydrogen bonding, π-conjugative and non-covalent dispersive interactions.     

Coupling of mixed finite elements and boundary elements

The symmetric coupling of mixed finite element and boundaryelement methods is analysed for a model interface problem withthe Laplacian. The coupling involves a further continuous ansatzfunction on the interface to link the discontinuous displacementfield to the necessarily continuous boundary ansatz function.Quasi-optimal a priori error estimates and sharp a posteriorierror estimates are established which justify adaptive mesh-refiningalgorithms. Numerical experiments prove the adaptive couplingas an efficient tool for the numerical treatment of transmissionproblems.     

过渡金属类立方烷原子簇化合物电子结构和二阶非线性光学性质的密度泛函理论研究

采用基于第一原理的含时密度泛函理论(TDDFT)对一系列具有类立方烷簇芯结构的过渡金属簇合物二阶非线性光学性质进行了研究。结果证明, 由于簇芯结构的对称性的影响, 这一类簇分子的二阶非线性光学系数的数值要小于三核欠完整类立方烷体系。通过对电子结构的分析, 发现二阶非线性光学性质主要是由簇芯内电荷的迁移造成的。轨道分析显示, -S原子对于电荷的迁移起主要的传递作用。定域化轨道分析证明簇分子中存在的多中心键有利于簇芯内电荷的迁移。分子模拟的研究表明:虽然类立方烷结构簇分子的值比较小, 但是通过合理的配体设计, 获得具有较大值非线性光学晶体是可能的。     

A note on maximizing the permanent of a positive definite hermitian matrix,given the eigenvalues ∗

As a step toward understanding the unsolved problem of determining how large the permanent of a positive semi-definite matrix can be, given the eigenvalues, we note that a necessary condition for A to be a permanent maximizing matrix is that A commute with its permanental adjoint.     

Theoretical Studies on the First Hyperpolarizabilities of One-dimensional Donor-bridge-acceptor Chromophores and New Applications of BLA in Determining Molecular First Hyperpolarizabilities

We present a quantum-chemical analysis of the relationship between the bond length alteration （BLA） and the static first hyperpolarizability of a series of one-dimensional （1D） chromophores with donor-bridge-acceptor （D-B-A） structures. The calculated results show that the parameter BLA can be considered as an indicator to evaluate the molecular first hyper- polarizability. Along the direction of molecular ground-state dipole moments, the evolutions of BLA can be classified into three categories： the first is a non-monotonic line, which represents most chromophores; the second is monotonic increasing; and the third, contrarily, is monotonic decreasing. On the whole, the first hyperpolarizabilities of these studied chromophores are the monotonic functions of BLA along the direction of dipole moments. Therefore, the first hyperpolarizability of these 1D chromophores can be preliminarily evaluated in terms of the development of BLA without a rigorous computation. In other words, one can roughly estimate the relative magnitude of the first hyperpolarizability according to the optimized geometry.     

Theoretical Studies on the Binding of Cd~（2＋） to Uracil and Its Thio-derivatives

The interaction of Cd2+ with uracil,2-thiouracil,4-thiouracil and 2,4-dithiouracil have been investigated by the density functional theory(DFT) calculations.For uracil and 2,4-dithiouracil,where the two basic sites are the same,Cd2+ attachment to the heteroatom at position 4 is preferred.However,for the systems where both types of basic centers,a carbonyl and a thiocarbonyl groups,are present,Cd2+ association with sulfur is favorable.The enhanced stability of these enolic and thiol forms comes from Cd2+ interaction with two basic sites simultaneously,which thereby triggers a significant aromatization of the ring.More significantly,the Cd2+ binding energy with uracil and its thio-derivatives is larger than the tautomerization barriers connecting the diketo-like forms with the corresponding enolic-like tautomers.Consequently,when associated with Cd2+,all tautomers are energetically accessible and should be observed in the gas phase.