Surface structure and reactivity study of phosphotungstic acid-nitrogenated ormosils

Supramolecular interactions between nitrogenated groups in hybrid ormosils bearing phosphotungstate nanocatalyst were used to tune the photocatalytical activity of these class-II hybrid materials obtained through sol–gel chemistry. Surface chemistry and morphology of the materials was studied by scanning electron microscopy, atomic force microscopy, X-ray photoelectron spectroscopy and water contact angle measurements. The photocatalytic efficiency of these hybrid films, measured by the degradation of crystal violet over-layer deposited on ormosils films, is higher for ormosils bearing neutral, more polar and less H-bonding nitrile groups than those bearing alkylamine/alkylammonium functionalities, despite the lower W/Si atomic ratio on the surface and lower tungsten percentage of the pure nitrile bearing ormosils. Such higher surface reactivity of the nitrile bearing ormosils is due to weaker interaction with the phosphotungstate and the lower activity of amine bearing ormosils is attributed to the competition among reversible photochromism and photocatalysis pathways in these materials.     

三核欠完整立方烷金属原子簇二阶非线性光学性质的理论研究

研究了具有欠完整立方烷构型的过渡金属原子簇分子的二阶非线性光学性质。利用TDDFT方法计算了选取的簇分子及相应模拟构造分子的静态和动态的一阶非线性光学超级化率(ijk);并计算了不同金属、桥原子和配体以及簇芯对该类化合物一阶超级化率的影响。选取其中的一个簇分子为基本模型,分析了该分子的电子结构和分子轨道,在微观水平上阐述了其非线性光学性质的可能起源。认为由过渡金属和硫原子组成的簇芯和与桥原子相连的配体对该类簇合物的二阶非线性光学性质的起决定性的作用。     

Ultra-incompressible Ternary Diborides Re_（0.5）Ir_（0.5）B_2,Re_（0.5）Tc_（0.5）B_2,Os_（0.5）W_（0.5）B_2 and Os_（0.5）Ru_（0.5）B_2：Density Functional Calculation

In this paper, density functional computations have been applied to the structural, elastic and electronic properties of ternary transition metal diborides Re0.5Ir0.5B2, Re0.5Tc0.5B2, Os0.5W0.5B2 and Os0.5Ru0.5B2 in hexagonal (P63/mmc) and orthorhombic (Pmmn) structures with both local density approximation and generalized gradient approximation. LDA gives smaller lattice parameters and larger elastic moduli than GGA. Both results show that the hexagonal ones are more stable than orthorhombic ones except Os0.5Ru0.5B2. Moreover, the hexagonal structure has superior elastic property than orthorhombic one. Generally speaking, the calculated elastic moduli of Re0.5Ir0.5B2 and Os0.5Ru0.5B2 are smaller than those values of Re0.5Tc0.5B2 and Os0.5W0.5B2 within the same structure because of the filling of antibonding states. The relativistic effects result in weaker bonds of Tc-B (Ru-B) than those of Re-B (Os-B). All the diborides are ultra-incompressible. Re0.5Tc0.5B2 has the largest shear modulus and it is a promising superhard diboride like Os0.5W0.5B2. The elastic properties are in high correlation with the bond strength. The shear moduli are more sensitive than the bulk moduli to the bond strength.     

酶促开环聚合合成双亲性H型嵌段共聚物及其自组装

通过固定化酶Novozyme435（NV435）催化聚乙二醇（PEG）开环聚合己内酯（CL）得到端基带有羟基的ABA型三嵌段聚合物,用2,2-二氯代乙酰氯将聚合物的端羟基功能化形成H型大分子引发剂,在CuCl／HMTETA体系中引发4-乙烯基吡啶（4VP）进行原子转移自由基聚合反应（ATRP）,得到了具有两亲性的H型五嵌段聚合物（PVP）2-b—PCL-b．PEG-PCL-（PVP）2,用红外光谱（FT IR）,核磁共振（^1H NMR）,凝胶渗透色谱（GPC）对其结构与分子量及其分子量分布进行了表征,结果表明：H型五嵌段聚合物分子量46121g／mol,分子量分布1．30．并利用动态光散射（DLS）和原子力显微镜（AFM）对聚合物在水溶液中的自组装行为进行了研究,H型嵌段聚合物的胶束呈球形结构,平均直径为70nm左右．     

TDDFT Study on the Electronic Excitations and First Hyperpolarizabilities of Mixed-metal Carbonyl Clusters W2Ir2（μ-L）（CO）8（η^5-C5H4Me）2（L = dppe/dppf）

Mixed-metal carbonyl clusters of W2Ir2（CO）10（η^5-C5H4Me）2 1 and W2Ir2（μ-L）（CO）8（η^5-C5H4Me）2 （L = dppe 2, dppf 3） have been studied by TDDFT method focusing on their electronic and nonlinear optical properties. These three clusters exhibit the first static hyperpolarizabilities of medium magnitude （βtot-10×10^-30 esu）. The origin of β is discussed by the new proposed orbital-pair decomposition scheme by Barandes et al. The result suggests that the β values of the two clusters are mainly originated from d-d electron transition within the metal skeleton, and d-p （π＊） electron transition from metals to carbonyls and phenyl. The additional coordination by the electron donor group, ferrocene, makes cluster 3 own much larger β values, and the relatively longer range charge transfer from d orbitals of ferrocene to d orbirals of Ir and W is responsible for the enhanced β values.     

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.     

Photophysical Methods for the Study of Sol-Gel Transition and Structure of Titania Gels

The sol to gel evolution of titania based systems in AOT (sodium 2-etil-hexil sulfosuccinate) reverse micelles is monitored by the fluorescence anisotropy of molecular probes located in the different phases of the system. In contrast with processes in homogeneous systems, hydrolysis and condensation reactions occur in different time windows. The obtained results allow to describe the location of the hydrolysis, the reorganisation of the surfactant and to predict the formation of precipitates.     

Net Charge Fluctuation and String Fragmentation

We present the simulation results of the net charge fluctuation in Au Au collisions at /Snn=130 GeV froma dynamic model, JPCIAE, and its revisions. The simulations are done for the quark-gluon matter, the directly producedpions, the pion matter, and the hadron matter. The simulated net charge fluctuation of the quark-gluon matter is closeto the thermal model prediction for the quark-gluon gas. However, the discrepancy exists comparing the simulated netcharge fluctuation for directly produced pions and the pion matter with the thermal model prediction for pion gas andthe resonance pion gas, respectively. The net charge fluctuation of hadron matter from default JPCIAE simulations isnearly 3.5 times larger than quark-gluon matter. A discussion is given for the net charge fluctuation as an evidence ofQGP phase transition.     

Stability of Runge-Kutta methods for delay differential systems with multiple delays

The stability of Runge-Kutta methods for systems of delay differentialequations (DDEs) with multiple delays is considered. The stabilityregions of explicit and implicit Runge-Kutta methods are discussedwhen they are applied to asymptotically stable linear DDEs withmultiple delays. A simple estimate on the stability regionsof explicit Runge-Kutta methods is presented. It is shown thatthe stable step-size for numerical integration of DDEs withmultiple delays can be easily selected by means of the estimate.