Stereoselective polymerization of rac-lactide using a monoethylaluminum Schiff base complex

A monoethylaluminum Schiff base complex (2) with formula LA1Et (L = N,N'-(2,2-dimethylpropylene)bis(3,5-di-tei-t-butylsalicylideneimine) was synthesized and employed for the stercoselective ring-opening polymerization of rac-lactide (rac-LA). The complex 2 was characterized by nuclear magnetic resonance, crystal structure, and elemental analysis. It contains a five-coordinate aluminum atom with distorted trigonal bipyramidal geornetry in the solid state. In the presence of 2-propanol, 2 showed high stereoselectivity for the polymerization of rac-LA. The polymerization yielded crystalline poly(rac-LA) with a high melting temperature (193-201 degreesC). NMR, differential scanning calorimetry, and wide-angle X-ray diffraction indicated that the poly(rac-LA) was highly isotactic, and a stereocomplex was formed between poly-L- and poly-D-lactide block sequences. By the analysis of electrospray-ionization mass spectrometry and H-1 NMR, the polymer was demonstrated to be endcapped in both terminals with an isopropyl ester and a hydroxy group, respectively. The polymerization was of first order in rac-LA concentration. The relationship between the rac-LA conversion and molecular weights of the polymer was linear so that the polymerization could be well controlled.

Kinetics of cerium(IV) extraction with DEHEHP from HNO3-HF medium using a constant interfacial cell with laminar flow

Studies of the extraction kinetics of cerium(IV) into n-heptane solutions of di(2-ethylhexyl)-2-ethylhexyl phosphonate DEHEHP from HNO3-HF solutions have been carried out using a constant interfacial cell with laminar flow. The experimental hydrodynamic conditions were chosen so that the contribution of diffusion to the measured rate of reaction was minimized. The data were analyzed in terms of pseudo-first order constants. The effects of the stirring rate, specific interfacial area, and temperature on the extraction rate showed that the most probable reaction zone is in the aqueous homogeneous phase. The results were compared with those of the system without HF. It was concluded that the presence of HF decreases the extraction rate of cerium. The addition of HF increases the activation energy for the forward reaction from 21.2 to 55.3 kJ/mol and for the reverse process from 57.9 to 79.0 kJ/mol. According to the experimental data correlated as a function of the concentration of the relevant species involved in the extraction reaction, the corresponding rate equation was deduced as follows:-d[Ce]/dt = k[Ce] center dot B-0.62 center dot HF-0.58 center dot [NO3-](0.57)

Assembly of the transition metal substituted polyoxometalates ZnW11M(H2O)O-39(n-) (M = Mn, Cu, Fe, Co, Cr, Ni, Zn) on 4-aminobenzoic acid modified glassy carbon electrode and their electrochemical study

Through layer-by-layer assembly, a series of undecatungstozincates monosubstituted by first-row transition metals, ZnW11M(H2O)O-39(n-) (M=Cr, Mn, Fe, Co, Ni, Cu. or Zn) were first successfully immobilized on a 4-aminobenzoic acid modified glassy carbon electrode surface. The electrochemical behaviors of these polyoxometalates were investigated. They exhibit some special properties in the films different from those in homogeneous aqueous solution. The Cu-centered reaction mechanism in the ZnW11Cu multilayer film was described. The electrocatalytic behaviors of these multilayer film electrodes to the reduction of H2O2 and BrO3- were comparatively studied.

Kinetics of cerium(IV) extraction from H2SO4-HF medium with Cyanex 923

Studies of the extraction kinetics of cerium(IV) from H2SO4-HF solutions with Cyanex 923 in n-heptane have been carried out using a constant interfacial area cell with laminar flow. The experimental hydrodynamic conditions were chosen so that the contribution of diffusion to the measured rate of reaction was minimized. The data were analyzed in terms of pseudo-first order constants. The results were compared with those of the system without HF. It was concluded that the addition of HF reduces the activation energy for the forward rate from 46.2 to 36.5 U mol(-1) while it has an opposite effect on the activation energy for the reverse process(the activation energy increased from 23.3 to 90.8 U mol(-1)). Thus, HF can accelerate the rate of cerium(IV) extraction. At the same time, the extraction rate is controlled by a mixed chemical reaction-diffusion rather than by a chemical reaction alone. A rate equation has also been obtained.

Formation of a metastable phase induced by a liquid crystalline phase in a novel chloropoly(aryl ether ketone)

The phase transition behavior of a thermotropic liquid crystalline poly(aryl ether ketone) synthesized by nucleophilic substitution reactions of 4,4'-biphenol (BP), and chlorohydroquinone (CH) with 1,4-bis(4-fluorobenzoyl)benzene (BF) has been investigated by differential scanning calorimetry (DSC) and wide angle X-ray diffraction (WAXD). The copolymer exhibits multiple first order phase transitions, which are associated with crystal-to-smectic liquid crystal transition and smectic liquid crystal-to-isotropic transition. When the cooling rate is low (<10C/min), only stable crystal from I is formed. With the cooling rate being high (>20 degreesC/min), the metastable crystal form II is formed, which always coexists with form I. The liquid crystalline phase plays an important role in the formation of metastable phase form II.

Influence of temperature on lattice spacings of melt-crystallized poly(iminosebacoyl iminodecamethylene)

The variation of lattice spacings of poly(iminosebacoyl iminodecamethylene) (nylon-10,10) with temperature was studied by wide-angle X-ray diffraction (WAXD) during both heating and cooling processes, which demonstrates a gradual and continuous transition with temperature. However, the crystal melts before the two peaks merge completely. Both WAXD and differential scanning calorimetry show that crystallization from molten sample results directly in the triclinic form. Additionally, this transition is thermodynamically reversible. Comparison of this transition with that of nylon-6,6, suggests that no hydrogen-bonded network is formed during or after the transition. We prefer to attribute this transition to asymmetrical thermal expansion in the nylon-10,10 crystals rather than to a true first-order phase transition. (C) 2001 Society of Chemical Industry.

Stereospecific polymerization of styrene using a homogeneous lanthanide catalyst

Stereospecific polymerization of styrene was catalyzed by homogeneous neodymium phosphonate [Nd(P-507)(3)]-H2O-Al(i-Bu)(3) catalytic system. The polymer was separated into isotactic polystyrene and atactic polystyrene by extracting the latter with boiling 2-butanone. The conversion of styrene and the yield of isotactic polystyrene (IY) were influenced by the [H2O]/[Al(i-Bu)(3)] mole ratio and the solvent polarity. The reaction is first order with respect to monomer at 70 degrees C.

Determination of Rate Constants of Catalytic Reaction by Spectroelectrochemistry with Microelectrodes

The at constants of catalytic reaction of ferrocyanide ascorbic acid and ferro cyanide histidine system were determined by transmitted spectroelectrochemistry using a group of cyclindrical microelectrodes, It is the first time to find that the reaction can still be considered as the pseudo first order reaction when tilt concentration of ascorbic acid or histidine is close to and even slightly lower than the concentration of ferrocyanide. The determined rate constants are in agreement with the reported values, A reasonable explanation was given,

SPECTROELECTROCHEMISTRY WITH CYLINDRICAL CARBON-FIBER MICROELECTRODES

Transmittance spectroelectrochemistry can be performed using a group of cylindrical microelectrodes. A dependence of absorbance on electrolytic charge during the potential step was derived. The rate constant of catalytic reaction of the ferrocyanide-ascorbic acid system was determined using single potential step-open circuit relaxation chronoabsorptometry. This is the first report that the reaction can still be considered as a pseudo-first-order reaction when the concentration of ascorbic acid is close to and even slightly lower than the concentration of ferrocyanide. The determined rate constant is in agreement with the reported value. The reason is that the diffusion of ascorbic acid toward electrode surface is contractive and the diffusion of the electrogenerated ferricyanide from the electrode surface to the bulk of solution is expansive.

Representation of microscale ocean wavenumber spectrum correct to the second order

In this paper, the analytical representations of four wave source functions in high-frequency spectrum range are given on the basis of ocean wave theory and dimensional analysis, and the perturbation method is used to solve the governing equations of ocean wave high-frequency spectrum on the basis of the temporally stationary and locally homogeneous scale relations of microscale wave. The microscale ocean wavenumber spectrum correct to the second order has an explicit structure, its first order part represents the equilibrium between different source functions, and its second order part represents the contribution of microscale wave propagation.

随机系统辨识在电力系统负荷预报中的应用

本文将随机系统状态模型辨识技术用于电力系统负荷预报。首先根据负荷的一系列历史数据建立负荷的状态空间模型,然后用滤波算法进行次日负荷预报,最后用电网实际数据在 PDP-11/23计算机上进行预报计算,得到比较满意的结果。

地震波模拟：非规则网格离散的数值解法、吸收边界及其实际应用

This dissertation presents a series of irregular-grid based numerical technique for modeling seismic wave propagation in heterogeneous media. The study involves the generation of the irregular numerical mesh corresponding to the irregular grid scheme, the discretized version of motion equations under the unstructured mesh, and irregular-grid absorbing boundary conditions. The resulting numerical technique has been used in generating the synthetic data sets on the realistic complex geologic models that can examine the migration schemes. The motion equation discretization and modeling are based on Grid Method. The key idea is to use the integral equilibrium principle to replace the operator at each grid in Finite Difference scheme and variational formulation in Finite Element Method. The irregular grids of complex geologic model is generated by the Paving Method, which allow varying grid spacing according to meshing constraints. The grids have great quality at domain boundaries and contain equal quantities of nodes at interfaces, which avoids the interpolation of parameters and variables. The irregular grid absorbing boundary conditions is developed by extending the Perfectly Matched Layer method to the rotated local coordinates. The splitted PML equations of the first-order system is derived by using integral equilibrium principle. The proposed scheme can build PML boundary of arbitrary geometry in the computational domain, avoiding the special treatment at corners in a standard PML method and saving considerable memory and computation cost. The numerical implementation demonstrates the desired qualities of irregular grid based modeling technique. In particular, (1) smaller memory requirements and computational time are needed by changing the grid spacing according to local velocity; (2) Arbitrary surfaces and interface topographies are described accurately, thus removing the artificial reflection resulting from the stair approximation of the curved or dipping interfaces; (3) computational domain is significantly reduced by flexibly building the curved artificial boundaries using the irregular-grid absorbing boundary conditions. The proposed irregular grid approach is apply to reverse time migration as the extrapolation algorithm. It can discretize the smoothed velocity model by irregular grid of variable scale, which contributes to reduce the computation cost. The topography. It can also handle data set of arbitrary topography and no field correction is needed.

旋转轴对称介质中的qP波一阶射线追踪

Elastic anisotropy is a very common phenomenon in the Earth’s interior, especial for sedimentary rock as important gas and oil reservoirs. But in the processing and interpretation of seismic data, it is assumption that the media in the Earth’s interior is completely elastic and isotropic, and then the methods based on isotropy are used to deal with anisotropic seismic data, so it makes the seismic resolution lower and the error on images is caused. The research on seismic wave simulation technology can improve our understanding on the rules of seismic wave propagation in anisotropic media, and it can help us to resolve problems caused by anisotropy of media in the processing and interpretation of seismic data. So researching on weakly anisotropic media with rotated axis of symmetry, we study systematically the rules of seismic wave propagation in this kind of media, simulate the process with numerical calculation, and get the better research results. The first-order ray tracing (FORT) formulas of qP wave derived can adapt to every anisotropic media with arbitrary symmetry. The equations are considerably simpler than the exact ray tracing equations. The equations allow qP waves to be treated independently from qS waves, just as in isotropic media. They simplify considerably in media with higher symmetry anisotropy. In isotropic media, they reduce to the exact ray tracing equations. In contrast to other perturbation techniques used to trace rays in weakly anisotropic media, our approach does not require calculation of reference rays in a reference isotropic medium. The FORT-method rays are obtained directly. They are computationally more effective than standard ray tracing equations. Moreover the second-order travel time corrections formula derived can be used to reduce effectively the travel time error, and improve the accuracy of travel time calculation. The tensor transformation equations of weak-anisotropy parameters in media with rotated axis of symmetry derived from the Bond transformation equations resolve effectively the problems of coordinate transformation caused by the difference between global system of coordinate and local system of coordinate. The calculated weak-anisotropy parameters are completely suitable to the first-order ray tracing used in this paper, and their forms are simpler than those from the Bond transformation. In the numerical simulation on ray tracing, we use the travel time table calculation method that the locations of the grids in the ray beam are determined, then the travel times of the grids are obtained by the reversed distance interpolation. We get better calculation efficiency and accuracy by this method. Finally we verify the validity and adaptability of this method used in this paper with numerical simulations for the rotated TI model with anisotropy of about 8% and the rotated ORTHO model with anisotropy of about 20%. The results indicate that this method has better accuracy for both media with different types and different anisotropic strength. Keywords: weak-anisotropy, numerical simulation, ray tracing equation, travel time, inhomogeneity

喜马拉雅西构造结区岩石圈演化三维有限元动力学数值模拟

The past three decades have seen numerous attempts to numerically model stress and strain patterns in the lithosphere of the Earth on both global and regional scales. This efforts have been indispensable in identifying the features we need to include in our endeavour to develop better models of our planet’s lithosphere and they have also raised our awareness for the many unresolved issue in the deep geodynamical issues that need to be addressed in the future. Nonetheless, in most models, the lithosphere is treated as a single layer with depth-averaged properties, and as the same distribution in the stress and strain fields, and as deforming under plane strain. All these above make a great hander for its reality and degree of recognition. As the beginning in this paper, some principal numerical models and results on the evolution of Tibetan plateau are reviewed and analyzed. Then, the geological and geophysical expedition on the Western Himalayan Syntaxis is briefly reviewed. Furthermore, we analysis the feature in deep geophysical field studies in this area and adjacent regions. Because, for most continents, stress models driven by plate boundary forces have successfully reproduced the main characteristics of the stress and strain field, we present a set of three-dimensional models of lithosphere system for a simplified geometry of the Western Himalayan Syntaxis area and its adjacent regions, where we try to match the first-order characteristics of the stress and strain fields of lithosphere since 10 Ma, and deformation and geodynamical evolution process in former 2Ma. Of course, the kinematic boundary conditions of the stress models driven by plate boundary forces were applied. The rheology plays a significant role in the lithospheric tectonics, which lead to different rheological parameters were used in different works although the have the same constitutive equations in models. So, in this paper we do not aim to produce all characteristics of the Western Himalayan Syntaxis areas’ stress and strain fields by the choices of various parameters, but rather the dynamic response between various rheological parameters and stress and strain fields. We have chosen to concentrate on the importance of rheology and lateral strength variations for lithospheric stress and strain patterns and use our findings to build a model of the Western Himalayan Syntaxis areas. In doing so, we want to go beyond purely elastic models or purely viscoelastic models. Compared the results of the crust viscosity in the Western Himalayan Syntaxis areas, we believed that, when various viscoelastic models are adopted, the selection of the coefficient of viscosity in the Western Syntaxis area has important influence on the its uplifts and evolutions. A wider uplift ranges and gently elevation was observed at the same time when a lower viscosity was used in our models, and vice versa. Data of stress magnitudes are not available, but it is clear that the stress levels must be at or below the failure threshold of rock under compression. Under these criteria, the calculation results show that the viscosity in the Western Syntaxis area should be smaller than 1023Pa.s When elastic model is adopted in relatively rigid Tarim basin, obvious changes are induced to the stress and strain fields of the whole Western Syntaxis area. We found that rigid block of lithosphere reduced stress levels within its interior and that, at the edges of such regions, stress orientation can change. Furthermore there is no evidence that such rigid regions act as stress barriers in that they shield areas in opposite sides of the structure from the influence of one another. In our models, the upper crustal material of the Western Syntaxis area does not turns to move westward. Whereas, because of the stress and strain fields have been decoupling at the interior of the lithosphere, we can get the results that the deep material must not move westward.

济阳地区深部结构与含油气性讨论

Oil and gas exploration of marine strata in China's Pre-Cenozoic residual basins is regarded as a worldwide puzzle because of existent problems and cruxes. Objectively speaking, the subsurface geologic structure is complicated, and the surface conditions of some areas are tough. On the other hand, there are still many problems to be solved in oil and gas exploration technologies of Pre-Cenozoic marine fades, and theoretic cognition about petroleum geology is not profound yet. Therefore, it is principal to explore integrated geophysical research ways of Pre-Cenozoic residual basins. Seismic prospecting and geophysical integrated interpretation technologies aimed at middle Paleozoic marine facies with deeper burial and complicated geologic conditions have not formed due to bad quality of deep strata data. Pre-Cenozoic strata, and especially extension, thickness and internal structure of Paleozoic strata can not be recognized from seismic profiles, so it is hard to systematically cognize structural features and oil-gas resources prospect of Pre-Cenozoic basins. To further investigation of fabric and structural features, basin prototype, formation and evolution pattern of Pre-Cenozoic basins, and also their control over formation, migration and aggregation of oil and gas, will play a guiding and promotive role in developing new surveying areas, selecting advantageous zones and predicting oil-gas resources.This paper follows the modem macrocontrol theory of "Region constrains local, deep strata controls shallow ones", and uses the integrated geophysical method of "One guide, two hinges, three combinations and multi feedbacks'*. Based on several years of geological and geophysical results of the Shengli Oilfield, and 14 newly-joint regional seismic profiles, deep structure and oil-gas bearing capacity of the Jiyang area are discussed and new cognitions are drawn as below.Seismic identification marks Tr, Tg, Tgl and Tg2 are established for importantPre-Cenozoic geological interfaces, and promoted to the whole Jiyang area.Through area-wide tracking and clogging of important seismic reflection marker,the isochronic framework of pre-Tertiary basin is set up in the Jiyang area for the firsttime, which is vital for basin research.Integrated with geological and geophysical research results, the Jiyang area isdivided into four first-order tectonic sequences- basement, lower tectonic layer,upper tectonic layer, and top tectonic layer. The basement and lower tectonic sequence which are related to Pre-Cenozoic are studied with emphasis.Through the research of regional seismic profiles, the point of view is given thatthe Kongdian Formation of Jiyang is structural transition period. The top-bottomunconformable interface of the Kongdian Formation is found out for the first time,and the basin model is determined primarily, which lay a basis for prototype basinresearch of the Jiyang Kongdian Formation.The distribution status of Middle-Paleozoic is delineated in the Jiyang area.The maximum thickness of Paleozoic lies in the top of the south declivity of half-graben. The thickness gets thinner towards the center of Mesozoic and Cenozoic half-graben basin, and even disappears. Structural action in the west-north affects the distribution of Paleozoic residual strata.6. The features of second-order tectonic sequence of the Jiyang depression isstudied and its evolution history of is rebuilt.Combined with the 5-stage evolution history of the China continent and structure evolution features of the Jiyang area, the structure sedimentary process since Paleozoic is divided into 5 periods - basement forming , Indosinian orogenic, Yanshan negative reversal, Himalayan extension and Neogene subsidence period.Combined with the research results of gravity, magnetic surveying and regionalprofiles, this paper brings forward the idea for the first time that the western boundaryof the Jiyang depression is the Ningjin-Yangpan fracture zone, and forms aside-column assemblage with the Wudi fracture zone.The opinion that under Middle-Cenozoic basins in the middle Jiyang area theremight superimpose an old residual basin is given for the first time. And if it is provedto be true, a new exploration space will be pioneered for Jiyang and even north China.There exists many types of tectonic-stratigraphic traps formed under piezotropy,extension and compound action in Pre-Cenozoic Jiyang. Therein all kinds of burialhills are the most important oil-gas trap type of Pre-Cenozoic, which should besurveyed layeredly according to the layout of oil sources.As such a new challenging project and field, the paper systematically analyses different geophysical responses of the Jiyang area, frames the deep structure of the area, and preliminarily recognizes the Pre-Cenozoic residual basins. It breaks through to a certain extent in both theory and practice, and is expected to provide new geophysical and geotectonic clues for deep exploration in Shengli.