Conformation studies on sol-gel transition in triblock copolymer solutions

The gelation of physically associating triblock copolymers in a good solvent was investigated by means of the Monte Carlo simulation and a gelation process based on the conformation transition of the copolymer that was described in detail. In our simulative system, it has been found that the gelation is closely related with chain conformations, and there exist four types of chains defined as free, dangling, loop, and bridge conformations. The copolymer chains with different conformations contribute to the formation of gel in different ways. We proposed a conformational transition model, by which we evaluated the role of these four types of chains in sol-gel transition. It was concluded that the free chains keeping the conformation transition equilibrium and the dangling conformation being the hinge of conformation transition, while the chain with loop conformation enlarges the size of the congeries and the chain with bridge conformations binds the congeries consisted of the copolymer chains. In addition, the effects of temperature and concentration on the physical gelation, the association of the copolymer congeries, and the copolymer chain conformations' distribution were discussed.

The influence of tip performance on scanning probe lithography

Scanning probe lithography (SPL), employing the tip of an atomic force microscope to mechanically pattern various materials in nanoscale region has provided a simple but significant method for making nanostructures. We use this technique for the lithography of several kinds of substrate surfaces. The tip performance has been found to be a crucial factor in the lithographic process. Four types of cantilevers are employed in nanolithography, including standard silicon nitride (DNP), tapping mode(TM) etched silicon (TESP(W)), uncoated silicon cantilever (NSC21/50) and conductive platinum/iridium-coated probe. Results demonstrate that tips with smaller spring constants can not be used for physically scribing and nanomanipulating in our experiment. The possible mechanism of our experiment is discussed.

Synthesis and self-assembly of cetyltrimethylammonium bromide-capped gold nanoparticles

In this article, cetyltrimethylammonium bromide (CTAB)-capped gold nanoparticles were synthesized successfully by using CTAB as a phase-transfer catalyst and stabilizer simultaneously in a two-phase toluene/water system. The as-prepared gold nanoparticles were characterized and analyzed by virtue of X-ray photoelectron spectroscopy, UV-visible absorbance spectroscopy, and infrared spectroscopy. The particle size information and collective self-assembling properties of the CTAB-capped gold nanoparticles on carbon-coated copper grid and mica were evaluated by transmission electron microscopy and atomic force microscopy, respectively. As a result it is demonstrated that the 3-D CTAB monolayers on a gold cluster are in the disordered liquid state. The interparticle spacing can be controlled either physically by the inherent particle-to-particle interactions or chemically by molecular linker. The assembly of both nanoparticles and linker-bridged nanonetworks on mica follows a hydrophobic interaction mechanism.

Study of electron transfer across the liquid/ice-like matrix interface by scanning electrochemical microscopy

In this work, we report the findings of a study on scanning electrochemical microscopy (SECM) to investigate the interfacial electron-transfer (ET) reaction between the 7,7,8,8-tetracyanoquinodimethane radical anion (TCNQ(.-)) in 1,2-dichloroethane and ferricyanide in an ice-like matrix (a mixture of insulting ice and conductive liquid) under low temperatures. Experimental results indicate that the formed liquid/ice-like matrix interface is superficially similar in electrochemical characteristics to a liquid/liquid interface at temperatures above -20 degreesC. Furthermore, imaging data show that the surface of the ice-like matrix is microscopically flat and physically stable and can be applied as either a conductive or an insulting substrate for SECM studies. Perchlorate ion was selected as the common ion in both phases, the concentrations of which controlled the interfacial potential difference. The effect of perchlorate concentration in the DCE phase on interfacial reactions has been studied in detail. The apparent heterogeneous rate constants for TCNQ(.-) oxidation by Fe(CN)(6)(3-) in another phase under different temperatures have been calculated by a best-fit analysis, where the experimental approach curves are compared with the theoretically derived relationships. Reaction rate data obey Butler-Volmer formulation before and after the freezing point, which is similar to most other known cases of ET reactions at liquid/liquid interfaces. However, there is a sharp change observed for heterogeneous rate constants around the freezing point of the aqueous phase, which reflects the phase transition. At temperatures below -20 degreesC, surface-confined voltammograms for the reduction of ferricyanide were obtained, and the ice-like matrix became an insulating one, which indicates that the aqueous phase is really a frozen phase.

Isothermal crystallization kinetics of PEO in poly(ethylene terephthalate)-poly(ethylene oxide) segmented copolymers. I. Effect of the sofi-block length

The isothermal crystallization kinetics of poly(ethylene oxide) (PEO) block in two poly(ethylene terephthalate) (PET)-PEO segmented copolymers was studied with differential scanning calorimetry. The Avrami equation failed to describe the overall crystallization process, but a modified Avrami equation, the Q equation, did. The crystallizability of the PET block and the different lengths of the PEO block exerted strong influences on the crystallization process, the crystallinity, and time final morphology of the PEO block. The mechanism of nucleation and the growth dimension of the PEG block were different because of the crystallizability of time PET block and the compositional heterogeneity. The crystallization of the PEO block was physically constrained by the microstructure of time PET crystalline phase, which resulted in a lower crystallization rate. However, this influence became weak with the increase in the soft-block length. (C) 2000 John Wiley & Sons, Inc.

Study of (TPP)H-2 vapor deposited film on iron

The film by tetraphenylporphyrin((TPP)H-2) vapor deposition on iron was investigated by means of XPS, SEM and visible spectroscopy. N(1s) binding energy characteristic of(TPP)H-2 was gained directly from the deposited samples. N(1s) binding energy of the surface was greatly changed after the deposited sample was washed with solvent. It is indicated that the deposited film is composed of an outer-layer of physically adsorbed (TPP)H-2, and an inner-layer of chemically modified (TPP)H-2.

Tip-induced dynamic characterization of multilayers and variable morphologies of cytochrome c molecules on highly oriented pyrolytic graphite revealed by in-situ scanning tunnelling microscopy

The dynamic states of cytochrome c multilayers on electrochemically pretreated highly oriented pyrolytic graphite (HOPG) have been studied by in-situ scanning tunnelling microscopy (STM) under potential control of both the tip and the substrate in cytochrome c and phosphate buffer solution. The dynamic characterization of cytochrome c multilayers and relatively stable adsorbed single cytochrome c molecules scattered on HOPG imply that physically adsorbed multilayers were more easily influenced by the STM tip than those of chemically adsorbed single molecules. In-situ STM images of chemically adsorbed cytochrome c molecules with discernible internal structures on HOPG revealed that morphologies of cytochrome c molecules also suffered tip influence; possible tip-sample-substrate interactions have been discussed.

地幔压力下CaSiO3 Perovskite状态方程和弹性常数的第一性原理研究

In the past decade density functional theory (DFT) has made its way from a peripheral position in quantum chemistry to center. Of course the often excellent accuracy of the DFT based methods has provided the primary driving force of this development. This dissertation is devoted to the study of physical and chemical properties of planetary materials by first-principle calculation. The concerned properties include the geometry, elastic constants and anisotropy. In the first chapter, we give a systematic introduction to theoretical background and review its progress. Development of quantum chemistry promotes the establishment of DFT. Theorem of Hohenberg-Kohn is the fundament of DFT and is developed to Kohn-Sham equation, which can be used to perform real calculations. Now, new corrections and extensions, together with developed exchange-correlation, have made DFT more accurate and suitable for larger systems. In the second chapter, we focus on the calculational methods and technical aspects of DFT. Although it is important to develop methods and program, external package are still often used. At the end of this chapter, we briefly some widely used simulation package and the application of DFT. In the third chapter, we begin to focus on properties of real materials by first principles calculation. We study a kind of minerals named Ca perovskite, investigate its possible structure and anisotropy at Earth’s mental condition. By understanding and predicting geo-physically important materials properties at extreme conditions, we can get the most accurate information to interpret seismic data in the context of likely geophysical processes.

地震波场延拓+菲涅尔体叠加方法及成像效果

In the increasingly enlarged exploration target, deep target layer(especially for the reservoir of lava) is a potential exploration area. As well known, the reflective energy becomes weak because the seismic signals of reflection in deep layer are absorbed and attenuate by upper layer. Caustics and multi-values traveltime in wavefield are aroused by the complexity of stratum. The ratio of signal to noise is not high and the fold numbers are finite(no more than 30). All the factors above affect the validity of conventional processing methods. So the high S/N section of stack can't always be got with the conventional stack methods even if the prestack depth migration is used. So it is inevitable to develop another kind of stack method instead. In the last a few years, the differential solution of wave equation was hold up by the condition of computation. Kirchhoff integral method rose in the initial stages of the ninetieth decade of last century. But there exist severe problems in it, which is are too difficult to resolve, so new method of stack is required for the oil and gas exploration. It is natural to think about upgrading the traditionally physic base of seismic exploration methods and improving those widely used techniques of stack. On the other hand, great progress is depended on the improvement in the wave differential equation prestack depth migration. The algorithm of wavefield continuation in it is utilized. In combination with the wavefield extrapolation and the Fresnel zone stack, new stack method is carried out It is well known that the seismic wavefield observed on surface comes from Fresnel zone physically, and doesn't comes from the same reflection points only. As to the more complex reflection in deep layer, it is difficult to describe the relationship between the reflective interface and the travel time. Extrapolation is used to eliminate caustic and simplify the expression of travel time. So the image quality is enhanced by Fresnel zone stack in target. Based on wave equation, high-frequency ray solution and its character are given to clarify theoretical foundation of the method. The hyperbolic and parabolic travel time of the reflection in layer media are presented in expression of matrix with paraxial ray theory. Because the reflective wave field mainly comes from the Fresnel Zone, thereby the conception of Fresnel Zone is explained. The matrix expression of Fresnel zone and projected Fresnel zone are given in sequence. With geometrical optics, the relationship between object point in model and image point in image space is built for the complex subsurface. The travel time formula of reflective point in the nonuniform media is deduced. Also the formula of reflective segment of zero-offset and nonzero offset section is provided. For convenient application, the interface model of subsurface and curve surface derived from conventional stacks DMO stack and prestack depth migration are analyzed, and the problem of these methods was pointed out in aspects of using data. Arc was put forward to describe the subsurface, thereby the amount of data to stack enlarged in Fresnel Zone. Based on the formula of hyperbolic travel time, the steps of implementation and the flow of Fresnel Zone stack were provided. The computation of three model data shows that the method of Fresnel Zone stack can enhance the signal energy and the ratio of signal to noise effectively. Practical data in Xui Jia Wei Zhi, a area in Daqing oilfield, was processed with this method. The processing results showed that the ability in increasing S/N ratio and enhancing the continuity of weak events as well as confirming the deep configuration of volcanic reservoir is better than others. In deeper target layer, there exists caustic caused by the complex media overburden and the great variation of velocity. Travel time of reflection can't be exactly described by the formula of travel time. Extrapolation is bring forward to resolve the questions above. With the combination of the phase operator and differential operator, extrapolating operator adaptable to the variation of lateral velocity is provided. With this method, seismic records were extrapolated from surface to any different deptlis below. Wave aberration and caustic caused by the inhomogenous layer overburden were eliminated and multi-value curve was transformed into the curve.of single value. The computation of Marmousi shows that it is feasible. Wave field continuation extends the Fresnel Zone stack's application.

黄土高原粉尘堆积源区环境及风化历史初步研究

In this study, we examined the surface features of quartz grains, the quartz oxygen isotopic ratios and the mineralogical compositions of the loess - paleosol - red clay sediments systematically. The surface features of quartz grains do not show significant changes of the dust deposits through the past seven million years. The particles were mainly created in the process of glacial and frost weathering of high mountains. Then the surfaces were altered in some degree by the flood and wind abrasion. The surface features registered all these processes. The assemblages of surface features changed for four times in the past seven million years, the occurrence ages are: 5.0~4.2MaBP, about 3.6MaBP, about 2.6MaBP and about 0.9MaBP, respectively. This may indicate that there were uplift events of the Tibetan Plateau during those times. The oxygen isotopic compositions of quartz in the sediments represent the oxygen isotopic compositions of the initial dusts because of the stable properties of quartz both physically and chemically. The oxygen isotopic compositions of 4~16um quartz changed significantly at about 2.6MaBP, decreasing from about 19.5%o to about 18.5%o. This decrease of quartz oxygen isotopic ratio suggests that the environments of the dust source areas changed at that time, or the range of dust source area changed at that time. The environmental change may result from the structural evolution of the Tibetan Plateau and global cooling at that time. The coarse fractions (>30μm) of the dust deposits were examined using the EDXA device for mineral identification. The quartz content has a decrease trend during 7~2MaBP, then increase rapidly at about 2MaBP. After 2MaBP, quartz content continues to decrease. The Ca-plagioclase content / quartz content ratio increase at about 3.6MaBP. The ratio shows a peak of 3-6 fold values at about 2.5~1.8MaBP, the cause of this is still unknown. The Ca-plagioclase content / quartz content ratio continues to increase after 1 MaBP. The flowing can be regarded as the conclusion remarks of this study: Some of the red clay sediment of the Chinese Loess Plateau (at least Lingtai and Jingchuan red clays) is eolian in origin. The quartz grains from dust deposits throughout the past seven million yeas showed the clues of glacial and frost processes. This indicates that the high mountains of western China reached a certain altitude to favor the glacial and/or frost processes at least seven millions years before. The weathering intensities of the past seven nnillion yeas have a decreasing trend. In about 5~4.5MaBP, the weathering is relatively weak, and the dust supply is relatively low. At about 3.6MaBP and 2.6MaBP, the dust supply increased significantly. The mineralogical composition, the quartz surface feature and the quartz oxygen isotope composition were influenced by the uplift of the Tibetan Plateau. The Plateau may have reached a certain altitude to generate the arid regions of inland China and favor the glacial and frost weathering. And it underwent a phased uplift, which have uplift events at about 3.6MaBP and 2.6MaBP.

Retention behavior of hydrophobic organic chemicals as a function of temperature in soil leaching column chromatography

To study the transport mechanism of hydrophobic organic chemicals (HOCs) and the energy change in soil/solvent system, a soil leaching column chromatographic (SLCC) experiment at an environmental temperature range of 20-40 degreesC was carried out, which utilized a reference soil (SP 14696) packed column and a methanol-water (1:4 by volume ratio) eluent. The transport process quickens with the increase of column temperature. The ratio of retention factors at 30 and 40 degreesC (k'(30)/k'(40)) ranged from 1.08 to 1.36. The lower enthalpy change of the solute transfer in SLCC (from eluent to soil) than in conventional reversed-phase liquid chromatography (e.g., from eluent to C-18) is consistent with the hypothesis that HOCs were dominantly and physically partitioned between solvent and soil. The results were also verified by the linear solvation energy relationships analysis. The chief factor controlling the retention was found to be the solute solvophobic partition, and the second important factor was the solute hydrogen-bond basicity, while the least important factors were the solute polarizability-dipolarity and hydrogen-bond acidity. With the increase of temperature, the contributions of the solute solvophobic partition and hydrogen-bond basicity gradually decrease, and the latter decreases faster than the former. (C) 2002 Elsevier Science Ltd. All rights reserved.

基底神经节的认知和记忆功能研究

The cognition and memory functions of the Basal Ganglia have been the focus of contemporary cognitive neuroscience researches. This study, from neuroanatomical and neurophysiological point of view, thoroughly surveyed the recent relevant research progress, carefully examined the evidences of the neurological basis for the Basal Ganglia possessing or participating cognition or memory functions. Moreover, it reviewed recent achievements on the cognitive functions of the basal ganglia based on researches on rodent animals, primate animals and human beings. Then it presented a series of experiments conducted, by neuropsychological and cognitive psychological methods, on neurological patients with focal lesions to the basal ganglia or combining with bilateral hippocampus or thalamus impaired to explore what the role of the basal ganglia play in human explicit and implicit memory. It was found that the lesions to the basal ganglia partially handicapped explicit verbal memory and completely impaired perceptual priming. It was also found that right cerebral cortex dysplasia but basal ganglia spared had no effects on priming tasks performances. The results suggested that the basal ganglia contain or accommodate higher cognitive functions and further suggested that priming be irrelevant to right cerebral cortex. It was posited that the basal ganglia, on the basis of interaction with prefrontal or temporal cortices, mediate movement function as well as cognition and memory functions.