Effects of Translational Nonequilibrium on Performance of Flowing Chemical Oxygen-Iodine Laser

The effect of the translational nonequilibrium on performance modeling of flowing chemical oxygen-iodine lasers (COIL) is emphasized in this paper. The spectral line broadening (SLB) model is a basic factor for predicting the performances of flowing COIL. The Voigt profile function is a well-known SLB model and is usually utilized. In the case of gas pressure in laser cavity less than 5 torr, a low pressure limit expression of the Voigt profile function is used. These two SLB models imply that ail lasing particles can interact with monochromatic laser radiation. Basically, the inhomogeneous broadening effects are not considered in these two SLB models and they cannot predict the spectral content. The latter requires consideration of finite translational relaxation rate. Unfortunately, it is rather difficult to solve simultaneously the Navier-Stokes (NS) equations and the conservation equations of the number of lasing particles per unit volume and per unit frequency interval. In the operating condition of flowing COIL, it is possible to obtain a perturbational solution of the conservational equations for lasing particles and deduce a new relation between the gain and the optical intensity, i.e., a new gain-saturation relation. By coupling the gain-saturation relation with other governing equations (such as the NS equations, chemical reaction equations and the optical model of gain-equal-loss), We have numerically calculated the performances of flowing COIL. The present results are compared with those obtained by the common rate-equation (RE) model, in which the Voigt profile function and its low pressure limit expression are used. The difference of different model's results is great. For instance, in the case of lasing frequency coinciding with the central frequency of line profile and very low gas pressure, the gain-saturation relation of the present model is quite different with that of the RE model.

State-to-state dynamics of elementary chemical reactions using Rydberg H-atom translational spectroscopy

In this review, a few examples of state-to-state dynamics studies of both unimolecular and bimolecular reactions using the H-atom Rydberg tagging TOF technique were presented. From the H2O photodissociation at 157 nm, a direction dissociation example is provided, while photodissociation of H2O at 121.6 has provided an excellent dynamical case of complicated, yet direct dissociation process through conical intersections. The studies of the O(D-1) + H-2 --> OH+H reaction has also been reviewed here. A prototype example of state-to-state dynamics of pure insertion chemical reaction is provided. Effect of the reagent rotational excitation and the isotope effect on the dynamics of this reaction have also been investigated. The detailed mechanism for abstraction channel in this reaction has also been closely studied. The experimental investigations of the simplest chemical reaction, the H-3 system, have also been described here. Through extensive collaborations between theory and experiment, the mechanism for forward scattering product at high collision energies for the H+HD reaction was clarified, which is attributed to a slow down mechanism on the top of a quantized barrier transition state. Oscillations in the product quantum state resolved different cross sections have also been observed in the H+D-2 reaction, and were attributed to the interference of adiabatic transition state pathways from detailed theoretical analysis. The results reviewed here clearly show the significant advances we have made in the studies of the state-to-state molecular reaction dynamics.

Photofragment translational spectroscopy of p-bromotoluene at 266 nm

Photodissociation of p-bromotoluene at 266 nm has been investigated on the universal crossed molecular beam machine, and translational energy distribution P(E-t) as well as the anisotropy parameter beta have been obtained. Photofragment translational energy distribution P(E-t) reveals that similar to 38.5% of the available energy is partitioned into translational energy. The anisotropy parameter beta is determined to be -0.4 +/- 0.2. From P(E-t) and beta, we deduce that p-bromotoluene photodissociation is a fast process and the perpendicular transition plays a central role at this wavelength. The possible mechanism has been discussed and comparison of p-bromotoluene with bromobenzene, o-bromotoluene has also been made. (C) 1999 Elsevier Science B.V. All rights reserved.

Photofragment translational spectroscopy of iodobenzene at 266 nm

The photofragmentation of C6H5I at 266 nn is investigated on the universal crossed molecular beam ma chine, and the translational spectroscopy as well as the angular distribution of I atom is measured. The results reveal that under the laser intensity of 10(R) W/cm(2) the single-photon dissociation competes with multi-photon processes. In single-photon dissociation the anisotropy parameter beta is 0.4 and the average translational energy is only 1.04 kcal/mol, which indicates that this process is a slow predissociation. In two-photon photofragmentation the average translational energy is 51.64 kcal/mol, which accounts for about 35% of the available energy. Another photofragmentation channel is even more faster, whose peak in time-of-flight spectra corresponds to four or five photon absorptions. The branching ratio of these three channels is determined to he about 3:3:4.

Finite Element Solutions for Plane Strain Mode I Crack with Strain Grading Effect

In this paper, a new phenomenological theory with strain gradient effects is proposed to account for the size dependence of plastic deformation at micro- and submicro-length scales. The theory fits within the framework of general couple stress theory and three rotational degrees of freedom omega(i) are introduced in addition to the conventional three translational degrees of freedom mu(i). omega(i) is called micro-rotation and is the sum of material rotation plus the particles' relative rotation. While the new theory is used to analyze the crack tip field or the indentation problems, the stretch gradient is considered through a new hardening law. The key features of the theory are that the rotation gradient influences the material character through the interaction between the Cauchy stresses and the couple stresses; the term of stretch gradient is represented as an internal variable to increase the tangent modulus. In fact the present new strain gradient theory is the combination of the strain gradient theory proposed by Chen and Wang (Int. J. Plast., in press) and the hardening law given by Chen and Wang (Acta Mater. 48 (2000a) 3997). In this paper we focus on the finite element method to investigate material fracture for an elastic-power law hardening solid. With remotely imposed classical K fields, the full field solutions are obtained numerically. It is found that the size of the strain gradient dominance zone is characterized by the intrinsic material length l(1). Outside the strain gradient dominance zone, the computed stress field tends to be a classical plasticity field and then K field. The singularity of stresses ahead of the crack tip is higher than that of the classical field and tends to the square root singularity, which has important consequences for crack growth in materials by decohesion at the atomic scale. (C) 2002 Elsevier Science Ltd. All rights reserved.

Cross-relaxation dynamics on anomalous saturation processes in low pressure supersonic cw HF chemical laser amplifier

It is assumed that both translational and rotational nonequilibrium cross-relaxations play a role simultaneoulsy in low pressure supersonic cw HF chemical laser amplifier. For two-type models of gas flow medium with laminar and turbulent flow diffusion mixing, the expressions of saturated gain spectrum are derived respectively, and the numerical calculations are performed as well. The numerical results show that turbulent flow diffusion mixing model is in the best agreement with the experimental result.

A New Deformation Theory with Strain Gradient Effects

A new phenomenological deformation theory with strain gradient effects is proposed. This theory, which belongs to nonlinear elasticity, fits within the framework of general couple stress theory and involves a single material length scale l. In the present theory three rotational degrees of freedom omega(i) are introduced in addition to the conventional three translational degrees of freedom u(i). omega(i) has no direct dependence upon ui and is called the micro-rotation, i.e. the material rotation theta(i) plus the particle relative rotation. The strain energy density is assumed to only be a function of the strain tensor and the overall curvature tensor, which results in symmetric Cauchy stresses. Minimum potential principle is developed for the strain gradient deformation theory version. In the limit of vanishing 1, it reduces to the conventional counterparts: J(2) deformation theory. Equilibrium equations, constitutive relations and boundary conditions are given in details. Comparisons between the present theory and the theory proposed by Shizawa and Zbib (Shizawa, K., Zbib, H.M., 1999. A thermodynamical theory gradient elastoplasticity with dislocation density Censor: fundamentals. Int. J. Plast. 15, 899) are given. With the same hardening law as Fleck et al. (Fleck, N.A., Muller, G.H., Ashby, M.F., Hutchinson, JW., 1994 Strain gradient plasticity: theory and experiment. Acta Metall. Mater 42, 475), the new strain gradient deformation theory is used to investigate two typical examples, i.e. thin metallic wire torsion and ultra-thin metallic beam bend. The results are compared with those given by Fleck et al, 1994 and Stolken and Evans (Stolken, J.S., Evans, A.G., 1998. A microbend test method for measuring the plasticity length scale. Acta Mater. 46, 5109). In addition, it is explained for a unit cell that the overall curvature tensor produced by the overall rotation vector is the work conjugate of the overall couple stress tensor. (C) 2002 Elsevier Science Ltd. All rights reserved.

Mesofracture mechanics: a necessary link

Classical fracture mechanics is based on the premise that small scale features could be averaged to give a larger scale property such that the assumption of material homogeneity would hold. Involvement of the material microstructure, however, necessitates different characteristic lengths for describing different geometric features. Macroscopic parameters could not be freely exchanged with those at the microscopic scale level. Such a practice could cause misinterpretation of test data. Ambiguities arising from the lack of a more precise range of limitations for the definitions of physical parameters are discussed in connection with material length scales. Physical events overlooked between the macroscopic and microscopic scale could be the link that is needed to bridge the gap. The classical models for the creation of free surface for a liquid and solid are oversimplified. They consider only the translational motion of individual atoms. Movements of groups or clusters of molecules deserve attention. Multiscale cracking behavior also requires the distinction of material damage involving at least two different scales in a single simulation. In this connection, special attention should be given to the use of asymptotic solution in contrast to the full field solution when applying fracture criteria. The former may leave out detail features that would have otherwise been included by the latter. Illustrations are provided for predicting the crack initiation sites of piezoceramics. No definite conclusions can be drawn from the atomistic simulation models such as those used in molecular dynamics until the non-equilibrium boundary conditions can be better understood. The specification of strain rates and temperatures should be synchronized as the specimen size is reduced to microns. Many of the results obtained at the atomic scale should be first identified with those at the mesoscale before they are assumed to be connected with macroscopic observations. Hopefully, "mesofracture mechanics" could serve as the link to bring macrofracture mechanics closer to microfracture mechanics.

Parallel Fully-Implicit Computation of MHD Acceleration Experiments

A three-dimensional MHD solver is described in the paper. The solver simulates reacting flows with nonequilibrium between translational-rotational, vibrational and electron translational modes. The conservation equations are discretized with implicit time marching and the second-order modified Steger-Warming scheme, and the resulted linear system is solved iteratively with Newton-Krylov-Schwarz method that is implemented by PETSc package. The results of convergence tests are plotted, which show good scalability and convergence around twice faster when compared with the DPLR method. Then five test runs are conducted simulating the experiments done at the NASA Ames MHD channel, and the calculated pressures, temperatures, electrical conductivity, back EMF, load factors and flow accelerations are shown to agree with the experimental data. Our computation shows that the electrical conductivity distribution is not uniform in the powered section of the MHD channel, and that it is important to include Joule heating in order to calculate the correct conductivity and the MHD acceleration.

噬菌体434单链阻遏蛋白的高亲和力DNA结合序列的设计和筛选

一． 设计和筛选单链阻遏蛋白的高亲和力DNA结合序列 　　单链阻遏蛋白RRTRES是噬菌体434阻遏蛋白的衍生物，它是噬菌体434阻 遏蛋白的N端DBD(1-69位氨基酸)组成的共价二聚体。这个单链分子有两个DBD，一个是野生型噬菌体434的DBD-R，另一个是突变了的DBD - RTRES，二者用重组接头以头接尾的方式连接起来。在RTRES的α3-螺旋中．1、1、2、5位氨基酸与DNA识别紧密相关，它们分别为T、R、E、S。为了筛选出突变的RTRES的DNA结合位点，设计了核心序列为CATACAAGAAAGNNNNNNTTTATG随机DNA库，通过RRTRES与随机DNA库的体外结合和循环筛选。将筛选到的群体克隆并测序。通过与单链阻遏蛋白RRTRES的亲和力测定，对每一个筛选到的序列进行特性分析。结果表明，当结合位点（上述划线部分）为TTAC或TTCC时为最适操纵区序列。它们与单链阻遏蛋白RRTRES的亲和力很高，Kd值在1-10pM的范围。其中随机部分为TTTACG的操纵区与RRTRES的亲和力最高，Kd值约为lpM;当结合位点为TTAC时，平均Kd值为3pM：当结合位点为 TTCC时，Kd值在5-lOpM之间。天然噬菌体434阻遏蛋白与其操纵区的亲和力的Kd值在nM数量级，与之相比，所筛选操纵区的亲和力明显提高。此外，亲和力大小还受到结合位点两侧的碱基的影响，特别是5'位碱基的影响。 　　表达纯化同源双突变的单链阻遏蛋白RTRESRTRE'根据RTRES的以上识别特一点，设计了一系列新的操纵区序列，它们的共有序列为GTAAGAAARNTTACN，或GGAAGAAARNTTCCN，并测定它们与RTRES RTRE之间的结合特异性。结果表明，它们可被RTRES RTRES特异识别，且亲和力也很高，Kd值在5-40pM之间。其中GTAAGAAAGTTTACG与RTRES RTRES之间结合的Kd值约为5pM。同样，表达了异源双突变的单链阻遏蛋白R*RTRES，然而它与 设计的相关操纵区的亲和力并不很高，Kd值约为lOOpM。利用本工作中的随机筛选和合理设计的原则，得到了新的具有特异性识别和高亲和力的蛋白一DNA相互作用。这个方法可望用于其他DBP的新的结合特异性的筛选。 二． 非同位素的方法筛选单链阻遏蛋白的最佳DNA结合序列初探 　　克隆和表达了带半胱氨酸尾的单链阻遏蛋白，利用已包被了马来酰胺的活性板可以与自由巯基结合的特性，将蛋白固定在活性板表面。体外筛选RTRES RTRES的最佳DNA结合序列，得到了一些与RTRES RTRES结合的序列，但Kd值nM数量级。此方法需进一步优化。

蓝藻应答高 pH 胁迫的亚细胞蛋白质组学研究

蓝藻是迄今地球上发现的最古老、分布最广和最具多样性的光合自养原核生物，其细胞结构简单，具有类似于植物的光合作用，是研究光合作用及其它代谢过程重要的模式生物。由于这类生物起源于远古前寒武纪，但至今依然繁多，在极端寒冷的南北极冰湖和近于沸腾温度的温泉，以及高盐、强碱的极端环境中均有存在,它们在漫长的进化过程中如何应对灾难性环境、针对随时可能遭遇的不同胁迫环境因子形成了怎样的分子适应机制，是近年来倍受关注但仍未诠释的问题之一。由于蓝藻与高等植物叶绿体在进化上密切相关，搞清楚这类生物适应不同胁迫环境因子的分子基础及其作用机制，对从进化的角度理解光合生物与环境相互作用、通过同源性发现作物抗逆育种新靶标，有重要的理论和实践意义。 逆境应答蛋白的表达是细胞对逆境胁迫的主要适应机制之一。在特定的逆境条件下，细胞通常会表达一组蛋白质，用于识别与传递环境胁迫信号、稳定细胞内环境、消除并修复逆境造成的损伤等。因此，逆境应答蛋白的系统鉴定和功能确认，是揭示逆境条件下细胞代谢网络及抗逆性分子机制的关键。单细胞模式蓝藻基因组序列的确定，极大地推动了蓝藻细胞蛋白质组成模式研究，也为系统发掘蓝藻逆境应答蛋白、理解和揭示分子适应机制提供了新的切入点。Synechocystis 6803是第一个完成基因组测序的放氧光合模式生物。由于其具有易培养、可转化、对环境条件变化反应快等优点，以该藻种为材料所展开的逆境应答特别是盐胁迫蛋白质组研究方面已经取得了重要的进展，而对高pH胁迫的蛋白质组研究还鲜有报道。因此，本论文以Synechocystis 6803为材料，从分离纯化的亚细胞组分入手，采用蛋白质组学研究手段，对蓝藻细胞应答高pH胁迫的蛋白质代谢网络进行探讨。利用蔗糖密度离心和水溶性两相分离法相结合的方法，分别获得了对照（pH7.5）和处理（pH11）细胞的质膜、外膜和类囊体膜，并分别构建了包括可溶性蛋白和膜组分的一维和二维蛋白质凝胶电泳图谱。分析结果表明，高pH胁迫下质膜和可溶性蛋白蛋白组分的变化较外膜和类囊体膜蛋白组分更为明显。在考马斯亮兰染色胶上共发现有近110个蛋白点上调或下调表达，其中有82个蛋白点来源于质膜。对质膜蛋白进行的差异荧光标记双向电泳（2-D DIGE）分析结果与考马斯亮兰染色结果基本一致。对质膜上的82个蛋白点进行胶内消化和MALDI-TOF和MALDI-TOF/TOF质谱鉴定，得到了39个不同基因产物，其中25个是上调蛋白，14个是下调蛋白。在这些发生变化的蛋白中，近1/3是ABC型转运蛋白，如3个磷转运蛋白（Sll0679，Sll0683，Sll0684）均在高pH胁迫下明显上调。其它高pH响应蛋白包括参与光合作用（PsaF，Sll0819；CpcA，Sll1578）、呼吸作用（CoxB，Sll0813）以及细胞分裂过程的蛋白（MinD，Sll0289）。还有LexA repressor (Sll1626)和Guanylyl cyclase(Cya2，Sll0646)等起调控作用的蛋白质。此外发现8个高pH胁迫响应蛋白为功能未知的新蛋白。生物信息学预测结果显示，在已鉴定的质膜响应蛋白中有17个蛋白具有信号肽。6个蛋白为具有跨膜域的膜蛋白，其中的3个膜蛋白是首次被证明定位于质膜上，且其表达与高pH胁迫有关。这些研究结果对从分子水平理解蓝藻细胞主动应对高pH胁迫、维护细胞内pH相对稳定机制有重要启示。