Enthalpy–Entropy Compensation Combined with Cohesive Free‐Energy Densities for Tuning the Melting Temperatures of Cyanobiphenyl Derivatives

This work illustrates how minor structural perturbations produced by methylation of 4′‐(dodecyloxy)‐4‐cyanobiphenyl leads to enthalpy–entropy compensation for their melting processes, a trend which can be analyzed within the frame of a simple intermolecular cohesive model. The transformation of the melting thermodynamic parameters collected at variable temperatures into cohesive free‐energy densities expressed at a common reference temperature results in a novel linear correlation, from which melting temperatures can be simply predicted from molecular volumes.     

Wild-type and molten globular chorismate mutase achieve comparable catalytic rates using very different enthalpy/entropy compensations

The origin of the catalytic power of enzymes with a meta-stable native state,e.g.molten globular state,is an unsolved challenging issue in biochemistry.To help understand the possible differences between this special class of enzymes and the typical ones,we report here computer simulations of the catalysis of both the well-folded wild-type and the molten globular mutant of chorismate mutase.Using the ab initio quantum mechanical/molecular mechanical minimum free-energy path method,we determined the height of reaction barriers that are in good agreement with experimental measurements.Enzyme-substrate interactions were analyzed in detail to identify factors contributing to catalysis.Computed angular order parameters of backbone N–H bonds and side-chain methyl groups suggested site-specific,non-uniform rigidity changes of the enzymes during catalysis.The change of conformational entropy from the ground state to the transition state revealed distinctly contrasting entropy/enthalpy compensations in the dimeric wild-type enzyme and its molten globular monomeric variant.A unique catalytic strategy was suggested for enzymes that are natively molten globules:some may possess large conformational flexibility to provide strong electrostatic interactions to stabilize the transition state of the substrate and compensate for the entropy loss in the transition state.The equilibrium conformational dynamics in the reactant state were analyzed to quantify their contributions to the structural transitions enzymes needed to reach the transition states.The results suggest that large-scale conformational dynamics make important catalytic contributions to sampling conformational regions in favor of binding the transition state of substrate.     

Calcium Carbonate Dissolution from the Laboratory to the Ocean: Kinetics and Mechanism

The ultimate fate, over the course of millennia, of nearly all of the carbon dioxide formed by humankind is for it to react with calcium carbonate in the world's oceans. Although, this reaction is of global relevance, aspects of the calcite dissolution reaction remain poorly described with apparent contradictions present throughout the expansive literature. In this perspective we aim to evidence how a lack of appreciation of the role of mass-transport may have hampered developments in this area. These insights have important implications for both idealised experiments performed under laboratory conditions and for the measurement and modelling of oceanic calcite sediment dissolution.     

基于黑体标定的红外图像非均匀性校正系统设计

为提高某中波红外探测器的图像质量,设计了基于FPGA的红外图像实时处理系统,系统能够完成实时的非均匀性校正与盲元补偿处理。介绍了目前常用的非均匀性校正、盲元识别和补偿算法,并结合实际工程需求采用多点法进行非均匀性校正以及8点平均法进行盲元补偿。在仿真实验成功的基础上,基于FPGA平台构建了硬件平台。系统可以实现系数自定义更新,可以手动或自动完成非均匀性较正系数计算,以及实现盲元列表的自动更新操作。利用某国产中波红外探测器对处理系统进行了测试试验,实验结果表明:校正后图像非均匀性0.3%,盲元率0.001%。系统工作稳定、可靠,图像处理满足实时性和精度要求。     

道威棱镜的偏振特性及偏振补偿研究

为了避免机载光电吊舱中共口径光学系统内部由于道威棱镜旋转引起的激光照射脉冲偏振态的变化,利用琼斯矩阵对道威棱镜的偏振特性与四分之一波片、半波片补偿道威棱镜旋转引起的激光脉冲偏振态变化进行了理论分析和实验验证。结果表明:线偏振的激光脉冲通过旋转一定角度的道威棱镜时,激光脉冲偏振态变为椭圆偏振,偏振态发生变化;而激光脉冲首先通过旋转一定角度的四分之一波片与半波片时,可使通过道威棱镜系统的激光脉冲偏振态保持不变,且两波片旋转角度与道威棱镜旋转角度之间存在一种非线性关系。采用偏振补偿方法可有效避免机载共口径光学系统中道威棱镜引起的激光脉冲偏振态变化,提高激光脉冲能量利用率,降低激光脉冲后向散射抑制难度。     

Research on application of polynomial fitting technique in rotary kiln infrared temperature measurement system

Aiming at the linear temperature compensation algorithm’s disadvantage of temperature measurement error in rotary kiln infrared scanning temperature measurement process, this paper proposes a precise nonlinear cubic polynomial fitting temperature compensation algorithm. The proposed algorithm compensates the temperature values of scanning points on rotary kiln surface by following steps: Calculating temperature difference between the real temperature value of rotary kiln and temperature value measured by infrared scanning temperature measurement system; Fitting the temperature difference data with cubic polynomial; Using the obtained function to compensate temperature. Experimental result shows that compared with the usual linear temperature compensation algorithm, the accuracy of proposed algorithm has raised about 2.25 times when cubic polynomial is used.     

适用于波前处理器的自适应光学系统非共光路像差补偿方法

提出了一种适合硬件形式波前处理器的非共光路像差校正方法.讨论了非共光路像差的产生原因和运用相位差异技术检测非共光路像差的方法.根据波前处理器的工作流程,推导了将非共光路像差折算到波前探测器参考点偏移量的算法,编写了实现算法的主控计算机软件模块.在望远镜光路中以光源为目标开展实验,用本文算法校正后,目标能量集中度提高了17.6%,证明了该方法的可行性.     

编码器动态检测系统高实时性高精度角度基准设计

在编码器动态特性检测中,角度基准的快速反应和精度直接影响着动态特性检测装置的准确性。为实现角度基准的快速响应,提高基准编码器的测角精度,本文设计了高精度快速细分角度基准编码器。首先,通过对目前角度基准不足对编码器动态特性检测影响的分析,得出动态检测精度主要受基准编码器的数据处理延时影响。其次,通过对基准编码器结构、细分电路、处理电路等的设计,完成了23位高实时性角度基准编码器的制作。最后,为提高检测精度,利用RBF神经网络对角度基准进行误差补偿。所设计的角度基准编码器分辨率达到0.15",并且可以在10 r/s速度时,保证逐分辨率输出。经过测量,补偿前基准编码器的精度为1.30",补偿后的基准编码器误差峰峰值不超过2.5",精度优于0.6"。高精度、高实时性角度基准编码器的研制,提高了编码器动态特性检测系统的检测精度,为研究编码器动态特性提供了基础。     

基于联合变换相关的机载航空相机像移测量

为了提高像移测量精度,针对机载航空摆扫相机提出一种坐标变换法和图像相关法相结合的像移测量方法。利用坐标变换法得到初始像移速度,利用图像联合变换相关法对像移速度残差进行补偿。联合图像通过一个面阵CCD获得,该面阵CCD放置在相机焦平面上并与成像线阵TDI CCD平行,其输出的当前图像与参考图像合并构成联合图像进行二维空间联合变换相关运算,得到像移修正矢量。对该矢量分别在相机摆扫方向和载机飞行方向进行分解,从而得到摆扫像移和前向像移的修正量。仿真实验结果表明,在输入图像信噪比为4 dB时,像移测量误差在0.1 pixel以内。