利用二维接力相关谱和J分解谱对里杜霉素质子信号的归属

本文采用二维接力相关技术(单接力和三接力COSY)和J分解谱对氨基糖苷类化合物里杜霉素的全部质子信号进行了归属,为进一步测定里杜霉素的构型和构象打下了基础.     

关附庚素的选择性远程DEPT、一维COSY和一维接力COSY谱的研究

由于谱峰拥挤和重迭、关附庚素的一部分~1H和~(13)C谱峰用一般核磁共振方法难于确定归属。本工作采用选择性远程DEPT、一维COSY和-维接力COSY等新技术作了研究,其~1H和~(13)C谱峰归属全部得到确定。结果有助于此类化合物的化学结构测定。     

关附庚素的选择性远程DEPT、一维COSY和一维接力COSY谱的研究

由于谱峰拥挤和重迭、关附庚素的一部分¹H和¹³C谱峰用一般核磁共振方法难于确定归属。本工作采用选择性远程DEPT、一维COSY和-维接力COSY等新技术作了研究,其¹H和¹³C谱峰归属全部得到确定。结果有助于此类化合物的化学结构测定。     

用适配体修饰纳米金做共振瑞利散射光谱探针检测妥布霉素

用硼氢化钠还原氯金酸制备了金纳米粒子(GN),用妥布霉素适配体(Apt)修饰GN可获得较稳定的Apt-GN探针。在pH 6.8 Na₂HPO₄-NaH₂PO₄(PBS)缓冲液及NaCl存在下,Apt-GN探针稳定而不聚集;当有妥布霉素(Tbc)存在时,它与Apt-GN探针中的Apt特异性结合并释放出纳米金,纳米金在NaCl作用下聚集,导致体系在368 nm处的共振瑞利散射光增强。在选定实验条件下,368 nm处的共振散射峰强度的增大值ΔI与抗生素妥布霉素(Tbc)浓度在1.9～58.3 ng·mL-1范围内呈良好线性关系,其线性回归方程为ΔI=35.3c-23,检出限为0.8 ng·mL-1 妥布霉素。分别对10.0,20.0和30.0 ng·mL-1 Tbc平行测定5次,求得其相对标准偏差分别为6.8%,5.0%和4.4%。考察了共存离子对测定38.9 ng·mL-1 妥布霉素的干扰情况。结果表明,当相对误差在±10%以内,80倍Zn2+;40倍L-谷氨酸,Cu2+,Mg2+,Ca2+;20倍葡萄糖、盐酸土霉素;10倍L-苯丙氨酸、甘氨酸;2倍L-天冬氨酸;6倍HSA和BSA不干扰测定。这说明本方法具有较好的选择性。该法用于分析测定妥布霉素滴眼液中的妥布霉素含量,结果令人满意,相对标准偏差在6.5%～7.6%之间,回收率在95.0%～107%之间。     

基于NMR指纹谱相关分析的生物类似药高级结构评价

建立了基于1H NMR指纹技术的生物类似药高级结构相似性分析方法,利用相关系数r和决定系数R2定量评估生物类似药与其原研药的结构相似度。将该方法应用在一种分子量为1620的抗菌性脂肽达托霉素上,比较了其类似药的活性原料成分(API)、类似药制剂与原研药克必信的高级结构相似性。实验结果显示,3个达托霉素样品的谱图存在显著差异,表明达托霉素类似药与其原研药在水溶液中存在结构差异。将该方法应用在分子量为145423的单克隆抗体药物曲妥珠单抗的高级结构比对上。对1个批次的赫赛汀原研药、4个批次的类似药的1H NMR谱进行相似性分析,相关系数r和决定系数 R2的结果显示,曲妥珠单抗的类似药与赫赛汀原研药相似度很高;进一步采用局部相关系数进行谱图分析,得到了曲妥珠单抗类似药与赫赛汀原研药之间的微小差异。研究表明,有效结合NMR指纹分析技术和统计分析方法,将在生物类似药质量控制中发挥重大的作用。     

水稻秸秆接力处理过程中的红外光谱研究

作物秸秆就地焚烧已经和正在引起严重的大气污染,土壤微生物对作物秸秆的较难分解是作物秸秆农业利用的主要限制因子之一。文章采用傅里叶红外光谱(FTIR)分析技术对水稻秸秆接力处理(化学水解—微生物培养)过程进行了研究,分析探讨了接力处理的化学机理。由红外光谱的分析可见,经过接力处理,水稻秸秆半纤维素和纤维素大大降低,C／N比也降低到适合微生物生长的范围,硅元素的含量也降低,水溶性的物质含量升高,其结果与化学分析的结果一致。文章提出的水稻秸秆接力处理方法能为作物秸秆的农业利用提供有效途径。     

二维接力-HOHAHA和NOE差谱法测定甙类化合物的结构

该文提出一种新的二维接力-HOHAHA实验方法.研究结果表明,该方法可用于从高度重迭的谱图中分离出各个糖体的¹H NMR信号,并且与NOE差谱实验相结合可以用于测定甙类化合物中糖体间和糖体与甙元间的连接位置.本方法以¹H NMR为基础,故其灵敏度比以¹³C NMR为基础的甙化位移方法高得多.     

自回归谱分析法在亚毫米波付里叶变换谱中的应用

付里叶变换是目前最常用的谱分析方法,它具有分辩率高、测量速度快、数据处理自动化等优点。但是,它的分辨率受到信号的信噪比、动镜的扫描长度和所用的窗口函数的限制。本文介绍了自回归谱分折法在亚毫米波付里叶变换谱中的应用。它是对取样得到的干涉图进行自回归谱分析,从而得到完整的功率谱信息。它的特点是消除了窗口函数的影响,并可对取样点以外的干涉图进行线性预测,从而大大提高了分辩率。本文详细地介绍了自回归谱分析法应用到亚毫米波付里叶变换谱中的实现方法和得到的结果。实验证明,应用了这种方法以后,现有的亚毫米波付里叶变换谱仪的分辨率可提高4倍左右。     

基于NMR指纹谱相关分析的生物类似药高级结构评价（英文）

建立了基于1H NMR指纹技术的生物类似药高级结构相似性分析方法,利用相关系数r和决定系数R2定量评估生物类似药与其原研药的结构相似度.将该方法应用在一种分子量为1 620的抗菌性脂肽达托霉素上,比较了其类似药的活性原料成分(API)、类似药制剂与原研药克必信的高级结构相似性.实验结果显示,3个达托霉素样品的谱图存在显著差异,表明达托霉素类似药与其原研药在水溶液中存在结构差异.将该方法应用在分子量为145 423的单克隆抗体药物曲妥珠单抗的高级结构比对上.对1个批次的赫赛汀原研药、4个批次的类似药的1H NMR谱进行相似性分析,相关系数r和决定系数R2的结果显示,曲妥珠单抗的类似药与赫赛汀原研药相似度很高;进一步采用局部相关系数进行谱图分析,得到了曲妥珠单抗类似药与赫赛汀原研药之间的微小差异.研究表明,有效结合NMR指纹分析技术和统计分析方法,将在生物类似药质量控制中发挥重大的作用.     

CCD接力测量船体变形研究

在舰船上,不少设备需要导航仪器提供姿态信息,船体变形会引起设备之间的姿态传递误差,导致设备效用降低。为了修正误差,获得精确的设备姿态测量结果,需要一套测量装置对船体变形进行测量。基于CCD的船体变形测量具有非接触性、精度高的优点。但当测量的两设备安装基座之间光路不能通视时,需要采用接力测量方法。阐述了CCD接力测量船体变形方法的原理和模型,并进行了模拟试验。试验结果表明,CCD接力测量船体变形方法可以高精度测量设备之间的相对姿态变化量。     

Exact solution of a coagulation equation with a product kernel in the multicomponent case

In this paper, we obtain the general solution for the continuous Smoluchowski equation in the multicomponent case with a product kernel as a series expansion. The solution of the problem involves the Laplace transform in several dimensions. We obtain a nonlinear partial differential equation (PDE) of the advective kind generalizing the one previously given by other authors for the mono-component case.As in its relative mono-component case, gelation is produced at some point, the conditions for its occurrence being the same as those for the mono-component case, though substituting a sum of derivatives by a derivative in the Laplace transform field. We demonstrate that for a multicomponent particle size distribution (PSD) of multiplicative form, it is sufficient for one of the marginal PSDs to generate instantaneous gelation for the occurrence of instantaneous gelation in the multicomponent PSD.The general solution is applied to several specific cases, a discrete case that recovers a previously known solution, and another two continuous cases which can be used to check numerical methods designed to directly solve the Smoluchowski equation in more general cases.We have compared the solutions for the multicomponent PSD for constant, additive and product kernels and we conjecture about the relation existing between the functional forms for the solutions both in the mono-component and the multicomponent case.Finally, we have analysed the shape of the solutions for multicomponent PSD for constant, additive and product kernels for very small masses of components, obtaining a qualitatively different behaviour for the product kernel. This has effects in the mixing state of the sol phase as time passes.     

基于Lorenz映射的混沌系统分支变换预报规律研究

尽管Lorenz系统具有混沌和非周期性质, 但其分支变换是可预报的.本文以强迫Lorenz系统为数学模型, 基于Lorenz映射, 研究了混沌系统分支变换的预报规律, 将原有关于分支开始变换条件和新分支持续时间的两条一般规律扩展到了3条, 并首次分析了系统当前状态达到变换条件所需时间的预报规律, 从而为预报混沌系统非周期演变提供了另一途径.结果表明: 映射尖点位置为分支变换的临界值, 当变量z超过相应临界值时, 系统在当前分支的运动即将结束, 下一循环将跳跃到另一分支运动; 系统在同一分支循环的次数随极值z_max单调减小, z_max 越小, 达到变换条件需循环的次数越多; 系统在新分支持续的时间是先前分支最大极值z_M 的单调增加函数, z_M越大, 持续时间增加的幅度也越大.此外, 外强迫影响着混沌系统分支变换的预报规律, 其不但使正负分支的变换条件出现差异, 且与新分支持续时间的增加速率和达到变换条件所需时间的递减速率密切相关. 关键词： Lorenz映射 分支变换 外强迫 预报规律     

旋涡流化床颗粒夹带和扬析的数学模型

本文结合气体湍流运动模型，颗粒运动的轨道模型和密相床层动力学的经验关联式，建立了旋涡流化床颗粒夹带和扬析的数学模型，发展了相应的求解程序。用本文提出的数学模型对普通鼓泡流化床中颗粒夹带的计算结果与前人的经验公式相符；对旋涡流化床和普通的鼓泡流化床颗粒扬析的计算结果与实验数据吻合较好。     

Line Broadening and Enthalpy: Some Empirical Calibrations of Solid Solution Behaviour from IR Spectra

Following recent developments in the application of autocorrelation analysis of line broadening in powder absorption IR spectra, the possibility that elastic strain heterogeneities are responsible both for such broadening and for enthalpy variations in solid solutions has been explored systematically. Recent data for five silicate solid solutions, augite-jadeite, almandine-grossular, albite-anorthite, anthophyllite-grunerite and clinoenstatite-clinoferrosilite, are reviewed. Variations in the autocorrelation parameter for line broadening, j corr, scale linearly with calorimetric data for enthalpy variations, j H , associated with cation substitutions and ordering in these systems. It is proposed that, while there may not be a universal calibration of j H in terms of j corr for all structures, it should be possible to produce empirical calibrations for groups of solid solutions with the same basic structure. Variations in j corr at different phonon frequency ranges provide additional insights into the structural mechanisms by which ordering, mixing, displacive and reconstructive processes occur in silicate solid solutions.     

势阱中粒子能级与波函数微扰计算的代数递推公式

利用超位力定理（HVT）和Hellmann-Feynman定理（HFT）,导出了由有精确解的势阱的能级值用微扰法直接计算一维势阱的各级近似能级的普遍代数公式,并导出由能级近似值计算定态波函数近似表达式的代数公式,给出了代数公式具体应用的几个典型一维势阱实例,此法可推广到二维势阱与三维势阱的情形。     

Some Observations about the MOLSCAT

For calculation of cross sections for collisional transitions between rotational levels in a molecule, a computer code, MOLSCAT is available. For the transitions between rotational levels in H₂CS due to collisions with He atom, we have calculated cross sections under the CS approximation, for example, for total energy 11 cm^-1. The calculations have been done for the single energy 11 cm^-1 and for ten combinations. We have found that the cross sections for the single energy 11 cm^-1, differ from those in the first seven combinations, but are in agreement with those in the last three combinations. The reason for the difference in the results appears that the MOLSCAT uses the intermediate data of calculations for one energy, in the calculations for other energies. The agreement with the last three combinations may be understood that when the energy of combination is in the decreasing trend, the cross sections for the first (common) energy are equal. It may be suggested to run the MOLSCAT for a single energy at a time.     

Linear and Fisher Separability of Random Points in the d-Dimensional Spherical Layer and Inside the d-Dimensional Cube

Stochastic separation theorems play important roles in high-dimensional data analysis and machine learning. It turns out that in high dimensional space, any point of a random set of points can be separated from other points by a hyperplane with high probability, even if the number of points is exponential in terms of dimensions. This and similar facts can be used for constructing correctors for artificial intelligent systems, for determining the intrinsic dimensionality of data and for explaining various natural intelligence phenomena. In this paper, we refine the estimations for the number of points and for the probability in stochastic separation theorems, thereby strengthening some results obtained earlier. We propose the boundaries for linear and Fisher separability, when the points are drawn randomly, independently and uniformly from a d-dimensional spherical layer and from the cube. These results allow us to better outline the applicability limits of the stochastic separation theorems in applications.     

Surface excitation probabilities in surface electron spectroscopies

The phenomenon of surface excitation is competitive in nature for elastic and other inelastic scattering processes in surface electron spectroscopies; the knowledge of influence of surface excitations in electron energy loss spectra is then essential for quantitative surface analysis with these spectroscopies. The inelastic scattering of an electron moving in the vicinity of a surface is considered in a self-energy formalism to estimate the contribution of surface excitation in electron-solid interactions via the total surface excitation probability. The formulation uses the optical bulk dielectric function and provides the spatial and angular dependence of the differential and total inelastic cross-sections. The kinetic energy range of probing electrons considered is 100-5000 eV and the numerical evaluation of total surface excitation probabilities are performed for several metals, Au, Ag, Cu, Ni, Fe and Ti; empirical formulae for the surface excitation probability are given for each of these materials and compared with experimental results for the surface excitation parameter. The total surface excitation probability is higher in Ag as compared to other metals under consideration, for identical conditions of electron-solid interactions.