Fuzzy theory in analytical chemistry

The concept of fuzzy theory is described in order to provide the analyst with the means for dealing with vague statements, uncertain observations or the fuzziness of human perception and interpretation, in general. In a theoretical part, basic notions of fuzzy theory are given, such as types of membership functions, operations with fuzzy sets, definitions of fuzzy numbers, points, functions, and relations, and the use of linguistic variables. The difference between fuzziness and probability is outlined. The applications section demonstrates advantages of fuzzy theory methods compared to common mathematical methods with respect to data handling for calibration of analytical methods, to classification of Chromatographie and spectroscopic patterns, to component identification and multicomponent analysis, and to designing fuzzy expert systems for selection of analytical procedures.     

Applications of maximum likelihood principal component analysis: incomplete data sets and calibration transfer

The application of a new method to the multivariate analysis of incomplete data sets is described. The new method, called maximum likelihood principal component analysis (MLPCA), is analogous to conventional principal component analysis (PCA), but incorporates measurement error variance information in the decomposition of multivariate data. Missing measurements can be handled in a reliable and simple manner by assigning large measurement uncertainties to them. The problem of missing data is pervasive in chemistry, and MLPCA is applied to three sets of experimental data to illustrate its utility. For exploratory data analysis, a data set from the analysis of archeological artifacts is used to show that the principal components extracted by MLPCA retain much of the original information even when a significant number of measurements are missing. Maximum likelihood projections of censored data can often preserve original clusters among the samples and can, through the propagation of error, indicate which samples are likely to be projected erroneously. To demonstrate its utility in modeling applications, MLPCA is also applied in the development of a model for chromatographic retention based on a data set which is only 80% complete. MLPCA can predict missing values and assign error estimates to these points. Finally, the problem of calibration transfer between instruments can be regarded as a missing data problem in which entire spectra are missing on the ‘slave’ instrument. Using NIR spectra obtained from two instruments, it is shown that spectra on the slave instrument can be predicted from a small subset of calibration transfer samples even if a different wavelength range is employed. Concentration prediction errors obtained by this approach were comparable to cross-validation errors obtained for the slave instrument when all spectra were available.     

Ligand-protein docking using a quantum stochastic tunneling optimization method

A novel hybrid optimization method called quantum stochastic tunneling has been recently introduced. Here, we report its implementation within a new docking program called EasyDock and a validation with the CCDC/Astex data set of ligand-protein complexes using the PLP score to represent the ligand-protein potential energy surface and ScreenScore to score the ligand-protein binding energies. When taking the top energy-ranked ligand binding mode pose, we were able to predict the correct crystallographic ligand binding mode in up to 75% of the cases. By using this novel optimization method run times for typical docking simulations are significantly shortened.     

Molekulares S=GeCl2 Matrix-IR-Untersuchungen und ab initio SCF-Rechnungen

The Molecule S?GeCl₂. Matrix IR Investigation and Ab initio SCF Calculation Molecular S?GeCl₂ is found in a matrix reaction between the high-temperature molecule Ge?S and Cl₂. A structure analog to that of phosgene can be derived from the isotopical shifts (⁷⁰Ge/⁷²Ge/⁷³Ge/⁷⁴Ge/⁷⁶Ge and ³⁵Cl/³⁷Cl) within the IR spectra. The normal coordinate analysis results for the Ge?S force constant a value of 4.21 mdyn/Å. The spectroscopic results are confirmed by ab initio SCF calculations.     

Optimisation of the connection between TA-MS systems together with improved data interpretation for TA-MS applications

TA-MS provides chemical and thermal response information. In order for this information to be meaningful sampling must be performed with minimum dead volume and without cold spots. Dead volume leads to response lag and peak broadening. Cold spots result in sample condensation, leading to inaccurate data and potentially inlet blockage. This paper describes a hot zone inlet system and 'in-situ' probe both of which provide fast response, zero dead volume sampling directly to the MS. The paper also discusses data interpretation methodologies and introduces 'soft ionisation' as a means of providing simplified analysis of complex mixtures. This revised version was published online in July 2006 with corrections to the Cover Date.     

Information content of data and variables and types of weighting in least-squares regression methods

Algorithms are given for evaluating the relative amount of useful information related to a particular parameter which is carried by individual data points and intervals of the variables. The algorithms provide an efficient means of using the information contained in a set of data. Applications to the optimization of weighting in regression methods are described. Several informational and combined informational-statistical types of weighting are studied as a means of improving the accuracy and precision of the parameters obtained by non-linear regression.     

宗教文化对泉州古城街道活力的影响分析

以泉州古城为例,利用多源数据构建街道活力与其影响因素的分析框架,建立包含街道物理环境影响因素和宗教文化影响因素的街道活力评价指标体系.分析宗教建筑对街道活力的影响,并进一步分析宗教建筑与街道的空间关系对街道活力的影响.研究结果表明：街道活力与街道两侧的寺庙宗祠的数量呈负相关,香火旺盛的寺庙宗祠会提升附近街道的活力,但与寺庙宗祠距离无显著相关关系;在寺庙宗祠入口设置广场或宽敞的步行区可以集聚人气,并在寺庙宗祠周围布置商业或与其他景点结合以形成连续的活力点,有助于提升街道活力.     

区间删失数据下基于OLLGG分布的多参数回归模型的参数估计

该文基于Ⅱ型区间删失数据,在OLLGG分布下提出多参数回归模型,通过线性回归刻画分布参数与协变量之间的关系,并通过极大似然方法给出了模型的参数估计,数值模拟验证了模型参数的估计有良好的性质,将提出的模型应用到血友病患者HIV感染的数据中,发现提出的模型对数据有灵活的拟合效果.     

基于多维行为分析的窃电高风险客户精准定位方法

窃电行为对国家电力系统及供电公司造成了极大的损失,故反窃电技术是电力行业的重要研究方向之一。传统的窃电用户定位方法存在定位不准确、查处效率低等问题,为了解决上述问题,提出基于多维行为分析的窃电高风险客户精准定位方法。首先通过相关矩阵R及特征值谱熵正则化完成用户数据去噪,其次在UFS-MI模型内提取用户数据特征,分析用户用电的多维行为,最后根据逻辑回归算法完成窃电高风险客户的精确定位。实验结果表明,所提方法的窃电高风险客户定位精准度较高,误判率较低,整体定位效果较好。     

数字孪生驱动下永磁同步电机滑模变结构一体化解耦控制

提出数字孪生驱动下永磁同步电机（PMSM）滑模变结构一体化解耦控制方法,改善永磁同步电机控制能力。构建基于数字孪生技术的永磁同步电机控制结构,通过设备层采集实际永磁同步电机运行数据及环境数据,作为数字孪生驱动数据来源,孪生建模层依据获取永磁同步电机数据,构建永磁同步电机的数字孪生驱动模型以及虚拟场景,经虚拟模型与虚拟场景耦合后,在虚拟场景中还原永磁同步电机运行状态;在孪生控制层中设计精确线性化解耦控制方法,并构建速度、电流一体化滑膜解耦控制器,在虚拟环境中通过解决永磁同步电机速度与电流之间的非线性耦合问题,完成实体电机解耦控制;同时数字孪生控制结构各层之间通过孪生数据传输实现数据交换与指令下发,实现有效的电机控制。经实验验证：经该方法控制后,永磁同步电机可在负载突加与突卸状态下保持平稳的电流与转矩,同时还可以迅速调整电机转速,使电机保持在理想状态下运行。