差分拉曼光谱技术结合K-means聚类法对牙膏的快速分类

建立了差分拉曼光谱技术结合K-means聚类法对牙膏快速分类的方法。对37个牙膏样品编号,将其分别涂抹于载玻片上,晾干,使用差分拉曼光谱仪进行扫描。调用R语言软件中fpc、factoextra、cluster数据库中的na.omit和scale函数对37个牙膏样品的差分拉曼光谱数据进行标准化处理,利用手肘法和Gap Statistic算法优化聚类数。在最佳聚类数为4的条件下,通过K-means聚类法对牙膏样品进行分类,并使用层次聚类分析法进行验证。结果显示,37个牙膏样品被分为4类,并且两种方法的分类结果一致。     

谱图相似度分析结合保留指数对单萜烯同分异构体的GC—MS定性分析

运用欧氏距离的最短距离聚类分析法,对在质谱数据库NIST02.L检索到的37种单萜烯同分异构体的93张质谱图进行了分类.结果显示,单萜烯被分成5类,大部分单萜烯聚到1类,包括30种单萜烯的77张质谱图.但部分谱图很近似,仅用传统的质谱库匹配鉴定其结构存在一定的困难.采用改进的谱图相似度分析结合保留指数实现了有效定性,并将该方法用于实际样品的定性分析.     

氮磷检测器裂解气相色谱法区分嗜热脂肪芽孢杆菌的研究

 ]用氮磷检测器和氢焰检测器分别对21株嗜热脂肪芽孢杆菌及其类属菌进行裂解气相色谱分析。借助电子计算机用聚类分析法解析细菌的裂解气相色谱图，所得树状谱中菌株间的关系与常规分类法和数值分类结果基本一致。实验结果表明，氮磷检测器在生物大分子和生物医学材料鉴别分析工作中的重要价值。     

聚类分析法用于西洋参样品分类研究

建立西洋参药材分类方法;分别采用电感耦合等离子体质谱（ICP—MS）法、高效液相色谱（HPLC）法以及蒽酮-硫酸分光光度法,对12个西洋参样品中的15种无机元素、7种人参皂苷和多糖进行测定,用SPSS聚类分析法对12个西洋参样品进行聚类分析;结果表明：以4种不同的聚类变量进行聚类分析,其聚类分组结果并不一致,将几种有效成分综合为聚类变量,对西洋参进行分类更为科学合理;聚类分析法是西洋参分类分析的有效方法,对西洋参品种与质量的鉴定有一定的理论意义和实用价值。     

利用拉曼光谱对塑料拖鞋鞋底样品的分类研究

为建立案件现场常见塑料拖鞋鞋底物证的分类方法,利用拉曼光谱对30个不同品牌、不同系列的塑料拖鞋鞋底样品进行了检验并进行分类。同时,结合多元统计学,分别利用系统聚类法、相关性分析法与主成分分析法对实验结果进行分析。结果表明,该方法简便快速、实验结果准确可靠,且无损检材,对样品的分类效果较好。     

超光谱技术结合化学计量法区分直液式走珠笔墨迹种类

为了填补直液式走珠笔墨迹种类区分的空白,试验对市面上常见的29种直液式走珠笔墨迹样品进行了400～1 000nm光谱区间的超光谱成像,将得到的光谱数据进行简单的平滑预处理后,按照其光谱走势进行了初步的鉴别分类,采用SPSS.25分析软件中的沃尔德系统聚类分析法进一步分类,并采用主成分分析法评价了聚类分析的分类结果。试验结果表明:按照650～1 000nm光谱区间曲线上升趋势的差异,可将29个墨迹样品分为第Ⅰ大类和第Ⅱ大类,根据系统聚类分析的树状图和按集中计划表绘制的散点图能够进一步将这29种墨迹样品分为8小类,利用主成分分析法分别提取Ⅰ、Ⅱ大类光谱数据中7个和4个主成分,其中,前两个主成分累计方差贡献率分别达到了87%,97%,用其绘制主成分得分图,结果显示8个小类中的样品均能聚在一起,表明系统聚类效果良好。     

基于多变量-系统聚类分析法区分蓝色圆珠笔色痕

综合应用不同的检验方法对110支不同产地、品牌的蓝色圆珠笔油墨进行检验及种类鉴定。采用气相色谱-质谱法和薄层色谱法分别研究了圆珠笔油墨中的溶剂组成和染料组成。通过数据预处理,分别建立了不同样品气相色谱法和薄层色谱法的共有谱图,采用二值法对特征数据进行提取,将定性信息数量化,将欧氏距离的平方作为样品之间差异的量度进行系统聚类分析,并将分类结果用于判别分析,建立相应的判别式函数。结果表明,基于多变量的系统聚类结果由于同时考察油墨的溶剂和染料在组成上的差异,将110支不同品牌、产地的蓝色圆珠笔分为了29类,可以达到品牌之间的区分和认定,较依据单一检验手段得到的分类结果更为精确、系统。尝试结合判别式函数对未知色痕进行分类,由于样本量较少,因此交叉验证得到的分类正确率仅为47.7%,但通过本实验将化学计量学中的相关算法引入到油墨种类的鉴别中,为添改文件、文件形成时间的检验提供了更加准确的结果,为建立油墨样本库提供了数据支持。     

PyGC法对海洛因样品定量分析方法的改进

本文采用PyGC法对不同来源的海洛因进行了分类研究,由于实验精确度的要求,对裂解气相色谱的进样方法进行了改进,提高了实验数据的重复性。     

X射线荧光光谱结合聚类分析对橡胶轮胎的检验

应用X射线荧光光谱结合系统聚类分析对30种不同的橡胶轮胎样本进行检验研究。利用X射线荧光光谱仪对橡胶轮胎中的主要元素及其含量进行测定,根据测定结果使用聚类分析对样本进行分类。选择最长距离法作为类与类之间距离的定义方法,采用平方欧式距离作为度量区间描述样品间亲疏程度进行系统聚类,最终将30个样本分为12类。该方法简单易行,分类结果可靠且无损轮胎样本,为实际案件的橡胶轮胎检验提供了一种检验思路。     

基于分层聚类的黑色签字笔笔迹拉曼光谱研究

提出一种结合分层聚类和判别分析对笔迹成分进行分类检验的方法。利用激光显微共聚焦拉曼光谱仪对收集的市面上常见的130支黑色签字笔笔迹样本进行检测。对测量数据进行Savitzky-Golay卷积平滑和Z-score标准化处理,利用组间连接法、组内连接法和离差平方和法三种分层聚类方法对数据进行分类,将三种聚类方法所得分类结果作为判别依据进行判别分析,检验聚类方法的正确率。结合聚类树状图与正确率,最终选择在分类数为4时原始分类结果正确率为100%、留一交叉验证分类结果正确率为98.5%的离差平方和法,提出了适用于黑色签字笔笔迹拉曼光谱数据的分层聚类方法和判别验证方法。     

利用手持技术改进测定乙醇分子结构实验

利用压强传感器代替排水集气法,改进测定乙醇分子结构实验的仪器装置,并探索最佳反应条件。另外,设计两个空白实验,结合压强变化曲线对实验误差进行相关讨论。     

光谱仪测试范围的扩展

由于石化行业的生产需要，其材质的使用具有多样性和广泛性，经常会出现顾客委托的测试样品的一个或几个元素跨越光谱仪现有测试程序测量范围的情况。本法通过对光谱仪测试原理的认识，根据光谱仪的测试能力及标样的采集，实现了一个或几个元素测量范围的扩展，并对其测量的影响因素进行了研究。     

Influence of viscosity of medium on processes of oxygen quenching of excited states of mesoporphyrin

The oxygen quenching rate constants for singlet and triplet excited states of the dimethyl ester of mesoporphyrin IX increase with decreasing viscosity of the medium and reach a maximum at a viscosity of approximately 0.4 mPa·sec, after which the rate constants begin to decrease. The drop in rate constant with increasing fluidity of the medium may be related to a nonequilibrium character of the elementary act in the interaction of the reactants in the solvent cage. In viscous media such as isopropyl alcohol, isobutyl alcohol, and isoamyl alcohol, the reaction radius is greater than the sum of the radii of the reacting particles. The long-range character of these processes is due to the relatively weak dependence of the quenching probability on distance.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 25, No. 2, pp. 161–167, March–April, 1989.     

Dichroism of absorption and polarization of phosphorescence of molecules of the closed form of nitrobenzospirothiopyran

The spectral-polarization characteristics of absorption and phosphorescence of molecules of the initial form of nitro-substituted indolinospirobenzothiopyran were studied in oriented polyethylene films and in solutions with different polarity. An oscillator model of the electron transitions responsible for the formation of absorption and luminescence spectra was suggested. It was established that the principal differences in the spectral and photophysical properties of the compound studied and its oxygen-containing analog are associated with the fact that the electronegativity of the S atom is lower than that of the O atom. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1143–1146, June, 1997.     

Determination of heats of detonation and influence of components of composite explosives on heats of detonation of high explosives

The heats of detonation of 20 simple high explosives and explosive mixtures were determined by means of an adiabatic detonation calorimeter designed by the authors. The results indicated that the performance of the instrument was reliable and the experimental data were very accurate. For explosive mixtures, there was a linear accumulative relationship between the heats of detonation of the explosive mixture and its components. Accordingly, the heats of detonation of explosive mixtures could be calculated directly from the heats of detonation of simple explosives and the characteristic heats of other components. The experiments showed that the gold or brass shell of the cylindrical charge could be substituted by a thick-walled porcelain shell, which had the advantage of cheapness.

     

物质分配系数的测定实验改进

实验教学目的是从解决实际问题出发,以实验技术训练和实验设计思想培养为目标。介绍了将单一的物质分配系数测定实验改进为综合实验,提高了实验效果及实验资源利用率。     

Neutral diterpenoids of oleoresins of five species of conifers of Transcarpathia

The compositions of the neutral diterpenoids of the oleoresins of five species of conifers growing in the Transcarpathia have been studied. It has been found that the oleoresins ofAbies alba M.,Larix decidua M., andPicea excelsa L. contain more than 50% of neutral diterpenoids. The group and qualitative compositions of the oxygen-containing diterpenoids have been determined. In the oleoresins ofAbies alba,Picea excelsa, andPicea abies tertiary alcohols — cis-abienol and isocembrol — predominate, while inLarix decidua the main component is the hydroxy ester larixyl acetate. Primary alcohols related to the resin acids have been found in all the oleoresins investigated. Features of the distribution of diterpenoids according to the species of conifers have been revealed. The results obtained are necessary for the chemotaxonomy of conifers of the family Pinceae.Novosibirsk Institute of Organic Chemistry, Siberian Branch, Academy of Sciences of the USSR. Translated from Khimiya Prirodynkh Soedinenii, No. 6, pp. 812–816, November–December, 1988.     

Calculation of enthalpies of hydrogenation of hydrocarbons

Sets of hydrogen molecule equivalents have been developed which permit the calculation of hydrogenation of different types of carbon-carbon bonds from ab initio total energies (3-21G and 6-31G* basis sets, and, to a more limited extent, for MP2/6-31G* data) of reactants and products. The calculated enthalpies of hydrogenation are in good agreement with experiment for unstrained molecules, with average errors on the order of 2 kcal/mol. The 6-31G* equivalents allow the enthalpies for strained molecules to be calculated accurately, but the 3-21G equivalents do not. The equivalents for both basis sets have been tested by calculating the enthalpies of hydrogenation of carbon-carbon bonds in nitrogen- and oxygen-containing organic molecules, free radicals, and classical carbocations. The results are in good agreement with experiment in most cases.     

非那雄胺合成工艺改进

非那雄胺能抑制5α-还原酶的活性,明显降低二氢睾酮水平,是一种治疗良性前列腺增生的有效药品。该合成工艺以甾烯酮酸为原料,将其与氯化亚砜反应,无须分离即与叔丁胺反应得17β-酰胺化合物,再氧化开环,环合,氢化,脱氢合成了非那雄胺。经元素分析、IR、1HNMR、13CNMR、MS分析表征了其结构。该法无须使用昂贵的2,2-二吡啶二硫化物和剧毒药品苯亚硒酸酐,且以乙酸铵代替氨气,降低了对设备的要求和腐蚀,更适用于工业生产。