基于交互式自模型混合物分析的近红外光谱波长变量优选方法

为了提高近红外光谱定量分析的预测精度和建模效率,提出了一种基于交互式自模型的混合物分析的波长优选方法,根据光谱各波长变量的纯度值和标准差值,选择含有用信息的波长变量,并引入相关权函数解决变量间共线性问题.通过依次迭代选择的变量建立定量校正模型,由交互验证均方根预测误差(RMSECV)确定最佳波长变量个数.应用该波长变量优选方法对具有不同葡萄糖含量的两组(四成分葡萄糖水溶液实验和人体血浆实验)近红外光谱数据进行分析,两组数据中分别只选择了全部变量的0.3%建立定量校正模型,其验证集葡萄糖浓度的均方根预测误差(RMSEP)分别减少为669和15 mg/L.与全谱范围及优选波段建立的定量校正模型比较,本方法能够通过波长变量优选最小化冗余信息、提高预测精度及建模效率.     

径向基函数网络在近红外人体无创伤血糖浓度检测基础研究中的应用

在近红外无创伤血糖浓度检测的基础研究中，对于多组分的混合物的分析，常因光谱与样品浓度之间呈现非线性响应，使得基于线性模型的校正方法失效。本文讨论了非线性校正方法径向基函数神经网络( RBFN )的有效性，并与线性校正方法中的主成分分析和偏最小二乘法作了对比研究。验证实验所用样品为①葡萄糖水溶液②包含牛血红蛋白和白蛋白的葡萄糖水溶液，结果表明：在①实验中PLS模型和RBFN预测标准偏差分别为8．2、8．9；在②实验中分别为15．6、8．8。可见在样品组分增多时，RBFN算法较线性PLS方法建立的模型预测能力强。     

浓度分段模型应用于人体血清葡萄糖的FTlR/ATR光谱分析

利用傅立叶变换红外光谱（ FTlR）和衰减全反射（ ATR）技术,建立了人血清葡萄糖的快速定量分析方法。根据葡萄糖水溶液与纯净水差谱得到葡萄糖的指纹吸收波段（1200~900 cm-1）,分别在全谱（4000~600 cm-1）和指纹波段建立偏最小二乘法（ PLS）模型,指纹波段的预测效果明显好于全谱。选择指纹波段后,提出一种根据浓度分段分别建模然后进行组合的建模方法。按照全部样品、低浓度样品、高浓度样品分别建立模型后,根据3个模型进行综合决策。应用独立的检验集对样品进行测试表明,按葡萄糖浓度范围分段建立组合模型的预测效果优于基于全部样品建模的预测效果。对于分段阈值附近的样本,低浓度和高浓度模型的预测效果差别不大。浓度分段组合模型的预测均方根偏差（ RMSEP）和预测相关系数（ Rp ）分别为0.732 mmol/L和0.948。     

仿凝集素微凝胶的制备及葡萄糖响应特性

葡萄糖响应高分子微凝胶有望用于设计构建可持续检测葡萄糖并输出反馈的系统，但如何实现高选择性识别水环境中葡萄糖是较大挑战.本工作优化了仿凝集素(s-Lectin)的合成路线，通过迈克尔加成、酰胺缩合等，4步合成出s-Lectin，进而将其包裹于聚异丙基丙烯酰胺(pNIPAM)交联网络中，制备得到新型的葡萄糖响应微凝胶.随着葡萄糖浓度在0～30 mmoL范围内逐渐增大，浊度法研究表明该仿凝集素微凝胶水溶液消光度呈现持续降低的趋势，而动态光散射法测试结果显示仿凝集素微凝胶粒径变大，即微凝胶发生了溶胀.进一步采用动态光散射法研究对葡萄糖、果糖、甘露糖、半乳糖等的识别选择性，结果表明仿凝集素微凝胶仅在水溶液中加入葡萄糖时发生溶胀，而在加入果糖、甘露糖、半乳糖等时则几乎没有发生粒径变化，展示出可高选择性识别水环境中葡萄糖的特性，有望用于血糖检测.     

基于曼尼希反应的聚集诱导发光效应用于灵敏检测甲醛

甲醛是一类无色无味的致癌物，严重危害人类健康，对甲醛的灵敏检测在环境监测、毒物评估、临床诊断和医疗保健等领域均具有非常重要的意义。本研究合成了具有聚集诱导发光（Aggregation-induced emission, AIE）效应的荧光探针四羟基四苯基乙烯（Tetra(4-hydroxyphenyl)ethylene, TPE-4OH），在1,2,4,5-苯四胺四盐酸盐（1,2,4,5-Benzenetetramine tetrahydrochloride, BTA）存在条件下，TPE-4OH与溶液中的甲醛分子发生曼尼希反应，从而发生AIE，引起荧光增强，荧光强度变化与体系中的甲醛水平密切相关，通过测定TPE-4OH的AIE强度可检测水溶液中甲醛浓度。优化了反应物浓度、溶液pH值以及反应时间等条件。在最优条件下，本方法检测甲醛的线性范围为1.0～2000μmol/L，检出限为1.0μmol/L。将本方法应用于血清样品中甲醛浓度的检测，回收率为93.7%～106.4%，显示了良好的实际应用价值，为水溶液中甲醛浓度检测提供了一种新方法。     

基于超高效液相色谱-质谱红花药材指纹图谱的建立

以红花为研究对象，建立超高效液相色谱-质谱（UPLC-MS）指纹图谱分析方法，为红花药材质量鉴别提供借鉴.通过考察检测波长、梯度洗脱条件、提取溶剂、提取方法等因素，在最优条件下对20个产地的红花样品进行分离分析.色谱柱：Thermo Hypersil Gold C₁₈，100 mm×2.1 mm，1.9 μm，流动相：0.1%甲酸水溶液（A）-乙腈（B）；流速：0.3 mL/min；柱温：30℃；检测波长：270 nm；进样量：2 μL，质谱条件：鞘气流速：45 arb，辅助气流速15 arb，雾化电压：3.3 KV，离子传输管温度：350℃，辅助气加热温度：400℃.试验结果：共确定了67个共有峰，通过UPLC-MS指认了其中11个共有峰，对20批不同产地的红花药材指纹图谱进行了相似度评价，其相似度在0.687~0.971之间.建立的UPLC-MS指纹图谱可为红花药材的质量控制提供参考依据.     

以组织液为替代媒介的无创血糖检测研究进展

人体血糖检测是糖尿病治疗的关键问题。传统的血糖检测方法需要采血,造成患者的痛苦和感染的危险。而在无创血糖检测方法的研究中,血液中存在的高浓度大分子物质会造成光谱的严重散射,检测精度无法达到医用需求。因此,避开血液中大分子物质的干扰,寻找到血液的替代媒介是无创血糖检测研究的突破口。本文总结了人体中组织液与血液的关系、组织液在皮肤中的分布、组织液与血液葡萄糖的含量关系、组织液与血液葡萄糖的时间延迟、组织液葡萄糖的检测研究进展,证明了借助组织液作为替代媒介进行近红外无创血糖检测的可行性。     

基于平行因子分析法提高近红外无创血糖校正模型稳健性的研究

采用近红外光谱进行无创血糖检测时, 样品背景变动造成的预测集样本与校正集样本量测体系不一致的问题是导致预测精度低的原因之一. 提出一种将母体背景作为变量引入回归建模中, 结合各个母体背景下的样本光谱信息构建三维光谱矩阵以提高校正模型稳健性的分析方法. 将平行因子分析(PARAFAC)与多元线性回归(MLR)相结合, 对人体三层皮肤模型的蒙特卡罗模拟实验和葡萄糖水溶液及其混合物的离体实验进行了验证. 实验结果表明, 与传统的单一母体背景所建立的偏最小二乘模型相比, 将母体背景作为建模元素采用PARAFAC-MLR法所建立的校正模型具有更好的预测能力和稳健性.     

HPLC法测定多西他赛中间体及其光学异构体

建立了HPLC法测定多西他赛中间体（1）及其光学异构体（2）。色谱柱采用Lux Cellulose-2手性柱（250 mm×4.6 mm, 5μm），以0.02%三氟乙酸溶液/甲醇（15∶85）为流动相，等度洗脱。检测波长为210 nm，柱温为25℃，流速为0.4 mL/min，进样量为5μL。结果显示，1和2分别在0.1～0.8 mg/mL和0.35～8.73μg/mL内线性关系良好，检测限分别为0.12、0.14μg/mL。低、中、高浓度的平均回收率（n=3）分别为100.8%、100.6%、101.3%,RSD分别为0.7%、0.5%、0.7%；精密度RSD(n=6)为0.6%。建立的方法灵敏度高、操作简单，可用于1中2的测定，也为多西他赛合成过程中的质量控制提供了参考。     

茜素红S光度法测定人血清白蛋白

１引言人体血液中的白蛋白是形成血浆胶渗压的主要成分，它在维持体液的正常分布，以及保持血容量及血压等方面起重要作用。同时，血浆白蛋白对人体具有营养作用。已有报道将它作为人体营养健康和疾病诊断、疗效观察的重要指标及资料数据。分析、测定、研究血浆中白蛋白的含量，对人体健康和生命科学的研究可提供重要的科学依据和研究价值。２实验部分２．１仪器与试剂ＵＶ－２６５分光光度计（Ｓｈｉｍａｄｚｕ）；７２４微机型分光光度计（上海光学仪器厂）；８２１型ｐＨ计（中山大学电子厂）。茜素红Ｓ（ＡＲＳ）５．０×１０－４ｍｏｌ…     

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.     

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。     

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.

     

Synthesis of phenolic components of Grains of Paradise

Two vanilloids, (5E)-8-(4-hydroxy-3-methoxyphenyl)oct-5-en-4-one (1) and 4-[3-hydroxydecyl]-2-methoxyphenol (2), isolated from the dried seeds of Grains of Paradise (Aframomum melegueta), were synthesized; the latter compound was made as the S-enantiomer and the material derived from the seeds was found to be a 1:1.7 mixture of the R and S isomers. The synthetic route used should allow the preparation of analogs having extended alkyl chains and consequently different lipophilicity, and 3, a homolog of 2, was also prepared.     

Summary of development of the theory of stability of colloids and thin films

In this review, the research of the author in the field of colloidal systems is summarized. The factors influencing colloidal stability are systematized and analyzed. Examples are presented to illustrate the practical utilization of the theory of stability of colloids and thin films.This review was prepared on the basis of the works of the author, which were awarded the State Premium for 1991 in the field of science and technology, chemistry section.Institute of Physical Chemistry, Russian Academy of Sciences, 117915 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1708–1717, August, 1992.     

Study of hydration of two cements of different strengths

Main hydration products of two cement pastes, i.e. CSH-gel, portlandite (P) (and specific surface S) were studied by static heating, and by SEM, TEM and XRD, as a function of cement strength (C-33 and C-43) hydration time (th) and subsequent hydration in water vapour.Total change in mass on hydration and air drying, M_o, increased with strength of cement paste and with hydration time. Content of water escaping at 110 to 220°C, defined as water bound with low energy, mainly interlayer and hydrate water, was independent on cement strength but its content increased with (th). Content of chemically bound (zeolitic) water in CSH-gel, escaping at 220-400°C, was slightly dependent on strength and increased with (th). It was possibly derived from the dehydroxylation of CSH-gel and AFm phase. Portlandite water, escaping at 400-500°C, was independent on cement strength and was higher on longer hydration. Large P crystals were formed in the weaker cement paste C-33. Smaller crystals were formed in C-43 but they increased with (th). Carbonate formated on contact with air (calcite, vaterite and aragonite), decomposed in cement at 600-700^oC. It was high in pastes C-33(1 month) and C-43(1 month), i.e. 5.7 and 3.3%, respectively; it was less than 1% after 6 hydration months (low sensitivity to carbonation) in agreement with the XRD study showing carbonates in the air dry paste (1month), and its absence on prolonged hydration (6 months) and on acetone treatment. Water vapour treatment of (6 months) pastes or wetting-drying increased this sensitivity.Nanosized P-crystals, detected by TEM, could contribute to the cement strength; carbonate was observed on the rims of gel clusters.This revised version was published online in November 2005 with corrections to the Cover Date.     

氯氧化镁生成热的研究

用氧化镁氯化镁水溶液制备了8水合氯氧化镁[nMg(OH)2·MgCl2·8H2O], 并测定了其在盐酸中的溶解热, 实验结果表明, 氯氧化镁溶解热与n值呈线性关系, 根据溶解热求出5Mg(OH)2·MgCl2·8H2O和3Mg(OH)2·MgCl2·8H2O的生成热分别为-7727.1和5888.1kJ·mol^1^-。     

Thermodynamics of the formation of oxosulfides of rare-earth elements

The enthalpies of solution of several oxosulfides of rare-earth elements and the high-temperature enthalpies of oxosulfides and oxosulfates of lanthanum and yttrium were measured using solution calorimetry and high-temperature microcalorimetry techniques. Standard enthalpies of formation and some thermodynamic properties of oxosulfides and oxosulfates were calculated. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2 pp. 294–297, February, 1997.     

探究“铁的锈蚀条件”实验创新设计

设计了铁的锈蚀实验,说明了铁钉的处理方法,增加了温度、酸、碱的影响条件,实现了铁跟蒸馏水及空气中氧气快速反应而生锈,使实验在5 min左右就能够得到准确的结果。