聚丙烯酸-铕-二苯甲酰甲烷配合物及其荧光性质的研究

将铕的有机配合物NaEu(DBM) 4与聚丙烯酸反应获得铕配位聚合物 (PAA Eu3+ DBM) .此配位聚合物是白色固体 ,不溶于大部分有机溶剂 ,只能溶于丙三醇和异丙醇的混合溶剂 .采用红外光谱、紫外光谱、X射线光电子能谱、电导率、元素分析和荧光光谱等手段对其结构和荧光性质进行表征 ,确定其配位组成和结构即每个铕离子分别与一个DBM分子和PAA分子中二个链节羧基发生配位 .荧光光谱表明PAA Eu3+ DBM有很好的荧光性     

爪形大分子柠檬酸-1,3-丁二醇-硬酯酸十六醇的合成、表征与降滤性质研究

以1，3-丁二醇、柠檬酸为原料，设计、合成了以1，3-丁二醇为核心的柠檬酸-1，3．丁二醇-柠檬酸（cBc）爪状物小分子；再用酯化反应依次与带有功能化集团的硬酯酸、十六醇接枝合成了多元酯类爪形大分子柠檬酸-1，3-丁二醇-柠檬酸-硬酯酸-十六醇（CBC-SH）．采用核磁共振、红外光谱对合成的两种化合物进行了结构表征，表明合成的CBC和CBC-SH与所设计的分子结构相吻合．元素分析确定了CBC和CBC-SH的化学组成依次为C16H22O14和C98H184O15．合成的CBC-SH溶于非极性的有机溶剂，不溶于水．将CBC-SH按600μg／g的加剂量添加到不同的轻柴油中，柴油的冷滤点可降低6℃．     

[Li（DME）3][η^5—MeCp）Nd（t—Bu）3[的合成及其对苯乙烯的催化聚合

将ＭｅＣｐＮｄＣｌ１．２ＬｉＣｌ，ｎＴＨＦ和２摩尔（ｇ－ＢｕＬｉ于四氢呋喃和戊烷混合溶剂中反应，合成得到一种新的阴离子型配合物用元素分析，红外光谱等作了表征，配合物溶于苯乙烯，可单独引发苯乙烯本体聚合，得无规聚苯乙烯。     

疏水缔合型丙烯酰胺类聚合物Ⅰ.疏水单体N-苯基甲酰胺-丙烯酰胺的合成与表征

通过异氰酸苯酯和丙烯酰胺(AM)的取代反应,制备了疏水缔合型单体N-苯基甲酰胺-丙烯酰胺(HMAM)。用红外光谱、核磁共振氢谱、质谱、元素分析和差示扫描量热仪对HMAM进行表征。结果表明,HMAM单体含有疏水和亲水基团,可用于制备新型水溶性疏水缔合型聚合物,该聚合物不溶于水和丙酮等强极性溶剂,但能溶于二甲亚砜和N,N-二甲基甲酰胺等中等极性的溶剂中。     

钛酸纳米管的化学修饰及发光性能的稳定化

钛酸纳米管表面富有羟基, 利用十六醇与Ti-OH发生脱水反应对钛酸纳米管进行化学修饰. 通过透射电子显微镜、红外光谱和荧光光谱等方法研究了表面修饰对钛酸纳米管的结构及光学性质的影响. 与未修饰的钛酸纳米管相比, 不溶于有机溶剂的钛酸纳米管修饰后溶于氯仿、甲苯中, 为进一步用LB膜技术组装钛酸纳米管提供了条件, 并且钛酸纳米管表面修饰的有机层有效抑制了纳米管表面对水的吸附, 解决了钛酸纳米管在空气中久置或有水气氛下特殊的可见区吸收和荧光发光现象受到影响的问题, 使钛酸纳米管的发光性质稳定, 为钛酸纳米管的广泛应用奠定了基础.     

乙二胺基乙磺酸钠的合成与表征

乙二胺基乙磺酸钠是水性聚氨酯合成中重要的亲水性扩链剂, 又可作为有机中间体、生化试剂应用于其它领域.采用乙二胺(EDA)和2-氯乙磺酸钠反应合成乙二胺基乙磺酸钠, 由红外光谱(FTIR)、核磁氢谱(1H NMR)和碳谱(13C NMR)、X射线衍射(XRD)、元素分析等手段表征了产物的结构与特性. 在EDA与2-氯乙磺酸钠物质的量比为6.5∶1时, 合成产物中乙二胺基乙磺酸钠含量高达94.4%. 产物极易溶于水, 微溶于甲醇, 乙醇, 不溶于丙酮, N,N-二甲基甲酰胺, 四氯化碳, 氯仿等有机溶剂.     

铽-噻吩甲酰三氟丙酮-聚丙烯酸的结构及荧光性质

将铽的有机配合物NaTb(TTA)4与聚丙烯酸反应获得铽配位聚合物（Tb-TTA-PAA)。此配位聚合物是褐色固体，不溶于大部分有机溶剂，只能溶于丙三醇和异丙醇的混合溶剂。采用红外光谱、紫外光谱、X射线光电子能谱、电导率、元素分析和荧光光谱等手段对其结构进行表征，确定其配位组成和结构即每个铽离子分别与一个TAA^-离子和PAA分子中二个链节羧基发生配位，得到该配合物的结构。Tb^3 离子在配合物Tb-TTA-PAA中含量为29.98%。荧光光谱表明，常温下配合物在紫外光下发出强荧光，主要是Tb离子的^5D4→^7F5的能量传递。     

杂多酸在活性炭表面含氧基团上的化学键合作用

杂多酸作为一种新型多功能催化剂，近年来匕成为催化领域的研究热点之一［’l杂多酸在均相对许多反应表现出优异催化性能，正逐步为工业催化过程所采用问．较早的研究表明，吸附在活性炭上的杂多酸可部分牢固地存留干其表面不被溶脱，并可保持一定的催化活性＊．关干活性炭表面上杂多酸吸附作用的本质，一直没有明确的结论．本文通过吸附在活性炭表面和溶于含氧有机溶剂中杂多酸的光谱特征，探讨活性炭表面上杂多酸吸附的化学键合作用．1实验部分（且）药品：杂多酸均为市售商品，未经任何处理，直接使用．硅钨酸分子式为儿出风。0。。‘24…     

光谱带宽与分析测试误差的关系

研究了光谱带宽与分析测试误差的关系．从理论上阐明了光谱带宽会引起吸收光谱仪器的分析测试误差,并给出了计算公式．用青霉素钠、青霉素钾的分析测试数据和文献报道的数据,进一步说明了光谱带宽对分析测试误差的影响．分析测试工作者一定要特别重视对光谱带宽的选择．     

稀土离子及其配合物对二棕榈酰磷脂酰乙醇胺酯双层结构的影响

随着稀土在工农业和医疗保健上的广泛应用，稀土的生物无机化学研究受到了普遍的关注．以往的研究多集中在稀土离子的宏观毒理学[1]，而研究稀土离子与生物膜的作用较少[2]．稀土的生物小分子配体的配合物与生物膜作用的研究则未见报道．本文介绍了用拉曼光谱研究稀土离子及其柠檬酸、二乙三胺五乙酸（DTPA）配合物对二栋相酸乙醇胺（DPPE）脂双层的流动性以及碳氢链的构象转变和晶格有序性排列的影响．1实验部分DPPE系Sigma公司产品。La2O3（99．9％）为跃龙化工厂产品，柠檬酸、DTPA为北京化工厂产品．L3Cl3溶液由L32O3溶于盐酸…     

Coherent two-dimensional infrared spectroscopy: quantitative analysis of protein secondary structure in solution

We present a method to quantitatively determine the secondary structure composition of globular proteins using coherent two-dimensional infrared (2DIR) spectroscopy of backbone amide I vibrations (1550-1720 cm(-1)). Sixteen proteins with known crystal structures were used to construct a library of 2DIR spectra, and the fraction of residues in α-helix, β-sheet, and unassigned conformations was determined by singular value decomposition (SVD) of the measured two-dimensional spectra. The method was benchmarked by removing each individual protein from the set and comparing the composition extracted from 2DIR against the composition determined from the crystal structures. To highlight the increased structural content extracted from 2DIR spectra a similar analysis was also carried out using conventional infrared absorption of the proteins in the library.     

Excitonic effects in two-dimensional vibrational spectra of liquid formamide

The linear and two-dimensional infrared (2DIR) responses of the amide I vibrational mode in liquid formamide are investigated experimentally and theoretically using molecular dynamics simulations. The recent method based on the numerical integration of the Schr?dinger equation is employed to calculate the 2DIR spectra. Special attention is devoted to the interplay of the structural dynamics and the excitonic nature of the amide I modes in determining the optical response of the studied system. In particular, combining experimental data, simulated spectra and analysis of the simulated atomic trajectory in terms of a transition dipole coupling model, we provide a convincing explanation of the peculiar features of the 2DIR spectra, which show a substantial increase of the antidiagonal bandwidth with increasing frequency. We point out that, at variance with liquid water, the 2DIR spectral profile of formamide is determined more by the excitonic nature of the vibrational states than by the fast structural dynamics responsible for the frequency fluctuations.     

近红外光谱相似性评估结合局部回归方法无损检测苹果糖度

基于Bayesian相似性评估方法结合偏最小二乘局部回归,对苹果近红外数据库进行数据挖掘。通过相似性计算方法搜索出与预测样品相近的近红外光谱,形成校正子集后采用局部回归方法获得待测样品的相关信息。该方法所建立局部模型的平均检验标准偏差(SEV)约为0.57,分析30个预测样品的预测标准偏差(SEP)约为0.61;基于马氏距离的传统方法建立的偏最小二乘局部模型的平均SEV为0.59,分析30个待测样品的预测SEP为0.64;而采用整个数据库建立的全局偏最小二乘模型的SEV约为0.65,分析30个预测样品SEP约为0.70。基于Bayesian相似性评估的局部回归方法在苹果糖度的近红外无损定量分析中获得较好的应用结果,在实际应用中该方法比全局回归方法具有更强的适用性,为近红外光谱分析提供了新的分析工具。     

Molecular dynamics integration and molecular vibrational theory. III. The infrared spectrum of water

The new symplectic molecular dynamics (MD) integrators presented in the first paper of this series were applied to perform MD simulations of water. The physical properties of a system of flexible TIP3P water molecules computed by the new integrators, such as diffusion coefficients, orientation correlation times, and infrared (IR) spectra, are in good agreement with results obtained by the standard method. The comparison between the new integrators' and the standard method's integration time step sizes indicates that the resulting algorithm allows a 3.0 fs long integration time step as opposed to the standard leap-frog Verlet method, a sixfold simulation speed-up. The accuracy of the method was confirmed, in particular, by computing the IR spectrum of water in which no blueshifting of the stretching normal mode frequencies is observed as occurs with the standard method.     

Bond connectivity measured via relaxation-assisted two-dimensional infrared spectroscopy

The relaxation-assisted two-dimensional infrared (RA 2DIR) method is a novel technique for probing structures of molecules, which relies on vibrational energy transport in molecules. In this article we demonstrate the ability of RA 2DIR to detect the bond connectivity patterns in molecules using two parameters, a characteristic intermode energy transport time (arrival time) and a cross-peak amplification coefficient. A correlation of the arrival time with the distance between the modes is demonstrated. An 18-fold amplification of the cross-peak amplitude for the modes separated by approximately 11 A is shown using RA 2DIR; larger cross-peak amplifications are expected for the modes separated by larger distances. The RA 2DIR method enhances the applicability of 2DIR spectroscopy by making practical the long-range measurements using a variety of structural reporters, including weak IR modes. The data presented demonstrate the analytical power of RA 2DIR which permits the speedy structural assessments of the bond connectivity patterns.     

The use of FT-NIR for API content assay in organic solvent media: a single calibration for multiple downstream processing streams

The use of near infrared spectroscopy (NIRS) in downstream solvent based processing steps of an active pharmaceutical ingredient (API) is reported. A single quantitative method was developed for API content assessment in the organic phase of a liquid–liquid extraction process and in multiple process streams of subsequent concentration and depuration steps. A new methodology based in spectra combinations and variable selection by genetic algorithm was used with an effective improvement in calibration model prediction ability. Root mean standard error of prediction (RMSEP) of 0.05 in the range of 0.20–3.00% (w/w) was achieved. With this method, it is possible to balance the calibration data set with spectra of desired concentrations, whenever acquisition of new spectra is no longer possible or improvements in model's accuracy for a specific selected range are necessary. The inclusion of artificial spectra prior to genetic algorithms use improved RMSEP by 10%. This method gave a relative RMSEP improvement of 46% compared with a standard PLS of full spectral length.     

A transferable electrostatic map for solvation effects on amide I vibrations and its application to linear and two-dimensional spectroscopy

A method for modeling infrared solvent shifts using the electrostatic field generated by the solvent is presented. The method is applied to the amide I vibration of N-methyl acetamide. Using ab initio calculations the fundamental frequency, anharmonicity, and the transition dipoles between the three lowest vibrational states are parametrized in terms of the electrostatic field. The generated map, which takes into account the electric field and its gradients at four molecular positions, is tested in a number of common solvents. Agreement of solvent shift and linewidths with experimental Fourier transform infrared (FTIR) data is found to within seven and four wave numbers, respectively, for polar solvents. This shows that in these solvents electrostatic contributions dominate solvation effects and the map is transferable between these types of solvents. The effect of motional narrowing arising from the fast solvent fluctuations is found to be substantial for the FTIR spectra. Also the two-dimensional infrared (2DIR) spectra, simulated using the constructed map, reproduce experimental results very well. The effect of anharmonicity fluctuations on the 2DIR spectra was found to be negligible.     

遗传算法结合神经网络用于傅里叶变换红外光谱法测定航空润滑油中水分

采用傅里叶变换红外光谱法测定了航空润滑油中的水分,通过遗传算法(GA)优化选取有效波数点,用误差反向传播神经网络(BP-ANN)进行水分预测计算。模型的预测相关系数为0.957,预测标准偏差为0.022。随机抽取某型航空润滑油样品进行预测并对预测结果进行配对t检验,结果表明:红外光谱定量分析结果与标准方法测定值没有显著性差异,模型可以用于该型在用航空润滑油水分含量现场快速检测。     

Improving the performance of hollow waveguide-based infrared gas sensors via tailored chemometrics

The use of chemometrics in order to improve the molecular selectivity of infrared (IR) spectra has been evaluated using classic least squares (CLS), partial least squares (PLS), science-based calibration (SBC), and multivariate curve resolution-alternate least squares (MCR-ALS) techniques for improving the discriminatory and quantitative performance of infrared hollow waveguide gas sensors. Spectra of mixtures of isobutylene, methane, carbon dioxide, butane, and cyclopropane were recorded, analyzed, and validated for optimizing the prediction of associated concentrations. PLS, CLS, and SBC provided equivalent results in the absence of interferences. After addition of the spectral characteristics of water by humidifying the sample mixtures, CLS and SBC results were similar to those obtained by PLS only if the water spectrum was included in the calibration model. In the presence of an unknown interferant, CLS revealed errors up to six times higher than those obtained by PLS. However, SBC provided similar results compared to PLS by adding a measured noise matrix to the model. Using MCR-ALS provided an excellent estimation of the spectra of the unknown interference. Furthermore, this method also provided a qualitative and quantitative estimation of the components of an unknown set of samples. In summary, using the most suitable chemometrics approach could improve the selectivity and quality of the calibration model derived for a sensor system, and may avoid the need to analyze expensive calibration data sets. The results obtained in the present study demonstrated that (1) if all sample components of the system are known, CLS provides a sufficiently accurate solution; (2) the selection between PLS and SBC methods depends on whether it is easier to measure a calibration data set or a noise matrix; and (3) MCR-ALS appears to be the most suitable method for detecting interferences within a sample. However, the latter approach requires the most extensive calculations and may thus result in limited temporal resolution, if the concentration of a component should be continuously monitored.     

Sulfoxide stretching mode as a structural reporter via dual-frequency two-dimensional infrared spectroscopy

The S=O stretching mode in sulfoxides, having a frequency in the 950-1150?cm(-1) range, is tested as a structural label via dual-frequency two-dimensional infrared (2DIR) spectroscopy. The properties of this structural reporter are studied in several compounds, including (4,4(')-dimethyl-2,2(')-bipyridyl)(o-methylsulfinylbenzoate) ruthenium II, [Ru(dmb)(2)(BzSO)](+), (RuBzSO), octylsulfinylpropionic acid (OSPA), and o- and p-methylsulfinyl-benzoic acid (oMSBA and pMSBA). The mode assignment in the fingerprint region for these compounds is made using a combination of density functional theory calculations and 2DIR and relaxation-assisted 2DIR (RA 2DIR) spectroscopies. The SO stretching mode frequency and IR intensity demonstrate substantial sensitivity to the molecular structure. Multiple cross peaks of the C=O and S=O stretching modes with modes in the fingerprint region (930-1450?cm(-1)) were recorded. The 2DIR and RA 2DIR spectra focusing at interactions of a high-frequency mode of a ligand with the modes in the fingerprint region provide a spectral fingerprint of a compound and help mode assignment in the often congested fingerprint region. The cross-peak amplitudes in oMSBA, pMSBA, and OSPA were compared with the theoretical predictions based on the computed values for the off-diagonal anharmonicities and a reasonable match is found. The SO stretching mode provides means for assigning other modes in the fingerprint region and constitutes a promising structural reporter for the 2DIR and RA 2DIR spectroscopy measurements.