N-十六烷基聚对苯二甲酰对苯二胺的红外光谱研究

以聚对苯二甲酰对苯二胺(PPTA)和1-溴正十六烷为原料,利用N-烷基化方法合成了N-十六烷基聚对苯二甲酰对苯二胺(PPTAC16),并采用DSC和FTIR方法进行了详细研究。DSC结果表明PPTAC16存在侧链结晶行为,但侧链结晶的完善程度低于正十六烷烃的结晶。红外光谱结果表明,烷基侧链结晶中亚甲基堆积的有序度低于正十六烷烃晶体,亚甲基的构象中存在相当数量的旁式构象。变温红外光谱结果表明随着温度的升高,亚甲基的伸缩振动谱带和变角振动谱带的峰位发生突变,说明侧链结晶的熔融;该结果与DSC测试结果一致。另外,伴随着十六烷基侧链结晶的熔融,PPTAC16的主链发生了一种不可逆的变化,且熔融后的烷基侧链所处的状态与液态十六烷烃存在差别。     

垂直排列液晶盒中反铁电液晶TFMHxPOCBC-D2偏振红外光谱研究

本文通过偏振红外吸收光谱研究了铁电与反铁电液晶分子TFMHxPOCBC-D₂(4-(trifluoromethylhexy-3-d₂ carbonyl)phenyl 4′-octyloxybiphenyl caboxylate)在垂直排列取向液晶盒中CD₂基团绕手征性烷基链转动的受阻行为.实验结果显示CD₂的偏振红外吸收在Sm-C相不同于Sm-C_A相.建立了一个CD₂转动受阻模型,在这一模型的基础上,对CD₂的偏振红外吸收进行了模拟计算,较好地解释了CD₂红外吸收在铁电和反铁电液晶相下的行为差异,得到了CD₂基团绕手征性烷基链转动受阻的结论. 关键词： 反铁电液晶 红外光谱 受阻转动     

可逆光异构化双分子层及结构转变的振动光谱

通过吸收,荧光,FT红外,示差扫描量热和X光研究了双链二苯乙烯两亲分子的聚集和光异构化,获得了固态和两个溶液相的双分子层厚度,振动光谱显示在反式二苯乙烯双层的固态和溶液相中存在反式排列的氢键,而在用365nm光照后的溶液相中氢键主要是顺式排列的。亚甲基链伸缩振动则表明烷基链非常有序的排列。     

肺正常组织与癌变组织的表面增强拉曼光谱

采用共焦显微拉曼光谱进行肺正常组织与癌变组织的表面增强拉曼光谱测试,拉曼位移测试范围为300～1700cm-1 。根据得到的肺正常和癌变组织的表面增强拉曼光谱,对比分析了两者的特点与差异。选取蛋白质主链构象中构象不灵敏的CH₂弯曲振动在1454cm-1的谱线为内标,发现相比肺正常组织,癌变组织蛋白质主链中酰胺Ⅲ和酰胺Ⅰ谱带的有序构象明显减少,对α螺旋和无规则卷曲的损伤比较严重,β回折几乎消失,而骨架C—N,C—C伸缩振动却出现了与前2个谱带截然相反的状况,有序构象显著增加,蛋白质侧链构象变化与主链相比则相对复杂;DNA的骨架磷酸基团、脱氧核糖、磷酸-脱氧核糖和碱基的含量总体呈增加趋势;RNA的情况与DNA类似;磷脂的链内纵向有序性参数明显下降。     

BaBPO5晶体晶格振动光谱研究与第一性原理计算

通过偏振拉曼光谱和第一性原理计算对非线性光学晶体BaBPO₅的 晶格振动模式进行了研究. 实验得到了不同几何配置下、在100–1600 cm^-1范围内的晶体偏振拉曼光 谱与傅里叶变换红外吸收谱, 结合因子群分析方法研究了晶体的外振动与内振动模式特征. 分析表明拉曼振动主要来自于PO₄四面体和BO₄四面体的振动, 且PO₄基团振动具有较强的拉曼与红外活性. 此外,根据第一性原理对晶体拉曼振动进行了数值模拟, 进一步明确了拉曼峰与晶体中原子振动的对应关系, 计算表明拉曼光谱中位于672 cm^-1峰位来自晶体中B–O–P键的伸缩振动, 这是晶体中PO₄四面体和BO₄四面体共顶点连接的特征结构在光谱中的体现.     

反铁电液晶TFMHxPOCBC-D2中CD2偏振红外光谱及手性烷基链受阻转动的研究

观测到反铁电液晶分子TFMHxPOCBC-D₂(4-(trifluoromethylhexy-3-d₂ carbonyl)phenyl 4'-octyloxybiphenyl caboxylate) 中CD₂的偏振红外光谱中液晶分子的手性烷基链的受阻转动，以及较大的双色吸收特性.应用一个分子模型，进行了偏振红外吸收的模拟计算，与实验结果相比较，得到液晶分子手性烷基链与分子长轴的夹角约为70°, 其受阻方向在液晶分子倾斜方向一侧的半圆内. 关键词：     

基于振动光谱成像技术的聚合物共混体系研究进展

振动光谱可以提供分子的振动信息,对于聚合物分子链的构象和链间的相互作用非常敏感。分子振动光谱成像作为一种原位无损检测技术,广泛应用于聚合物共混体系结晶、相态分布、界面扩散等性质的研究。本文综述了拉曼(Raman)光谱和红外(IR)光谱成像技术以及其衍生的具有高空间分辨率的红外-原子力联用技术(IR-AFM)、拉曼-原子力联用技术(Raman-AFM)以及针尖增强拉曼光谱技术(TERS)在聚合物共混体系研究中的最新应用进展,以探索并扩展振动光谱成像技术在高分子领域中的应用。     

苯海拉明的拉曼光谱和红外光谱研究

测量并分析了盐酸苯海拉明的红外光谱和拉曼光谱。在Raman光谱中, 1001 cm-1出现一个极强峰, 在1030 cm-1和618 cm-1各有一个中等峰,此外,在红外光谱中, 714 cm-1和757 cm-1附近出现极强的吸收峰,认定这个化合物中存在单取代苯。C-N的对称伸缩振动出现在837 cm-1, 1433 cm-1和1470 cm-1分别为CH2和CH3的变形振动, 在红外光谱中, 1020 cm-1处明显的吸收峰属于C-O-C反对称伸缩振动。此外, 测量得到含量为25 mg苯海拉明药片的拉曼光谱与纯苯海拉明的拉曼峰比较一致, 可作为无损快速检测该药物的手段。     

木糖醇的红外光谱和拉曼光谱研究

实验测量了木糖醇的拉曼光谱和红外光谱,在相关文献的帮助下,对其谱带进行了初步指认。在拉曼光谱中,1000cm-1～1110cm-1之间的中等强度振动属于C-O伸缩振动和H-C-O弯曲振动。850cm-1到920cm-1之间的振动属于C-C伸缩振动。羟基面内弯曲振动在红外吸收光谱中出现在1300～1500cm-1,O-H的变形振动δO-H出现在1420～1380cm-1。     

基于拉曼光谱实验与密度泛函理论的宝石级红珊瑚拉曼谱峰归属研究

红珊瑚是一种珍贵的有机宝石,自古以来因其红润的颜色与细腻的质地深受人们的喜爱与追捧。颜色漂亮的天然红珊瑚产量稀少,故有些红珊瑚会经过染色处理来改善其外观。拉曼光谱测试是鉴定红珊瑚有无经过染色处理的有力手段,故红珊瑚拉曼谱峰的归属对于鉴定有着重要的理论指导意义。由于红珊瑚拉曼峰的归属问题一直没有被深入研究,基于此,该研究测试了三颗颜色深浅不同的红珊瑚（Corallium rubrum）的拉曼光谱。同时,使用量子化学程序Gaussian 16运用密度泛函理论计算了红珊瑚中色素分子角黄素的理论拉曼光谱。创新性对比红珊瑚的实验拉曼光谱与角黄素分子的理论拉曼光谱,并进一步分析红珊瑚拉曼峰的归属。结果发现,红珊瑚的拉曼光谱中主要有1 514,1 295,1 177,1 125,1 086和1 016 cm-1拉曼峰,其中1 086 cm-1处的拉曼峰是方解石的CO2-₃引起的。红珊瑚的红色越深,1 514,1 295,1 177,1 125和1 016 cm-1拉曼峰的强度越强,反之,红珊瑚的红色越浅,这些拉曼峰的强度越弱。红珊瑚拉曼光谱中的1 514,1 295,1 177,1 125和1 016 cm-1峰强与红珊瑚的红色深浅呈现出正相关的关系,故推测这套拉曼峰是由红珊瑚中的色素产生的。角黄素理论拉曼光谱中主要存在的拉曼峰位于1 512,1 269,1 189,1 159和999 cm-1处,与红珊瑚实验拉曼光谱中的1 514,1 295,1 177,1 125和1 016 cm-1峰的形状位置高度吻合。振动分析结果表明,角黄素的1 512,1 269,1 189,1 159和999 cm-1拉曼峰分别是由CC伸缩振动,C-H摇摆振动,C-C伸缩振动,C-C伸缩振动与甲基摇摆振动引起的。因此将红珊瑚拉曼光谱中的1 514,1 295,1 177,1 125和1 016 cm-1峰归属为CC伸缩振动,C-H摇摆振动,C-C伸缩振动,C-C伸缩振动与甲基摇摆振动。使用密度泛函理论的计算方法研究了红珊瑚拉曼谱峰的归属并对红珊瑚的拉曼谱峰进行了指认,为使用拉曼光谱鉴定红珊瑚提供了理论基础。同时为研究这类生物宝石材料拉曼谱峰的归属提供了一种新的方法。     

红木的近红外光谱分析

红木珍贵、种类多,大多数人对红木种类及真伪难以或无法鉴别。利用近红外光谱技术对国家标准中八类红木的近红外光谱进行分析,研究结果表明:(1)近红外光谱与红木色度学参数(L*,a*和b*)之间存在非常高的相关性,预测值与实测红木L*,a*和b*值的相关性分别达到0.988,0.991和0.993;(2)利用化学计量学中的主成分分析(PCA)方法可以将八类红木清楚地区分成八个相应的类别,利用三个主成份信息绘制的三维PCA得分图比二维图更能直观地展现八类红木的区别。研究结果说明应用近红外光谱技术识别红木类别具有可行性,这为开发红木的鉴定或识别提供新的方法和研究思路。     

双光谱二维异步相关光谱表征分子间相互作用的可行性研究

双光谱二维异步相关光谱(2T2D-异步相关光谱)是一种利用两幅一维光谱创建异步相关光谱的新方法。相对于最少需要三幅一维光谱的传统异步相关光谱, 2T2D-异步相关光谱可简化实验过程,有利于样品昂贵体系的表征。利用数学分析、模拟及实际体系实验对2T2D-异步相关光谱应用于表征分子间相互作用的可行性进行了研究。首先建立一个包含P和Q两种溶质的模拟体系,设定P有光谱峰, Q没有光谱峰。数学分析表明:(1)不正确设置P和Q初始浓度,可导致2T2D-异步相关光谱的强度恒为零;(2) 2T2D-异步相关光谱不能反映与分子间相互作用相关的峰强变化;因此,利用2T2D-异步相关光谱表征分子间相互作用可能得到错误的结论。为将2T2D-异步相关光谱发展成为表征分子间相互作用的可靠方法,首先对2T2D-异步相关光谱中P和Q初始浓度的设置方法进行了研究,得出当P和Q初始浓度满足文中式(6)时,可避免不正确设置P和Q初始浓度导致2T2D-异步相关光谱强度恒为零的情况;在此基础上,为解决2T2D-异步相关光谱不能反映与分子间相互作用相关的峰强变化问题,通过向体系中加入具有独立光谱峰和适合浓度的虚拟物质S,发展出带有辅助交叉峰的2T2D-异步相关光谱(ASAP-2T2D-异步相关光谱)。模拟体系实验表明ASAP-2T2D-异步相关光谱可正确反映与分子间相互作用相关的峰宽、峰位及峰强变化,是表征分子间相互作用的可靠方法。最后,将ASAP-2T2D-异步相关光谱应用于表征苯并-15-冠醚-5(BC)与Li^+间的相互作用,实验结果表明ASAP-2T2D-异步相关光谱可同时反映BC特征峰的峰位及峰强变化,进一步证实ASAP-2T2D-异步相关光谱可正确表征分子间相互作用。     

基于二维相关中红外光谱技术的无创血糖检测特异性研究

葡萄糖的特异性是实现血糖浓度检测的前提,也是论证一种血糖检测方法可行性的基础。二维相关光谱技术以其高分辨率和便捷的时序规则(Noda规则)两大优势被广泛地应用在分子间(内)反应、物质相变以及物质信息提取等研究领域。旨在应用二维相关光谱技术验证中红外光谱法无创血糖检测技术的葡萄糖特异性,首先通过分析各种离体溶液样本的二维相关光谱证明方法的理论可行性,然后开展了人体手指的中红外ATR光谱采集实验,参考OGTT方法调节实验过程中人体的血糖水平,并运用二维相关光谱技术验证所得人体光谱中的葡萄糖特征信息,从而论证中红外光谱无创血糖检测技术的可行性。     

Intravoxel incoherent motion diffusion-weighted imaging in head and neck squamous cell carcinoma: Assessment of perfusion-related parameters compared to dynamic contrast-enhanced MRI

Purpose

To investigate the correlation between perfusion-related parameters obtained with intravoxel incoherent motion (IVIM) and classical perfusion parameters obtained with dynamic contrast-enhanced (DCE) magnetic resonance imaging in patients with head and neck squamous cell carcinoma (HNSCC), and to compare direct and asymptotic fitting, the pixel-by-pixel approach, and a region of interest (ROI)-based approach respectively for IVIM parameter calculation.

Materials and methods

Seventeen patients with HNSCC were included in this retrospective study. All magnetic resonance (MR) scanning was performed using a 3 T MR unit. Acquisition of IVIM was performed using single-shot spin-echo echo-planar imaging with three orthogonal gradients with 12 b-values (0, 10, 20, 30, 50, 80, 100, 200, 400, 800, 1000, and 2000). Perfusion-related parameters of perfusion fraction ‘f’ and the pseudo-diffusion coefficient ‘D*’ were calculated from IVIM data by using least square fitting with the two fitting methods of direct and asymptotic fitting, respectively. DCE perfusion was performed in a total of 64 dynamic phases with a 3.2-s phase interval. The two-compartment exchange model was used for the quantification of tumor blood volume (TBV) and tumor blood flow (TBF). Each tumor was delineated with a polygonal ROI for the calculation of f, f ? D* performed using both the pixel-by-pixel approach and the ROI-based approach. In the pixel-by-pixel approach, after fitting each pixel to obtain f, f ? D* maps, the mean value in the delineated ROI on these maps was calculated. In the ROI-based approach, the mean value of signal intensity was calculated within the ROI for each b-value in IVIM images, and then fitting was performed using these values. Correlations between f in a total of four combinations (direct or asymptotic fitting and pixel-by-pixel or ROI-based approach) and TBV were respectively analyzed using Pearson's correlation coefficients. Correlations between f ? D* and TBF were also similarly analyzed.

Results

In all combinations of f and TBV, f ? D* and TBF, there was a significant correlation. In the comparison of f and TBV, a moderate correlation was observed only between f obtained by direct fitting with the pixel-by-pixel approach, whereas a good correlation was observed in the comparisons using the other three combinations. In the comparison of f ? D* and TBF, a good correlation was observed only with f ? D* obtained by asymptotic fitting with the ROI-based approach. In contrast, moderate correlations were observed in the comparisons using the other three combinations.

Conclusion

IVIM was found to be feasible for the analysis of perfusion-related parameters in patients with HNSCC. Especially, the combination of asymptotic fitting with the ROI-based approach was better correlated with DCE perfusion.     

On the use of 2D correlation and exchange NMR spectroscopy in organic porous materials

Two-dimensional (2D) nuclear magnetic resonance (NMR) methods for the investigation of correlation and exchange have been introduced in recent years and have been applied to a range of different systems. Here, we report on the use of 2D NMR diffusion-diffusion correlation spectroscopy for the investigation of diffusion anisotropy in cellular plant tissues and of diffusion-diffusion exchange spectroscopy for the study of the diffusive exchange of dextran in a dispersion of polyelectrolyte multilayer hollow capsules. Furthermore, diffusion-relaxation correlation spectroscopy was applied to both systems.     

New Approaches to Generalized Two‐Dimensional Correlation Spectroscopy and Its Applications

Abstract

This review is focused on the recent approaches to generalized 2D correlation spectroscopy, a technique widely used for the analysis of spectral data. A brief introduction of generalized 2D correlation spectroscopy is described first. Then the powerful combination of generalized 2D correlation spectroscopy and multivariate chemometircs techniques, such as the data reconstruction by principal component analysis (PCA), eigenvalue manipulation transformation (EMT), and self‐modeling curve resolution (SMCR) analysis are explored. Examples of successful applications of new approaches to generalized 2D correlation spectroscopy are highlighted.     

Evidence for further charmonium vector resonances

We discuss the shape of threshold signals in production cross sections of the reaction e<'+>e<,-> → D<'*>D<'*>, at the opening of the D<,s><'*>D<,s><'*> and Λ<,c><'+>Λ<,c><'-> channels. Furthermore, evidence for the ψ(3D), ψ(5S), ψ(4D), ψ(6S), ψ(5D), ψ(7S), ψ(6D), and ψ(8S) new charmonium vector resonances is presented, on the basis of data recently published by the BABAR Collaboration. Central masses and resonance widths are estimated. Confirmation of these resonances would be a huge step in lifting the precision level of hadron spectroscopy towards that of atomic spectroscopy, with far-reaching consequences for theory.     

Effectiveness Evaluation of the Fat Percentage Determination in Multi-Echo T2-Corrected Single-Voxel Spectroscopy by Comparing the 3-Point Dixon and the 6-Point Interference Dixon Techniques

This study compared fat percentage in the HISTO method and chemical-shift imaging method, a 3-echo 3D gradient echo sequence with a T2*-corrected Dixon (3-point Dixon) and 6-echo interference Dixon magnetic resonance (MR) imaging (6-point Dixon) method, to evaluate clinical significance of fatty liver quantification by multi-echo T2*-corrected single-voxel spectroscopy Histo (HISTO). A total of 21 liver donors underwent MR imaging examination. The 3-T MR system (Siemens Healthcare Tim Verio, Erlangen, Germany) was used for all studies. For fat percentage evaluations, a 3-echo 3D gradient echo sequence with T2*-corrected Dixon (3-point Dixon) and 6-Echo Interference Dixon (6-point Dixon) pulse sequences, including HISTO, were applied in sequence. Using fat percentages obtained from each pulse sequence, levels of fatty liver were classified as: non-fatty liver, <5 %; mild fatty liver, >5 but <31 %; and severe fatty liver, >31 %. The correlation between methods was calculated with a correlation coefficient (R ²): HISTO and 3-point Dixon, 0.936 (p < 0.001); HISTO and 6-point Dixon, 0.944 (p < 0.001); and 3-point Dixon and 6-point Dixon, 0.984 (p < 0.001). The HISTO, which was used to investigate fat percentages after T2* correction, showed a high correlation with 3-point Dixon and 6-point Dixon, suggesting that the multi-echo method is useful for accurately determining fat percentages.     

二维相关光谱分析在无创血糖检测特异性研究中的应用

主要利用二维相关光谱分析方法考察了血液中主要成分、测量过程中的系统漂移等因素对近红外光谱中的葡萄糖分子特异性的影响。首先测量了葡萄糖水溶液的近红外透射光谱,以葡萄糖浓度为外扰,计算二维相关同步谱及异步谱,通过对比分析确定了葡萄糖在合频和倍频区域的特征吸收峰位置。当葡萄糖水溶液中加入少量白蛋白后,其二维相关谱中葡萄糖的一级倍频吸收峰(1 590 nm)和二级倍频吸收峰(1 195 nm)出现了不同源的现象,表明白蛋白可能破坏了葡萄糖的特异性;进一步开展了人体口服葡萄糖耐量实验,测量了手掌部位的漫反射光谱,其二维相关谱中葡萄糖的同源性吸收也遭到破坏。另外,由于葡萄糖浓度变化引起的光谱变异信息较小,很容易被系统漂移掩盖,一般需要进行背景修正。在葡萄糖水溶液的透射实验和人体漫反射实验中,分别引入纯水样本和5%标准漫反射板作为参考,以时间为扰动的二维相关光谱分析的结果表明,经过参考样本的背景校正后,系统漂移在二维同步切线谱中引起的谱峰偏移变小,葡萄糖的特征吸收被增强。因此,在近红外光谱无创血糖检测中,应尽量避开与葡萄糖特征吸收不同源的波段,并有必要采取一定的参考测量方法以提高检测的特异性。     

Magnetic phase in the near-surface region of an FeBO3 single crystal

An FeBO3 single crystal was studied from 291 K up to the Neel temperature T(N) = 348.35 K by depth selective conversion electron Mossbauer spectroscopy in ultrahigh vacuum (10(-9) mbar). A new magnetic near-surface phase was found. Its thickness D diverges on approaching T(N) and gives a critical exponent for the correlation length of nu = 0.59(4). The phase boundary between the bulk and near-surface phase could be identified.