引入离子基团改善聚苯乙烯与热致液晶聚合物的相容性Ⅱ.用FTIR研究分子间特殊相互作用

向聚苯乙烯(PS)中引入磺酸基团可以有效地改善PS与一种热致液晶聚合物(LCP)之间的相容性.用溶液共混的方法制备了PS和磺化聚苯乙烯(HSPS)与LCP的共混物.用FTIR以及红外光谱的合成技术对LCP共混体系进行了表征.共混物中组分聚合物特征吸收的位置和谱图的形状表明在LCP与PS分子间没有相互作用发生,而在LCP与HSPS分子间则存在较强的相互作用.谱图差减技术确认了LCP分子中C==O与C--O基团和HSPS中的磺酸基团参与了相互作用,使得这些基团的特征吸收发生了偏移.     

抗坏血酸升温氧化过程的二维相关红外光谱分析

采用傅里叶变换红外光谱法 (FTIR)和二维相关分析 (2DCorrelationAnalysis)技术研究了固态抗坏血酸在 2 0℃～ 1 60℃的升温氧化过程。结果表明 :抗坏血酸随着温度升高的红外光谱的特征峰在一维图上变化不明显。借助于二维相关分析 ,不仅提高了谱图的分辨率 ,将一维红外谱图上 1 674cm- 1 处的单峰分解为两个自相关峰 ,显示了抗坏血酸的互变异构体中酮式结构的CO基团和醇式结构的CC基团的振动 ;还揭示了分子内各官能团之间的相互作用 ,反映了在升温氧化过程中这些基团之间的协同关系和变化的先后顺序。抗坏血酸分子中CO、CC和COC基团发生了相互作用 ,其变化的顺序是CC先于COC发生偶极矩的变化 ,最后是CO发生变化 ,此现象与抗坏血酸的氧化反应机理相一致。总之 ,二维相关红外分析可以作为研究抗坏血酸升温氧化过程中结构动态变化的一种新方法 ,也为抗坏血酸在氧化过程中的机理研究提供了一个重要的理论依据。     

正常与癌症肺组织的傅里叶变换红外光谱差异的研究

傅里叶变换红外(FTIR)光谱可以在分子水平上研究细胞和组织等复杂的生命体系,提供分子结构和组成的信息.我们发展了一种用于直接测定肿瘤及正常组织红外光谱的方法,对16例肺癌及其癌旁正常组织进行了测定.结果表明,对于正常和癌变的肺组织,FTIR光谱中存在显著差异,相关谱带的相对峰高比可以表征这些差异.因此,傅里叶变换红外光谱可以用来诊断癌症与正常的肺组织,有望成为肿瘤快速诊断的新方法.     

傅里叶红外光谱法检测癌变细胞

用傅里叶变换红外光谱法对正常组织细胞和宫颈癌患者的癌变细胞进行分析检测,与妇女普检中53例样品的病理诊断结果进行对比。该方法能在分子水平上揭示癌变细胞与正常细胞的明显差别,通过谱图解析可直接阐明引起谱图变化的主要原因和细胞癌变的可能机理,为肿瘤疾病的早期诊断开辟了新的途径。     

关于宫颈癌变细胞红外光谱测定方法的研究

提出了一种测定癌变细胞的新方法，利用高分辨傅里叶变换红外光谱（ＦＴＩＲ），对正常人的细胞和千余名宫颈癌患者的细胞进行了对比研究，初步得出该法能在分子水平上揭示出肿瘤细胞与正常细胞的明显差别，并且通过谱图解析，可直接阐明引起谱图变化的主要原因、细胞癌变的可能机理，从而对病程进行预测，为肿瘤疾病的早期诊断展现了良好的前景。     

有机物红外和拉曼光谱联合解析的程序化

有机分子的取代基和分子骨架有特征振动频率,红外和拉曼光谱已成为化学家验证有机基团的常规手段。简单分子或仅含孤立基团的分子用“对号入座”的方法就能容易地获得可信的结果。用这种方法解析复杂分子则较困难,有时甚至无从下手。本文介绍近年     

点击化学法制备含有肉桂酸酯基团的线性聚合物的研究

利用点击化学方法合成了一种侧链上含有肉桂酸酯基团的线性聚合物,利用核磁共振(1H NMR)、红外光谱(FTIR)、凝胶渗透色谱(GPC)和示差扫描量热分析(DSC)等方法对该聚合物的结构和性能进行了表征。DSC谱图显示,在170℃附近出现一个明显的放热峰,通过进一步的实验证明,该放热峰是由聚合物侧链上残余的叠氮基团与肉桂酸酯基团上的碳碳双键发生反应引起的。另外,实验证明,通过稀盐酸处理,可以消除聚合物中残余的叠氮基团。     

傅里叶变换红外光谱结合模式识别法快速鉴别食用油的真伪

采用傅里叶变换红外光谱(FTIR)结合簇类独立软模式识别技术(SIMCA)建立了真伪食用油的快速鉴别方法. 该方法依据FTIR 的指纹特性, 收集并分析了53 个合格食用油和13 个伪造食用油的FTIR 谱图; 通过对谱图取二阶导数和标准化处理, 主成分分析(PCA)提取特征变量; 采用SIMCA 方法分别随机选取43 个合格食用油和9 个伪食用油样品的FTIR 谱图组成训练集, 构建得到真伪食用油的SIMCA 分类模型. 该模型经过剩余10 个合格食用油和4 个伪食用油的验证, 正确识别率达到了100%. 说明FTIR 结合SIMCA 可能成为快速鉴别食用油真伪的一种新方法.     

电化学原位步进扫描时间分辨显微镜FTIR反射光谱

结合步进扫描傅立叶变换红外光谱仪和红外显微镜，建立了电化学原位步进扫描时间分辨显微镜FTIR反射光谱.采用微电极和利用纳米结构表面的异常红外效应，显著提高表面吸附物种的红外检测灵敏度和红外电极表面对极化电位的响应速度，使广泛应用的外反射型薄层红外电解池的时间常数(τ=R1Cd)从使用常规盘电极的约40 ms降低到0.65 ms.研究了酸性介质中CO在Pt电极上的吸附过程，谱图的时间分辨率达50 μs.     

大鼠胰腺及癌组织红外光谱连续小波特征提取及径向基人工神经网络识别

采用水平衰减全反射(HATR)傅里叶变换红外光谱法(FTIR)测定了SD大鼠胰腺正常组织与非正常组织的谱图,提出了一种新的基于FTIR的连续小波特征提取与径向基人工神经网络分类方法以提高FTIR对早期SD大鼠胰腺癌的诊断准确率。利用连续小波多分辨率分析法提取FTIR特征量,对于提取的特征量采用径向基函数神经网络进行模式分类。对SD大鼠的胰腺正常组织、早期癌组织及进展期癌组织的FTIR,利用连续小波多分辨率分析法提取9个特征量,进行RBF神经网络分类判断。当目标误差为0.01,径向基函数的分布常数为5时,网络达到最优化,总的正确识别率为96.67%。并对影响分类结果的网络参数、目标误差和分布常数对分类样品的影响做了讨论。实验结果表明:此方法对早期胰腺癌具有较高的诊断率。     

The vibrational spectrum of alpha-AlOOH diaspore: an ab initio study with the CRYSTAL code

The vibrational spectrum of alpha-AlOOH diaspore has been calculated at the B3LYP level of theory with a double-zeta quality Gaussian-type basis set by using the periodic ab initio CRYSTAL code. Harmonic frequencies at the Gamma point and the corresponding 48 normal modes are analyzed and classified in terms of simple models (octahedra modes, hydrogen stretching, bending, rotations) by direct inspection of eigenvectors, graphical representation, and isotopic substitution. Hydrogen modes are fully separated from the octahedra modes appearing under 800 cm(-1); bending modes are located in the range of 1040-1290 cm(-1), whereas stretching modes appear at 3130-3170 cm(-1). The available experimental IR and Raman spectra are characterized by broad bands, in some cases as large as 800 cm(-1), and individual peaks are obtained by decomposing these bands in terms of Lorentz-Gauss product functions; such a fitting procedure is affected by a relatively large degree of arbitrariness. The comparison of our calculated data with the most complete sets of experimental data shows, nevertheless, a relatively good agreement for all but the H modes; the mean absolute differences for modes not involving H are 10.9 and 7.2 cm(-1) for the IR and the Raman spectra, respectively, the maximum differences being 15.5 and 18.2 cm(-1). For the H bending modes, differences increase to 30 and 37 cm(-1), and for the stretching modes, the calculated frequencies are about 200 cm(-1) higher than the experimental ones; this is not surprising, as anharmonicity is expected to red shift the OH stretching by about 150 cm(-1) in isolated OH groups and even more when the latter is involved in strong hydrogen bonds, as is the case here.     

Energy transfer of highly vibrationally excited 2-methylnaphthalene: Methylation effects

The methylation effects in the energy transfer between Kr atoms and highly vibrationally excited 2-methylnaphthalene in the triplet state were investigated using crossed-beam/time-sliced velocity-map ion imaging at a translational collision energy of approximately 520 cm(-1). Comparison of the energy transfer between naphthalene and 2-methylnaphthalene shows that the difference in total collisional cross section and the difference in energy transfer probability density functions are small. The ratio of the total cross sections is sigma(naphthalene): sigma(methylnaphthalene)=1.08+/-0.05:1. The energy transfer probability density function shows that naphthalene has a little larger probability at small T-->VR energy transfer, DeltaE(u)<300 cm(-1), and 2-methylnaphthalene has a little larger probability at large V-->T energy transfer, -800 cm(-1)相似文献   

The specific vibrational modes of GTP in solution and bound to Ras: a detailed theoretical analysis by QM/MM simulations

The hydrolysis of guanosine triphosphate (GTP) in general, and especially by GTPases like the Ras protein, is in the focus of biological investigations. A huge amount of experimental data from Fourier-transformed infrared studies is currently available, and many vibrational bands of free GTP, GTP·Mg(2+), and Ras·GTP·Mg(2+) in solution have been assigned by isotopic labeling. In the Ras environment, bands between 800 cm(-1) and 1300 cm(-1) have already been assigned, but not those below 800 cm(-1). The combination of quantum and molecular mechanics (QM/MM) methods takes the quantum effects for selected relevant atoms into account. This provides structural details, vibrational frequencies and electron distributions of the region of interest. We therefore used MM and QM/MM simulations to investigate the normal vibrational modes of GTP, GTP·Mg(2+), and Ras·GTP·Mg(2+) in solution, and assigned the vibrational frequencies for each normal vibration mode. In this study, the quantum box contains the nucleoside and the Mg(2+). The comparison of calculated and experimental vibrational spectra provides a very good control for the quality of the calculations. Structurally, MM and QM/MM simulations reveal a stable tridentate coordination of the Mg(2+) by GTP in water, and a stable bidentate coordination by GTP in complex with Ras. For validation, we compare the calculated frequencies and isotopic shifts with the experimental results available in the range of 800 cm(-1) to 1300 cm(-1). For the first time we suggest band assignments of the vibrational modes below 800 cm(-1) by comparison of calculated and experimental spectra.     

Infrared multiphoton dissociation spectroscopy of gas-phase mass-selected hydrocarbon-Fe+ complexes

Infrared spectra in the mid-infrared region (800-1600 cm(-1)) of highly unsaturated Fe(+)-hydrocarbon complexes isolated in the gas phase are presented. These organometallic complexes were selectively prepared by ion-molecule reactions in a Fourier transform ion cycloton mass spectrometer (FTICR-MS). The infrared multiphoton dissociation (IRMPD) technique has been employed using the free electron laser facility CLIO (Orsay, France) to record the infrared spectra of the mass selected complexes. The experimental IRMPD spectra present the main features of the corresponding IR absorption spectra calculated ab initio. As predicted by these calculations, the experimental spectra of three selectively prepared isomers of Fe+(butene) present differences in the 800-1100 cm(-1) range. On the basis of the comparison with calculated IR spectra, the IRMPD spectrum of Fe(butadiene)(+) suggests that the ligand presents the s-trans isomeric form. This study further confirms the potentialities of IRMPD spectroscopy for the structural characterization of organometallic ionic highly reactive intermediates in the gas phase. In conjunction with soft ionization techniques such as electrospray, this opens the door to the gas-phase characterization of reactive intermediates associated with condensed phase catalysts.     

Carotenoid triplet states associated with the long-wavelength-emitting chlorophyll forms of photosystem I in isolated thylakoid membranes

The carotenoid triplet populations associated with the long-wavelength-emitting chlorophyll forms of photosystem I (PS I)(dagger) have been investigated in isolated spinach thylakoids by means of fluorescence-detected magnetic resonance in zero field. The spectra collected in the 730-800 nm emission range can be globally fitted assuming the presence of four different carotenoid triplet states coupled to long-wavelength-emitting forms of PS I, having zero-field-splitting parameters /D/ = 0.0359 cm(-1) and /E/ = 0.00371 cm(-1), /D/ = 0.0382 cm(-1) and /E/ = 0.00388 cm(-1), /D/ = 0.0395 cm(-1) and /E/ = 0.00397 cm(-1), and /D/ = 0.0405 cm(-1) and /E/ = 0.00411 cm(-1). On the basis of the triplet-associated fluorescence emission profile, it is suggested that those triplets are associated with light-harvesting complex I, the peripheral antenna complex of PS I.     

Kinetics of the CH2Cl + CH3 and CHCl2 + CH3 radical-radical reactions

The CH2Cl + CH3 (1) and CHCl2 + CH3 (2) cross-radical reactions were studied by laser photolysis/photoionization mass spectroscopy. Overall rate constants were obtained in direct real-time experiments in the temperature region 301-800 K and bath gas (helium) density (6-12) x 10(16) atom cm(-3). The observed rate constant of reaction 1 can be represented by an Arrhenius expression k1 = 3.93 x 10(-11) exp(91 K/T) cm3 molecule(-1) s(-1) (+/-25%) or as an average temperature-independent value of k1= (4.8 +/- 0.7) x 10(-11) cm3 molecule(-1) s(-1). The rate constant of reaction 2 can be expressed as k2= 1.66 x 10(-11) exp(359 K/T) cm3 molecule(-1) s(-1) (+/-25%). C2H4 and C2H3Cl were detected as the primary products of reactions 1 and 2, respectively. The experimental values of the rate constant are in reasonable agreement with the prediction based on the "geometric mean rule." A separate experimental attempt to determine the rate constants of the high-temperature CH2Cl + O2 (10) and CHCl2 + O2 (11) reaction resulted in an upper limit of 1.2 x 10(-16) cm(3) molecule(-1) s(-1) for k10 and k11 at 800 K.     

Infrared multiphoton ionization of superhot C60: experiment and model calculations

We address, both experimentally and theoretically, the issue of infrared (IR) resonance enhanced multiphoton ionization (IR-REMPI) and thermally induced redshifts of IR absorption lines in a very large and highly vibrationally excited molecular system. Isolated superhot C60 molecules with well defined and variable average vibrational energy in the range of 9-19 eV, effusing out of a constant flux thermal source, are excited and ionized after the absorption of multiple (500-800) infrared photons in the 450-1800 cm(-1) spectral energy range. Recording the mass-selected ion signal as a function of IR wavelength gives well resolved IR-REMPI spectra, with zero off-resonance background signal. An enhancement of the ion signal of about a factor of 10 is observed when the temperature is increased from 1200 to 1800 K under otherwise identical conditions. A pronounced temperature dependent redshift of some of the IR absorption lines is observed. The observations are found to be in good agreement with a model which is based on the sequential absorption of single photons, always followed by instantaneous vibrational energy redistribution. The mass spectra (C60(+) fragmentation pattern) are found to be strongly excitation wavelength dependent. Extensive fragmentation down to C32(+) is observed following the absorption of 1350-1400 cm(-1) as well as 1500-1530 cm(-1) photons while negligible fragmentation is observed when exciting around 520 cm(-1).     

铒铁钴系复合氧化物的制备及其导电性

采用Sol-Gel法制备了ErFe1-xCoxO3-δ稀土复合氧化物纳米晶,用SEM观察了其微粒的大小及形貌,用XRD进行了物相及烧成温度分析,用四探针测试仪及导电仪等测试了其不同温度下的导电性,讨论了不同的铁钴元素比例对导电性的影响,其比例为1∶4、温度为800℃时电导率为1.2Scm-1.     

Infrared determination of calcium or lithium nitrate in acetone solution determination of calcium or lithium in the presence of strontium or barium

A method is proposed for the infrared determination of calcium or lithium in the presence of strontium or barium. A mixture of the nitrates is treated with acetone which dissolves only the calcium or lithium nitrate. The strontium or barium nitrate is filtered off. The nitrate is evaporated to about 2 ml with a stream of dry air and then diluted to 5 ml with acetone. The infrared spectrum is scanned from 860 to 800 cm(-1) and the nitrate peak at 824 cm(-1) for calcium and 827 cm(-1) for lithium is measured. The recommended range is 1-80 mg of calcium or lithium nitrate in the presence of up to about 200 mg of strontium or barium nitrate.     

Excited-state lifetime of adenine near the first electronic band origin

The excited-state lifetime of supersonically cooled adenine was measured in the gas phase by femtosecond pump-probe transient ionization as a function of excitation energy between 36?100 and 37?500cm(-1). The excited-state lifetime of adenine is ～2ps around the 0-0 band of the (1)L(b) ππ(?) state (36?105cm(-1)). The lifetime drops to ～1ps when adenine is excited to the (1)L(a) ππ(?) state with the pump energy at 36?800cm(-1) and above. The excited-state lifetimes of (1)L(a) and (1)L(b) ππ(?) states are differentiated in accordance with previous frequency-resolved and computational studies.