傅里叶变换红外光谱新技术与新发展

傅里叶变换红外光谱联用技术 气相色谱(GC)与液相色谱(LC)是分离复杂混合物的有效方法,但仅靠保留指数定性分析未知物或未知组分始终存在着许多困难。而傅里叶变换红外光谱(FTIR)作为重要的结构测定手段,能提供许多色谱难以得到的结构信息,但它要求所分析的样品尽可能简单、纯净,而不能是复杂的混合物。因此,将色谱技术的优良分离能力与红外光谱技术独特的结构鉴别能力相结合,即两种方法的联用就可以达到取长补短的效果,无疑是一种具有很高实用价值的分离鉴别手段。例如GC/FTIR联用技     

傅里叶变换红外光谱和傅里叶变换拉曼光谱法无损鉴别药材的真伪

利用傅里叶变换红外（FT-IR）和近红外傅里叶变换拉曼（NIR FT-aman）光谱法对大黄（西宁大黄）与伪品大黄（华北大黄、山大黄、水根大黄）进行了无损快速的鉴别。结果表明：尽管正品大黄与伪品大黄差别较小，有大部分的化学成分有很大的相同之处，但在红外、拉曼谱图中各自的特征峰较突出，根据谱峰的强度和位置可容易地将它们区别开来。红外和拉曼光谱法相互印证，相互补充，具有快速、准确、操作简单、重复性好、不需对样品进行分离提取，可直接鉴别等特点。     

女性乳腺肿瘤的傅里叶变换红外光谱鉴别方法的探索

通过75例女性良,恶性乳腺肿瘤及正常乳腺组织的傅里叶变换红外光谱(FTIR)对比研究发现,它们之间存在着明显而规律的光谱差异,这反 映了组织中蛋白质,核酸和脂类等生物分子在不同性质的乳腺肿瘤中的构型与构像及以及相对含量上的差别,研究表明,FTIR可从分子水平上揭示肿瘤组织的特性,能对良,恶性乳腺肿瘤的鉴别提供丰富而可靠的结构信息,极有可能发展成为一种肿瘤鉴别方法.     

傅里叶变换红外光谱诊断地中海贫血症

为建立简单快速的地中海贫血诊断方法,本研究探讨了以傅里叶变换红外光谱结合水平衰减全反射(FTIR-HATR)技术在地中海贫血诊断中的制样方法及光谱的数据处理方法.在制样预处理中,通过对样品进行稀释并干燥成膜消除水分子对光谱吸收干扰,保持ATR光谱中各波长对样品的穿透深度一致.结果表明,当1652 cm-1吸收度小于1.5时(即透射率T小于4%时),各波峰强度与血红蛋白浓度呈良好的线性关系(r>0.995)及实验重复性(RSD<4%).在数据处理上,改进的相对强度方法用于800～1780 cm-1和2480～3600 cm-1区间的分析.通过与常规的傅里叶去卷积谱及差谱方法相比,本方法可消除样品浓度所带来的影响因素,灵敏地揭示群体数据中组分与结构在不同组间的显著差异,如1638 cm-1处重叠的蛋白二级结构峰,1172 cm-1、1440 cm-1表征脂类物质的吸收峰,1064 cm-1表征磷酸化合物峰位及表征SH的2553 cm-1附近的吸收峰在正常组与地中海贫血组间存在显著差异.从而避免了几个峰位的相对强度所反映的信息不足及选择参比峰的困扰,对揭示整体的差异变化规律有着重要的作用.     

傅里叶变换红外光谱法检测脑肿瘤

应用傅里叶变换红外光谱法检测了28例液氮冻存的离体脑肿瘤样本及其残留物(将脑肿瘤样本从ATR的ZnSe晶片上取下,样本在ZnSe晶片上沾染后留下的物质).结果发现,神经鞘瘤和神经上皮组织肿瘤(如星形细胞瘤等)的主要特征吸收峰存在明显差异,因此可从各个特征吸收峰的峰位、峰形及不同谱峰强度比的变化来初步鉴别脑肿瘤的性质,脑肿瘤组织样品残留物的红外光谱也可反映不同性质脑肿瘤的差异.与脂类糖蛋白以及核酸相关的谱带变化分析表明,通过特征峰强比(I1460cm-1/I1400cm-1,I1160cm-1/I1120cm-1和I1160cm-1/I1080cm-1)来鉴别肿瘤的性质与病理诊断结果的符合率超过85%.     

36种灵芝产品傅里叶变换红外光谱快速鉴别研究

利用傅里叶变换红外光谱法（FTIR）无损快速鉴别了36种灵芝类产品。灵芝、孢子粉和菌丝体的红外谱图差别较显著;不同厂家所生产的灵芝产品由于所选用灵芝的产地不同、所用辅料的种类以及辅料所添加的多少不同,均引起了谱图的相对峰强度和波数位置的改变。结果表明：36种灵芝产品均可以根据红外的特征谱图进行分类鉴别。该方法快速、不需对灵芝产品进行分离提取。     

傅里叶变换红外光谱及其联用技术在反应研究中的新进展

综述了傅里叶变换红外光谱（ＦＴＩＲ）及其联用技术在界面与电化学反应、生物反应、催化反应和动力学研究中的最新进展，参考文献５７篇。     

用傅里叶变换红外光谱测定汽油有关性质

用傅里叶变换红外光谱仪（FTIR）,在1550－660cm^-1波数范围内,采用化学计量学的偏最小二乘法（PLS）,测定汽油的辛烷值（RON）、密度、馏程（50％、90％）、芳烃、烯烃等质量性质。 试验结果表明,实验室标准方法测定的真值和红外光谱预测值的相关性好,检验结果符合国家标准方法的再现性要求。     

大气开放光路傅里叶变换红外光谱的定性分析

通过目标波段熵最小化(BTEM)和目标因子分析(TFA)两种化学计量学方法研究了大气开放光路傅里叶变换红外(OP/FT-IR)光谱,从多组分测量数据重建特定目标分子的光谱特征,以实现对大气这种复杂体系的定性分析。在牧场周围完成了5次连续OP/FT-IR光谱测量,将光谱按照测量时间顺序排列,获得5个数据矩阵作为研究对象。结果表明,BTEM和TFA两种方法均可从多组分光谱数据矩阵重建出目标分子的光谱特征,重建效果略有差异。TFA能够克服干扰,提取出目标分子的光谱特征,其重建光谱与相应的参考光谱高度相似。BTEM方法无需目标分子的参考光谱,目标函数最优解所对应的谱图就是纯组分光谱。本研究利用两种方法各自的优势,用化学计量学方法定性分析OP/FT-IR光谱,不仅将BTEM方法应用于OP/FT-IR光谱,而且比较这两种方法的应用,为实现多组分OP/FT-IR光谱定性分析提供了新思路。     

傅里叶变换红外光谱体表无创探测乳腺肿瘤

利用傅里叶变换红外(FTIR)光谱仪联合衰减全反射(ATR)探头的中红外光导纤维对46名健康志愿者及113名乳腺肿物患者的体表皮肤进行无创红外光谱测定, 并从分子水平比较、分析了正常乳腺和有肿物乳腺体表皮肤的红外光谱特征. 结果表明, 健康志愿者乳房皮肤8个FTIR光谱测定部位的图谱趋于一致; 正常乳腺体表与有肿瘤乳腺体表的吸收峰差异明显, 而1080 cm^-1处核酸相关吸收峰的变化对鉴别肿瘤的良、 恶性有重要意义.     

Influence of temperature on FTIR spectra of various organic compounds analyzed by on-line carbon dioxide SFC/FTIR

The development of an on-line SFC-FTIR method with supercritical carbon dioxide as mobile phase requires information about the nature of the FTIR spectrum of a solute dissolved in supercritical or liquid CO₂. The wavenumber of maximum absorbance of the carbonyl stretching vibration was quantitatively studied versus temperature and CO₂ density. FTIR spectra recorded in supercritical or liquid CO₂ have been compared to their vapor-phase and condensed-phase spectra for various solutes.     

Temperature‐dependent polymorphic crystalline structure and melting behavior of poly(butylene adipate) investigated by time‐resolved FTIR spectroscopy

The polymorphic crystalline structure and melting behavior of biodegradable poly(butylene adipate) (PBA) samples melt‐crystallized at different crystallization temperatures were studied by differential scanning calorimetry (DSC) and fourier transform infrared (FTIR) spectroscopy. The crystalline structure and melting behavior of PBA were found to be greatly dependent on the crystallization temperature. By comparison of the FTIR spectra and the corresponding second derivatives between the α‐ and β‐crystal of PBA, the spectral differences were identified for the IR bands appeared at 1485, 1271, 1183, and 930 cm^?1 and the possible reasons were presented. Especially, the 930 cm^?1 band was found to be a characteristic band for the β‐crystal. Combining the DSC data with the analysis of normalized intensity changes of several main IR bands during the melting process, the melting behaviors of the α‐ and β‐crystal were clarified in detail. It is demonstrated by the in situ IR measurement that the β‐crystalline phase would transform into the α‐crystalline phase during the melting process, and the solid–solid phase transition from the β‐ to α‐crystal was well elucidated by comparing the intensity changes of the 1170 and 930 cm^?1 bands. The dependence of the β‐ to α‐crystal phase transition on the heating rate was revealed by monitoring the intensity ratio of the 909 and 930 cm^?1 band. It was suggested that at the heating rate of 0.5 or 1 °C/min, the percent amount of the transformed α‐crystal from the β‐crystal was much higher than that at the higher heating rate. The β‐crystal transforms into the α‐crystal incompletely at the higher heating rate because of the less time available for the phase transition. In addition, the β‐ to α‐crystal phase transition was further confirmed by the IR band shifts during the melting process. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1997–2007, 2009     

High Resolution FTIR Spectroscopy of Borazine: The Parallel Bands ν8 and ν9 of 10B314N31H6

The high resolution (0.002 cm^–1) FTIR spectra of the A ‐fundamental bands ν₈ and ν₉ of ¹⁰B₃¹⁴N₃¹H₆ were investigated for the first time. Both fundamental bands show a typical parallel band structure, thus confirming the D_3h symmetry of the molecule under consideration. Whilst ν₉ is unperturbed at the present level of precision, ν₈ is heavily perturbed, probably by an α^BB‐resonance with the IR‐forbidden combination tone ν₁₀ + ν₁₇. The molecular constants of the ground state and of the states v₈ = 1 and v₉ = 1, respectively, are given.     

加速溶剂萃取-流体控制系统净化-高分辨气相色谱/高分辨质谱定量测定底泥中的二噁英

采用高分辨气相色谱/高分辨质谱(HRGC/HRMS)定量测定了底泥中的17种2,3,7,8位多氯代二噁英和呋喃(PCDD/Fs) ,并测定了四至八氯取代的二噁英和呋喃总量。样品经加速溶剂萃取,然后通过流体控制系统（FMS）自动过硅胶柱、氧化 铝柱和碳柱净化,最后浓缩。以HRGC/HRMS电压选择离子检测模式对样品中的PCDD/Fs进行了定性分析,采用同位素稀释 技术定量,该方法可精确定量到pg/g水平。结果表明该方法分析的17种二噁英和呋喃异构体的检出限可达0.1 pg/g。同 位素标准的回收率为49.8%～85.3%,样品中各异构体的回收率为93.2%～115.6%。该方法不但满足国际标准的要求,还大 大提高了分析速度,使分析周期从原来的2周缩短到2 d以内。     

Classification of Rat FTIR Colon Cancer Data Using Waveletsand BPNN

本文提出了一种新的基于水平衰减全反射-傅里叶变换红外光谱（HATR-FTIR）的小波特征提取与反向传播人工神经网络模式分类方法以提高FTIR对早期大鼠结肠癌的诊断准确率．对60只DMH诱导的SD大鼠,44只诱导鼠的第二代鼠,36只正常SD大鼠的结肠正常组织、异常增生、早癌及进展期癌组织所获得的的HATR-FTIR,利用连续小波多尺度分析法提取12个特征量,采用反向传播人工神经网络进行分类,识别准确率分别为100%、94%、97.5%及100%．实验结果表明此方法对早期结肠癌具有较高的诊断率．     

FTIR和ESR法研究离聚体溶液中的离子相互作用

磺化乙丙三元共聚物(SEPDM)离聚体在二甲苯/5％正己醇混合溶剂中具有特异的粘浓关系和粘温关系,估计是由于金属离子被己醇溶剂化而影响离子间相互作用引起的,但尚未有更多的实验数据加以验证.本文用FTIR和ESR方法对SEPDM离聚体溶液作进一步考察,发现金属离子与己醇确实存在溶剂化效应,溶剂化程度与离子的大小、浓度和温度有关,它直接影响离子在溶液中存在的状态(单离子或离子聚集体),这些结果为从分子水平了解离聚体溶液性质提供了理论根据.用波谱方法研究离聚体溶液中的离子相互作用尚鲜见报道.     

The effect of TiO2 on the structure and devitrification behavior of potassium titanium germanate glass

The effect of replacing 20 mol% of GeO₂ by TiO₂ on the properties of potassium germanate glass was investigated. The structure and devitrification behaviour of glasses were studied by Fourier transform infrared spectroscopy (FTIR), differential thermal analysis (DTA) and X-ray diffraction (XRD). It was observed that potassium titanium germanate has a higher glass transition temperature and a higher thermal stability vs. crystallization. The presence of two exothermic peaks on the DTA curve of potassium germanate glass indicates the complex crystallization process. The XRD pattern of this glass heated at the temperature of the first crystallization peak indicated that the GeO₂ and K₂Ge₇O₁₅ were formed. Only the K₂TiGe₃O₉ phase was identified, in a case when potassium titanium germanate glass was heated at the temperature of the crystallization peak.     

近红外光谱分辨率对定量分析的影响

利用近红外光谱建立了多组分混合物中对乙酰氨基苯酚和乙水杨胺的定量分析模型。定量模型可以快速准确地测定混合物中对乙酰氨基苯酚和乙水杨胺的含量。研究发现,光谱分辨率对定量分析模型有重要影响。以光谱分辨率4cm-1获得的光谱数据建立的对乙酰氨基苯酚定量模型,其校正集回归系数达到0·9992;其标准偏差为0.2120;同时模型的验证集回归系数为0.9996,而标准偏差达到0.1848。以分辨率1cm-1和8cm-1收集的光谱为基础获得的定量模型,其预测能力呈现不同程度下降趋势。研究结果表明,针对具体样品的特定组分,需要选择合适的光谱分辨率,进而获得最佳的定量分析结果。     

Quantitative analysis of near surfaces three‐dimensional orientation of polymer chains in PET and PEN films using polarized ATR FTIR spectroscopy

Polarized attenuated total reflection (ATR) Fourier transform infrared (FTIR) spectroscopy was utilized to characterize the three‐dimensional orientation of polymer chains near highly anisotropic surfaces generated by uniaxial drawing. A versatile method was proposed to analyze the molecular orientation of the polymers by combining the experimental refractive indices and optimized contact pressure by an anvil for solving the optical contact problem. This method is effective even when changes in the molecular orientation along the thickness direction caused by drawing are remarkable. In addition, this method enables quantitative comparison of the molecular orientation among different polymers in the same coordinate system. From the molecular orientation analysis of poly (ethylene terephthalate) (PET) and poly (ethylene naphthalate) (PEN), it was revealed that this method has a broader range of applications with high accuracy in estimating the molecular orientation of polymers compared with the conventional methods. The significant changes in the molecular orientation caused by uniaxial and biaxial drawing of PET and PEN films were quantitatively analyzed, and the reasons for the significant in‐plane orientation of PEN chains on the film plane are discussed. In addition, the difference in the molecular orientation between both sides of the films was also demonstrated. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 870–879, 2010     

内噪声作用下的随机共振算法对弱信号的检测

基于随机共振理论提出了一种简便、有效地检测弱信号的方法。在内噪声协同作用下，通过调节输入噪声信号的大小能较好地提高系统输出信号的信噪比，从而实现检测背景噪声很强的弱信号的目的。应用于模拟信号和实验信号的结果证明了方法是可行的。