Infrared spectroscopy of organometallic ions in the gas phase: from model to real world complexes

Gas phase mid-infrared spectroscopy of molecular ions can nowadays be performed with high performance mass spectrometers coupled to free electron lasers (FEL). The wide and continuous tunability of highly intense FELs in the mid-infrared region can be exploited for performing infrared multiple photon dissociation (IRMPD) spectroscopy of molecular ions. This review will focus on gas phase IRMPD spectroscopic investigations aiming at probing the structure and the reactivity of transition metal complexes. The performance of infrared spectroscopy for characterizing the coordination mode of polydentate ligands and the spin state of the metal will be illustrated. Infrared spectroscopy has also been exploited to probe the reactivity of metal complexes, and a special attention will be given to the infrared spectroscopy of reactive intermediates.     

Mid infrared microspectroscopic mapping and imaging: a bio-analytical tool for spatially and chemically resolved tissue characterization and evaluation of drug permeation within tissues

The combination of the two classical biophysical methods, microscopy and infrared spectroscopy, has led to the development of a potent analytical technology termed infrared microspectroscopy. It combines high lateral resolution as obtained by microscopy and the chemical identification of the sample components by infrared spectroscopy. The two approaches mainly utilized in microspectroscopy are the mapping and the imaging techniques, which are introduced and presented. Especially, since the development of so called focal plane array detectors, which are implemented in the imaging methods (microspectroscopic imaging) has become a promising bio-analytical tool for ultrastructural medical diagnostics, due to the fact that the time required for analyzing a sample has been reduced dramatically and the lateral resolution improved to approximately 4 microm. Mid infrared microscopy allows a direct access to spatially resolved molecular and structural information of the analyzed area. The image contrast is generated on the basis of the tissue's intrinsic biochemical composition. The current investigation shows how mid infrared microspectroscopic mapping and imaging is used for the bio-analytical characterization and identification of specific molecular components of a tissue sample at high lateral resolution of a few microns (approaching the mid infrared diffraction limit). Furthermore, the potential of these methods for monitoring the penetration and distribution of drugs within biological tissues are presented. Due to the fact, that mid infrared microspectroscopy is a noninvasive, nondestructive technique for the analyzed sample, requiring no complicated and time consuming staining procedures, it is a convenient method for histological and pathological investigations, allowing the generation of a huge amount of biochemical information not yet available with other nonvibrational techniques. The strength of the presented microscopic technique is the fact that the infrared images are directly comparable to outcomes of classical histological staining procedures and can be interpreted by nonspectroscopists.     

Determination of surface structure and the depth profile of silica glass by infrared spectroscopy

1Introduction Thesurfacestructureandphysicalproper tiesofcondensedmaterandthinfilmsarediffer entfromthoseofbulk.Thegradientinmicro structurecanextendtomicrometerdepth,de pendingonthepreparationprocessesandchemi calspecies[12].Theformationofsurfacelayersis duetothecorrosionreactions,diffusions,ion implantationandfilmdeposition,exhibitingthe depthprofileinbothmicrostructureandchemi calcomposition.Ithaslongbeenobservedthat attheBrewsterangleofincidenceonthepolishedglasssurface,thereflectedelectr…     

近红外光谱分析技术发展和应用现状

近红外光谱是目前国际公认的最有应用价值的分析技术之一,它在国民经济中日益发挥着越来越重要的作用。本文主要介绍近5年国内外近红外光谱分析技术的发展及应用现状,并对我国在这一技术方向的研发提出建议。     

Fixed-point and stratified analysis of the fine structure and composition of five gallstones with Fourier transform infrared (FT-IR) specular reflection spectroscopy

By investigating the identities, amounts, and distributions of the major components of human gallstones, the formation mechanism of calculi may be elucidated. Using FT-IR specular reflection spectroscopy, the compositions of five common types of gallstones, including cholesterol calculus, bile pigment calculus, cholesterol-bilirubin calculus, mixed calculus, and black stones, were positionally, qualitatively, and quantitatively analyzed. Several organic and inorganic substances were found in human gallstones, including cholesterol, calcium bilirubinate, calcium carbonate, calcium phosphate, and calcium stearate. Among them, cholesterol and calcium bilirubinate were the main components. The amounts of these substances varied in different types of gallstone. The distributions of cholesterol and calcium salts (with the exception of calcium bilirubinate) were also closely associated with location. In the various calculi, the amounts of cholesterol and calcium bilirubinate in the cores, the layered structures outside the cores, and the outer shells were higher than those of other substances. The identities of the major components of calculi were similar in different types of gallstones, but their amounts and distributions were significantly different. The analytical method used in this study, which was able to accurately determine the location, quality, and quantity of the major components of gallstones, would be an effective tool to study the formation mechanism of calculi.     

基于MALDI源红外光解离质谱-光谱技术的金属-氨基酸配合物离子的结构研究

红外光解离(IRPD)质谱-光谱技术是研究气相离子结构的有力工具。本工作结合傅里叶变换离子回旋共振质谱(FT-ICR-MS)和台式光学参量振荡器(OPO)红外激光系统,针对气相中铷-组氨酸和铷-赖氨酸配合物离子进行红外光解离光谱研究。实验中配合物离子通过基质辅助激光解吸电离(MALDI)产生,而非由常用的电喷雾离子源(ESI)产生。光谱结果显示,两种配合物离子[His+Rb]+和[Lys+Rb]+分别在3 500 cm-1和2 935 cm-1处存在最大吸收。通过密度泛函理论(DFT)计算方法对[His+Rb]+的结构进行进一步研究,结果表明,[His+Rb]+离子主要来源于His+Rb-03,而非其最低能量构型His+Rb-01。     

Potential of 'flat' fibre evanescent wave spectroscopy to discriminate between normal and malignant cells in vitro

The present study focuses on evaluating the potential of flattened AgClBr fibre‐optic evanescent wave spectroscopy (FTIR‐FEWS) technique for detection and identification of cancer cells in vitro using cell culture as a model system. The FTIR‐FEWS results are compared to those from FTIR‐microspectroscopy (FTIR‐MSP) method extensively used to identify spectral properties of intact cells. Ten different samples of control and malignant cells were measured in parallel by the above two methods. Our results show a significant similarity between the results obtained by the two methodologies. The absorbance level of Amide I/Amide II, phosphates and carbohydrates were significantly altered in malignant compared to the normal cells using both systems. Thus, common biomarkers such as Amide I/Amide II, phosphate and carbohydrate levels can be derived to discern between normal and cancer cells. However, marked differences are also noted between the two methodologies in the protein bands due to CH₃ bending vibration (1480–1350 cm⁻¹). The spectral differences may be attributed to the variation in the penetration depth of the two methodologies. The use of flattened fibre rather than the standard cylindrical fibre has several practical advantages and is considered as an important step towards in vivo measurements in real time, such as that of skin nevi and melanoma using special designs of fibre‐optic–based sensors.     

红外光谱结合核隐变量正交投影法判别掺杂牛奶

为了快速、准确地检测掺杂牛奶,采用基于核隐变量正交投影(K-OPLS)法分析了掺杂牛奶的光谱.选用高斯函数作为核函数,内部交叉验证均方根(RMSECV)最小值作为评价指标,优选了核函数中的核宽度σ以及Y正交成分数.配置含四环素牛奶(0.01～0.3 gL-1)、三聚氰胺牛奶(0.01～～0.3 gL-1)和葡萄糖牛奶(0.01～～0.3 gL-1)各36个,采集纯牛奶及掺杂牛奶样品的红外光谱,采用K (PLS建立各掺杂牛奶与纯牛奶的判别模型.利用这些模型对未知样品进行判别,结果显示对掺杂四环素、三聚氰胺、葡萄糖牛奶的判别正确率分别为100％、100％、95.8％o.建立了同时判别3种掺杂牛奶与纯牛奶的K-OPLS模型,该模型对未知样品的判别正确率为93.1％;同时,与偏最小二乘判别PLS-DA方法的预测结果进行了比较,结果表明:K-OPLS建模方法对于复杂的牛奶体系具有较好的预测能力.     

近红外光谱结合极限学习机识别贮藏期的损伤猕猴桃

为了及时、准确地识别采摘后贮藏期间的损伤猕猴桃,降低果实腐烂及交叉感染带来的损失,采用近红外漫反射光谱技术结合极限学习机(ELM)建立了采摘后2℃冷藏下10天内的碰撞损伤猕猴桃、挤压损伤猕猴桃与无损猕猴桃的动态判别模型.分别比较了无信息变量消除法(UVE)与连续投影算法(SPA)结合UVE优选特征波数建模对简化模型、提高预测性能的影响.结果表明,碰撞损伤猕猴桃比挤压损伤猕猴桃更容易同无损猕猴桃区分开来,且随着贮藏时间的延长,损伤猕猴桃更容易被识别;UVE-SPA-ELM模型的判别效果最好,在采后贮藏10天内预测集中损伤猕猴桃和无损猕猴桃的总正确识别率为92.4％.该检测技术具有较高的检测精度和适用性,可用于快速、无损鉴别损伤猕猴桃.     

Monitoring of the hydrolysis process of bear bile powder using near infrared spectroscopy and chemometrics

A near infrared (NIR) spectroscopy-based method was developed for monitoring the hydrolysis process of bear bile powder. During the hydrolysis process, samples were collected and measured using both NIR spectrometer and high performance liquid chromatography. The quantitative calibration models were established with the collected NIR spectra and the reference concentrations of tauroursodeoxycholic acid (TUDCA), taurochenodeoxycholic acid (TCDCA), ursodeoxycholic acid (UDCA), and chenodeoxycholic acid (CDCA) using partial least squares regression algorithm. After the models were established and validated, the samples of new batches can be determined rapidly, and the hydrolysis process of bear bile powder can be monitored quantitatively. Additionally, a moving block of standard deviation (MBSD) method was also developed for the endpoint determination of the hydrolysis process. The proposed methods have reduced the laborious workload of process sample analysis significantly, and the fast analytical results have contributed to the understanding and controlling of the bear bile powder hydrolysis process.     

二维红外相关光谱在两面针与单面针鉴别中的应用

利用傅里叶变换红外光谱法及二维红外相关光谱法对两面针与单面针进行研究,探讨其一维、二维红外光谱特征及其差异,为快速鉴定两面针样品提供依据。两面针与单面针均为芸香科花椒属木本植物,均可入药,2者外形极为相似,药材市场常用靡价的单面针制成饮片冒充两面针。本实验结果表明:两面针与单面针的一维红外光谱差别甚小,但通过二阶导数光谱结合二维傅里叶红外光谱的方法可以将2者完全区分开采。本方法快速、廉价、有效,对两面针的鉴别提供一种新的方法和技术。     

Surface chemistry-mechanical property relationship of low density polyethylene: an IR+visible sum frequency generation spectroscopy and atomic force microscopy study

Surface-specific IR+visible sum frequency generation (SFG) spectroscopy was used to obtain chemical composition of two polymer surfaces. The SFG surface vibrational spectrum of pure low density polyethylene and that of a commercial sample of the same kind of polymer, which contains additives, are markedly different. This correlates well with the very different surface mechanical properties, i.e., stiffness (indicative of the elastic modulus) and friction, which were measured by atomic force microscopy (AFM) on the same polymer surfaces. The surface of CLDPE is dominated by methoxy (−OCH₃) contained additives, segregated from the bulk, which explains a lower stiffness, adhesion and friction of the surface, as measured by AFM. This revised version was published online in August 2006 with corrections to the Cover Date.     

基于PCA-SVM融合离子迁移谱与拉曼光谱的毒品鉴别方法

光学检测的指纹图谱具有专属性强、稳定性好、重现性好的特性。通过离子迁移谱毒品探测仪(IMS)与易制毒化学品拉曼快速检查仪分别采集离子与拉曼光谱的双谱图数据,然后将两个谱图进行创新数据融合后,结合主成分分析(PCA)和支持向量机(SVM)分类法对毒品进行鉴别。实验结果表明,融合后的数据相较于分别用单谱图数据进行鉴别,有效提高了对毒品的识别率和准确性。为鉴别毒品提供了一种安全、快速、可靠的新分析方法。     

Characterization of human ovarian teratoma hair by using AFM, FT-IR, and Raman spectroscopy

The structural, physical, and chemical properties of hair taken from an ovarian teratoma (teratoma hair) was first examined by atomic force microscopy (AFM), Fourier transform infrared (FT-IR), and Raman spectroscopy. The similarities and differences between the teratoma hair and scalp hair were also investigated. Teratoma hair showed a similar morphology and chemical composition to scalp hair. Teratoma hair was covered with a cuticle in the same manner as scalp hair and showed the same amide bonding modes as scalp hair according to FT-IR and Raman spectroscopy. On the other hand, teratoma hair showed different physical properties and cysteic acid bands from scalp hair: the surface was rougher and the adhesive force was lower than the scalp hair. The cystine oxides modes did not change with the position unlike scalp hair. These differences can be understood by environmental effects not by the intrinsic properties of the teratoma hair.     

Detailed characterisation of heavy alkylated benzene fluids by multipulse one‐ and two‐dimensional NMR spectroscopy

In this paper, the results of a characterisation of heavy alkylated benzenes (HAB) using multipulse NMR spectroscopy are presented. Four commercial samples of heavy alkylated benzene have been characterised in detail in terms of various structural parameters, such as percentage aromatic carbon (Ca), degree of aromatic substitution, average alkyl chain length, type of alkyl chain and their proportions. Three of the HAB samples were very similar in structure, whereas, in the fourth, the structures present were entirely different. The latter had an abundance of 2‐phenyl alkane‐type structures, and did not contain methyl substituted tetralin or naphthalene type molecules. The influence of the structures on lubricating oil properties, including viscosity index, pour point, and viscosity, as well as Freon^TM floc point, are also discussed.     

Microscopic and spectroscopic characterization of rice and corn starch

Starch granules from rice and corn were isolated, and their molecular mechanism on interaction with α‐amylase was characterized through biochemical test, microscopic imaging, and spectroscopic measurements. The micro‐scale structure of starch granules were observed under an optical microscope and their average size was in the range 1–100 μm. The surface topological structures of starch with micro‐holes due to the effect of α‐ amylase were also visualized under scanning electron microscope. The crystallinity was confirmed by X‐ray diffraction patterns as well as second‐harmonic generation microscopy. The change in chemical bonds before and after hydrolysis of the starch granules by α‐ amylase was determined by Fourier transform infrared spectroscopy. Combination of microscopy and spectroscopy techniques relates structural and chemical features that explain starch enzymatic hydrolysis which will provide a valid basis for future studies in food science and insights into the energy transformation dynamics.     

Composition,microstructure and element study of urinary calculi

To better understand the basis of urinary calculi formation, we studied the composition, microstructure, and element analysis of different types of urinary calculi. Sixty people with urinary stones in Shanxi province were selected randomly. The composition of urinary stones was analyzed using Fourier transform infrared spectroscopy. The microstructure of material components was observed by a scanning electron microscopy and the elemental distribution and composition were analyzed by an X‐ray energy spectrometer. Furthermore, general information, BMI, history of medicine, chronic medical history, family history, and recurrence rates were collected. Female‐to‐male ratio was 1:2.5; median age was 43.2 years old. Of the patients, 13.3% were found definite family history and 46.6% of patients for recurrence history. It was found that mixed stones account for the largest proportion (65%), followed by calcium oxalate monohydrate calculi (26.67%). In mixed stones, the mixture of calcium oxalate monohydrate and hydroxyapatite had the largest proportion, accounting for 71.79%. Stones showed different microcosmic characteristics and element distribution. Stones varied widely in distribution, infrared spectrum, microstructure, and element composition, which provided an important basis for urinary calculi research regarding urinary stone formation.