An in situ Fourier transform infrared spectroscopy method for collecting real-time data for the liquid-phase reaction of CO2 and mono-ethanolamine in alcoholic solvent systems

A novel Fourier transform infrared (FTIR) spectroscopy method of analysis was developed to study the industrially important reaction of CO₂ with the primary amine, mono-ethanolamine (MEA), in n-propanol as representative alcoholic solvent. A semi-batch reactor with a piston like ‘floating’ head was specifically designed in order to study the reaction in the liquid phase, thereby eliminating the mass transfer limitations of a gas-liquid system. An attenuated total reflectance (ATR) probe was used to monitor the change in reagent and product concentrations in-situ. Successful spectral peak identification and calibrations were performed in order to collect real time, reaction kinetic data. Data analysis confirmed that the zwitterion reaction mechanism most accurately describes the reaction in non-aqueous systems.     

涂石蜡大米傅立叶变换红外吸收光谱识别分析

针对11种未涂石蜡大米和18个涂不同量石蜡的大米样品,以石油醚提取的油脂为试样,采用傅立叶变换红外光谱仪,扫描样品的傅立叶变换红外吸收光谱,并对光谱进行预处理,提取红外特征信息,将2855与1746、1462与1163 cm-1处特征峰的面积比值为坐标,采用Origín 6.0软件作识别分类图.结果表明:特征峰的面积比值与所涂石蜡量成线性变化,大米油脂的特征峰面积比值在一定的区域分布,涂以0.05%以上石蜡的大米,其油脂特征峰面积比值与未涂石蜡米油脂的值有一定区别.     

Correlating light and thermal stability of silver carboxylate complexes by infrared and 13C NMR spectroscopy

Bond nature of carboxylic groups can play an important role in Ag(I)-carboxylate compounds because light and thermal stability are important requirements for future applications such as antibacterial additives. A linear correlation between bond character and light stability of silver carboxylate complexes has been predicted by a direct relationship of infrared and ¹³C NMR spectroscopic data. This correlation is in agreement with the thermogravimetric analysis and provides a new approach to explore the interaction and the physical properties of metal-carboxylate bonds.     

松杉灵芝不同部位的红外光谱分析研究

采用红外光谱三级鉴定法对松杉灵芝菌盖、表皮、菌柄、子实体不同部位的红外光谱图进行了整体分析。结果表明:松杉灵芝的各部位均含萜类、甾醇类、氨基酸、多肽、蛋白质和糖苷类等物质。在松杉灵芝的一维红外光谱中,菌盖的1 649cm-1峰的相对强度明显比表皮、菌柄和子实体强,说明菌盖中所含的氨基酸、多肽、蛋白质物质的量比其它部位高;在二阶导数谱中,四者在1 720~1 600cm-1范围内峰形差别较大,进一步说明松杉灵芝不同部位所含氨基酸、多肽、蛋白质物质不一致;而二维相关红外光谱中,各部位自动峰的数目、峰位置和峰相对强度都有所不同,可推断松杉灵芝各部位本身所含的糖苷类物质是不一致的。     

Depolymerization behavior of thermoplastic poly(urethane) (TPU) and its dependence on initial molecular weight

The quantitative and qualitative depolymerization behavior of thermoplastic poly(urethane) (TPU) consisting of 4,4′-methylenediphenyldiisocyanate (MDI), 1,6-hexanediol (HD) and 1-hexanol (HEX) was described using temperature-modulated differential scanning calorimetry and Fourier transform infrared (FT-IR) spectroscopy. The depolymerization behavior could be altered by lowering the starting molecular weight. This resulted not only in a higher ceiling temperature, but also in a faster decrease of the molecular weight as a function of temperature once the depolymerization has started. The increase in the ceiling temperature for low molecular weight TPUs is attributed to the lower entropy of polymerization for these compounds compared to high molecular weight TPUs.     

Determination of sucrose by flow injection analysis with fourier transform infrared detection

A new methodology for the determination of sucrose in complex aqueous matrices by flow injection analysis with FTIR detection is presented. The methodology based on the enzymatic hydrolytic cleavage of sucrose by means of invertase to -D-glucose and -D-fructose. A special manifold consisting of two internally coupled injection valves being switched simultaneously is applied to facilitate recording FTIR spectra of the sample before and after the enzymatic reaction. The analytical readout is taken from the resulting difference spectrum obtained by subtracting the FTIR spectra of the sample before and after the reaction. The developed methodology uses a GC-IR software to continuously record the FTIR spectra of the effluent from the manifold. The proposed method gives linear results in the range of 10 to 100 mmol/l and has been successfully applied to the analysis of sucrose in synthetic mixtures as well as in real samples such as soft drinks.     

Simultaneous determination of three surfactants and water in shampoo and liquid soap by ATR-FTIR

It is demonstrated for the first time that the principal constituents of a shampoo as well as of a liquid soap -three surfactants and water- can be determined directly, simultaneously and quickly in undiluted samples by attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy in the middle infrared region, despite the broad absorption bands of the solvent. Two of the surfactants, sodium lauryl ether sulfate (SLES) and cocoamidopropyl betaine (CAPB), are common to both formulations; alkylpolyglucoside (APG) is the third surfactant of the liquid soap and cocodiethanolamide (CDEA), the corresponding ingredient of the shampoo. Absorbance data of the undiluted samples and of the calibration standards was collected in the middle infrared region of the spectrum (800-1600 and 1900-3000 cm⁻¹). Two methods of multivariate quantification were compared: classical least squares (CLS), where absorbance data measured at 200 wavenumbers was processed, and inverse least squares (ILS), where data at 10 selected wavenumbers was analyzed. A spectra normalization procedure, based on a dominating water band, was examined. Twenty-seven standard mixtures were used for each application, consisting of all combinations at three concentration levels of each surfactant, respectively the lower limit, the expected value and the upper limit accepted in quality control. By favoring wavenumbers where absorption bands of the minor components (APG in the liquid soap and CDEA in the shampoo) are more intense, good results were obtained for 18 simulated samples of shampoo and 18 samples of liquid soap, no matter if calculations were made by CLS or ILS. The relative errors for water (major component, 84-88%) and SLES (7-10%) were always below 2%; for CAPB (2-4%), APG (<2%) and CDEA (<2%), they occasionally reached 5% of the component, an uncertainty of less than 0.07% in terms of the sample weight.     

Effect of low-energy ion impact on the structure of hexagonal boron nitride films studied in surface-wave plasma

A high-density surface-wave plasma source is used to deposit hexagonal boron nitride (hBN) films in a gas mixture of He, H₂, N₂, Ar, and BF₃ under a high ion flux condition using low-energy ion irradiation. The ion energy is controlled between around zero and 100 eV by applying a negative or positive bias voltage to a substrate, while the ion flux is increased by locating a substrate upstream in the diffusive plasma. For ion energies above ∼37 eV, the structure of the films depends upon ion energy more than substrate temperature, typical of subplantation processes. As a result, the structural order and crystallinity of sp²-bonded phase in the films characterized by Fourier transform infrared spectroscopy and X-ray diffraction are increased with decreasing ion energy, while the mass density of the films characterized by X-ray reflectivity is retained relatively high with a slight dependence upon ion energy.     

Miscibility,specific interactions,and self‐assembly behavior of phenolic/polyhedral oligomeric silsesquioxane hybrids

The miscibility of a phenolic resin with polyhedral oligomeric silsesquioxane (POSS) hybrids and the specific interactions between them were investigated with Fourier transform infrared (FTIR) spectroscopy and wide‐angle X‐ray diffraction (WAXD). An analysis of the morphology and microstructure was performed with polarized optical microscopy and atomic force microscopy (AFM). The interassociation equilibrium constant between the phenolic resin and POSS (38.7) was lower than the self‐association equilibrium constant of pure phenolic (52.3) according to the Painter–Coleman association model. This result indicated that POSS was partially miscible with the phenolic resin. A polarized optical microscopy image of a phenolic/POSS hybrid material (20 wt % POSS) indicated that the crystals of POSS were arranged evenly in the phenolic matrix; the self‐assembled array of POSS crystals was also confirmed by AFM. This phenomenon was consistent with the FTIR spectroscopy and WAXD analyses. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1127–1136, 2004     

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     

Mössbauer, vibrational spectroscopic and solution X-ray diffraction studies of the structure of iron(III) complexes formed with indole-3-alkanoic acids in acidic aqueous solutions

The chemical reactions between iron(III) and indole-3-acetic (IAA), -propionic (IPA), and -butyric (IBA) acids were studied in acidic aqueous solutions. The motivation of this work was that IAA is one of the most powerful natural plant-growth-regulating substances (phytohormones of the auxin series). Mössbauer spectra of the frozen aqueous solutions of iron(III) with indole-3-alkanoic acids as ligands (L), showed parallel reactions between Fe³⁺ and the ligands. Partly, it resulted in a complex formation which precipitated in aqueous solution and partly, in a redox process with iron(II) and the oxidised indole-3-alkanoic acids as products. The Mössbauer parameters of the Fe²⁺ species suggested a hexaaquo coordination environment. The chemical composition and coordination structure of the precipitated complexes were investigated using elemental analysis, Mössbauer spectroscopy, Fourier transform infrared (FTIR) and Raman spectroscopic techniques. The complexes were soluble in some organic solvents. So, Mössbauer, FTIR and solution X-ray diffraction measurements were carried out on the solution of complexes in acetone, hexadeutero acetone and methanol, respectively. The data obtained supported the existence of the μ-dihydroxo-bridging structure of the dimer: [L₂Fe<(OH)₂>FeL₂] (where L is indole-3-propionate, -acetate or -butyrate).     

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     

In situ FTIR diagnostics of the radio-frequency plasma decomposition of N2O

The decomposition of N₂O in a 13.56-MHz parallel-plate system was studied usingin situ Fourier transform infrared (FTIR) spectroscopy. Areas of two infrared absorption bands of N₂O recorded at 8 cm^–1 resolution were used to estimate relative gas-phase dissociation as a function of rf power and flow rate at 500 mT. Flow rate was found to strongly affect band areas over the range of powers investigated (10–90 W). The effect of rf power on band areas diminished above 40 W, probably due to poor plasma confinement. Distortion of the band shapes by the plasma permitted rotational temperatures to be estimated. Rotational temperature increased essentially linearly with power at constant flow rate, reaching 450 K at 80 W, but was independent of flow rate at constant power. Rotational temperatures were also found to depend on the temperature of the electrodes, which were heated by plasma exposure. No infrared-active product species were observed even under batch conditions where all N₂O was irreversibly dissociated. This lack of detectable products and a 50% pressure rise observed in a batch study suggest that N₂ and O₂ are the primary stable discharge products.     

运用二维相关红外光谱分析技术研究芦丁的热微扰过程

采用傅里叶变换红外光谱法(FTIR)和二维相关分析(2D correlation analysis)技术研究了固态芦丁20℃～160℃的升温过程。实验结果显示，芦丁红外光谱的特征峰在红外图上随着温度升高变化不明显，说明实验中芦丁分子没有发生氧化反应。借助于二维相关分析，提高了谱图的分辨率，将芦丁分子中不同苯环的骨架振动峰在二维同步图上显示并区分开来。同时还揭示了芦丁分子内各官能团之间的相互作用，反映了在热微扰过程中这些基因之间的协同关系和变化的先后顺序。分析结果表明；芦丁分子中两个苯环，杂环的C=O及=C-O-C基因发生了相互作用。其变化的顺序是和含氧杂环相连的苯环，C=O，=C-O-C和含氧杂环相并的苯环。此结论与芦丁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芦丁热微扰过程中结构动态变化的一种新方法，也为芦丁在氧化过程中的机理研究提供了一个重要的理论依据。     

Attenuated total reflectance/fourier transform infrared studies on the phase‐separation process of aqueous solutions of poly(n‐isopropylacrylamide)

Temperature‐induced phase separation of poly(N‐isopropylacrylamide) in aqueous solutions was studied by attenuated total reflectance (ATR)/Fourier transform infrared spectroscopy. The main objectives of the study were to understand, on a molecular level, the role of hydrogen bonding and hydrophobic effects below and above the phase‐separation temperature and to derive the scenario leading to this process. Understanding the behavior of this particular system could be quite relevant to many biological phenomena, such as protein denaturation. The temperature‐induced phase transition was easily detected by the ATR method. A sharp increase in the peaks of both hydrophobic and hydrophilic groups of the polymer and a decrease in the water‐related signals could be explained in terms of the formation of a polymer‐enriched film near the ATR crystal. Deconvolution of the amide I and amide II peaks and the O? H stretch envelope of water revealed that the phase‐separation scenario could be divided, below the phase‐separation temperature, into two steps. The first step consisted of the breaking of intermolecular hydrogen bonds between the amide groups of the polymer and the solvent and the formation of free amide groups, and the second step consisted of an increase in intramolecular hydrogen bonding, which induced a coil–globule transition. No changes in the hydrophobic signals below the separation temperature could be observed, suggesting that hydrophobic interactions played a dominant role during the aggregation of the collapsed chains but not before. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1665–1677, 2001     

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.     

聚乙烯醇与葡激酶的相互作用及其对葡激酶二级结构的影响

在生理条件下, 使用凝胶过滤色谱、荧光光谱、差示扫描量热分析、傅里叶变换红外光谱(FTIR)和葡激酶的纤溶活性分析研究了聚乙烯醇(PVA)和葡激酶的相互作用及其对葡激酶高级结构的影响. 凝胶过滤色谱研究结果表明, PVA与葡激酶之间形成了复合物; 荧光光谱和差示扫描量热分析结果提示, 葡激酶与PVA之间的相互作用没有破坏葡激酶的高级结构; 进一步使用红外光谱法结合可增强分辨率的傅里叶去卷积技术和高斯曲线拟合技术, 用于对葡激酶与PVA复合物冻干粉中葡激酶酰胺Ⅰ带的定量分析发现, 复合物冻干粉葡激酶分子中易导致蛋白质变性的分子间β-折叠组分含量明显减少. 纤溶活性分析结果进一步确认, PVA与葡激酶的相互作用未影响葡激酶的活性, 并对蛋白质的活性起保护作用.     

FOURIER TRANSFORM FAR INFRARED SPECTRA AND NORMAL COORDINATE ANALYSIS OF FIFTEEN RARE-EARTH OXALATE HYDRATES

The Fourier transform far infrared spectra of oxalate hydrates of whole rare-earth series except Pm and Sc are investigated in the range of 100-400 cm~(-1). The assignment of vibrational frequencies is made on the basis of normal coordinate analysis using our NORVIB program. The model used for the hghter elements of the lanthanide series (La to Eu) is based on the crystal structure of Nd_2(C_2O_4)_3. 10H_2O, in which each lanthanide ion is surrounded by nine O atoms, six from three oxalate ions and three from Water molecules.The model adopted for the heavier elements of the lanthanide series (Gd to Lu) and Ytterbium is based on the crystal structure of Yb_2(C_2O_4)_3· 6H_2O, in which each ion is surrounded by eight atoms, six from three oxalate ions and two from water molecules. The variation of the metal-ligand frequencies and force constants with the atomic numbers of lanthanides is plotted and discussed.     

Noninvasive Surface Detection of Papillary Thyroid Carcinoma by Fourier Transform Infrared Spectroscopy

Previously Fourier transform infrared(FTIR) spectroscopy has been applied to detecting thyroid cancer during operations and to discriminating cervical metastatic ones from non-metastatic lymph nodes. This study explored the possibility of establishing a sensitive, accurate and noninvasive screen or diagnosis by preoperative FTIR spectroscopy. 111 patients undergone a thyroid operation and 50 healthy volunteers were enrolled in the study. The FTIR spectra were obtained by two mid-infrared optical fibers with an attenuated total reflectance(ATR) probe closely contacting the subjects' skin on the thyroid nodules. The FTIR spectra obtained from normal thyroid, nodular goiter(NG) and papillary thyroid carcinoma(PTC) patients were compared. A Fisher's discriminant analysis was created based on these data. There were 41 PTC patients and 70 NG patients according to their histopathological examinations. A total of 23(of 39) parameters were statistically different among the three groups(P<0.05). The F₁₃₀₀ and F₁₀₈₀ parameters were significantly different between the three groups. In total, 9 out of 39 FTIR parameters were selected as independent factors by the Wilks' lambda stepwise discriminant analysis. The discrimination accuracy of papillary thyroid carcinoma in the three groups was 88.8%. Surface detection of PTC by FTIR spectroscopy is feasible. FTIR spectroscopy can be used for rapid and noninvasive PTC screen and auxiliary diagnosis.     

水汽在涂层中的扩散传输行为和存在形式

利用石英晶体微天平(QCM)为主要手段,研究了水汽在醇酸清漆和聚氨酯清漆涂层中的扩散传输行为.当相对湿度(RH)大于30％时,吸附和脱附动力学都符合Fick第二扩散定律,溶解性遵守Henry定律.计算出了平均扩散系数D.当吸水后的样品重新暴露于干燥空气时,总有一部分水残留于涂层中.傅利叶变换红外光谱仪(FTIR)测定表明吸水前和脱水后涂层分子结构发生了变化.残留水与涂层分子中的羰基C=O形成了氢键.水在涂层中有相当部分可能是以相互置换的链传递方式传输.形成氢键的速度比扩散速度快得多,当RH大于30％时,涂层中水的浓度足以支持其反应,扩散为吸水过程的控制步骤,此时表现为符合Fick第二扩散定律;当RH低于30％时,涂层中水的浓度不足以支持其反应,反应速度降到和扩散速度可相比,此时吸水过程开始偏离Fick第二扩散定律.