Near-infrared combination and overtone bands of the CH2 sequence in CH2X2, CH2XCHX2, and CH3(CH2)5CH3 and their characteristic frequency zones

We characterized near-infrared spectra of the CH2 sequence in CH2X2 (X=halogen), CH2ClCHCl2, and CH3(CH2)5CH3. Each near-infrared absorption in the region from 3500 to 10,000 cm-1 is consistently assigned to one of the five different combination or overtone groups, in the order of increasing frequency, of the {[v(CH)]+[delta(CH)]} (A), {[v(CH)]+[2delta(CH)]} (B), [2v(CH)] (C), {[2v(CH)]+[delta(CH)]} (D), and [3v(CH)] (E) types, where v(CH) and delta(CH) denote the CH stretching and CH deformation normal modes, respectively. Each group has its own characteristic frequency zone. The bands of B, D, and E, which are second-order combinations or overtones, are weaker by 1/10-1/50 than those of A and C, which are first-order combinations or overtones. The near-infrared spectra of the CH2 sequence show "window zones" of very weak or no absorptions. This suggests that we can perceive the characteristic near-infrared bands of a functional group through the window zones, and we give an example to demonstrate this. The first-order combination bands of type A only of CH2X2 are reasonably assigned to a pair of the normal modes of v(CH) and delta(CH). From this we predict that the first-order combination bands should give structural information on the CH2 chain, similar to the infrared fundamental bands.     

Short-wavelength near-infrared spectra of sucrose, glucose, and fructose with respect to sugar concentration and temperature

Short-wavelength near-infrared (SW-NIR) (700-1100 nm) spectra of aqueous solutions of sucrose, D-glucose, and D-fructose were monitored with respect to change in temperature and sugar concentration. Sugar OH and CH related vibrations were identified by analysis of the spectra of sugar solutions in deuterium oxide (D2O), and of sucrose-d8 solutions in D2O. Absorption spectra were explained in terms of the second and third overtones of OH stretching vibrations and the third overtone of CH2 and CH stretchings. In deuterated solutions, CH and CH2 higher overtone vibration bands became apparent. The major spectral effect of decreased temperature or increased sugar concentration was a decrease in absorbance at 960 nm and an increase in absorbance at 984 nm, interpreted as an increase in the degree of H bonding. Partial least-squares (PLS) calibrations on sugar concentrations (with spectra collected at several sample temperatures) relied strongly on the 910 nm sugar CH related bands, whereas calibrations on temperature depended equally on all OH associated vibrations (750, 840, 960, and 985 nm).     

Two-dimensional correlation study of uniaxially drawn poly(ethylene terephthalate) films by using attenuated total reflection based dynamic compression modulation step-scan fourier transform infrared in combination with spectral simulation analysis by density functional theory

Attenuated total reflection (ATR) based dynamic compression modulation two-dimensional (2D) correlation studies of uniaxially drawn poly(ethylene terephthalate) (PET) films have been performed in combination with spectral simulation analysis by density functional theory (DFT). The dynamic 2D infrared (IR) correlation spectra in the region of the CCO stretching mode vibrations show four distinct correlation peaks located around 1290, 1265, 1248, and 1234 cm(-1). These bands can be clearly assigned to the combination bands or coupling modes of the CH in-plane bend of the benzene ring or the CH(2) deformation of the ethylene glycol unit, as well as CCO stretching vibrations, which are gauche conformer's characteristic bands, by DFT analysis. The sequential analysis of 2D correlation data shows that, upon applying the dynamic compression, the response of the side chain regions (ester groups) occurs first, followed by that of the backbone regions (benzene rings). The ATR based dynamic compression modulation 2D correlation spectroscopy in combination with DFT analysis can be a powerful tool for various polymer characterizations.     

Structure analysis of poly(N-isopropylacrylamide) using near-infrared spectroscopy and generalized two-dimensional correlation infrared spectroscopy

Based on a detailed study of the fundamental vibrations in the mid-infrared (MIR) region and supported by NH-proton deuteration results, the assignment of the overtone and combination bands in the near-infrared (NIR) spectrum of poly(N-isopropylacrylamide) (PNIPAM) is presented. Variable-temperature experiments and two-dimensional correlation infrared spectroscopy are used to determine the chemical mechanism and changing sequence of groups in PNIPAM; we conclude that bonded NH groups turn into free NH groups during the heating process, while the CH groups on the side-chains change prior to those on the main chains. A heterospectral dynamical correlation between the NIR and MIR regions or H-included groups in both regions was also performed. The temperature-induced dissociation of the hydrogen-bonded NH groups is found to proceed earlier than the conformational changes in the hydrocarbon chains.     

Characterization of infrared and near-infrared absorptions of free alcoholic OH groups in hydrocarbon

We have demonstrated that the near-infrared and infrared absorptions in the 8000-3200 cm(-1) region of an OH group of 2-nonanol, 1-nonanol, etc., in n-heptane are excellently separated by subtraction without any serious interference down to very low concentrations at which OH groups are completely free. The separated sharp absorptions are assigned to the fundamental, combination, and overtone bands that are concerned with the OH stretching of free OH. Two components of a sharp overtone band around 7100 cm(-1), which are observed for primary and secondary alcohols, are assigned to coexisting internal rotational isomers of an OH group around the O-C bond. The frequencies of the OH stretching fundamental and overtone bands that are assigned to internal rotational positions are consistent for all the investigated alcohols, including methanol and tertiary butanol. Comparison of the separated spectrum of 2-nonanol in n-heptane with that in 1-chlorooctane or in carbon tetrachloride makes it clear that hydrocarbon is an inert solvent that does not disturb the intrinsic nature of an alcohol OH group. There actually exists a constant anharmonicity shift of 169-175 cm(-1) between the double frequency (2nu(OH)o) of the observed fundamental and the observed overtone frequency ([2nu(OH)]o) for free OH of various alcohols in n-heptane.     

Temperature-dependent structural changes in hydrogen bonds in microcrystalline cellulose studied by infrared and near-infrared spectroscopy with perturbation-correlation moving-window two-dimensional correlation analysis

Temperature-dependent structural changes in hydrogen bonds (H-bonds) in microcrystalline cellulose (MCC) were investigated by infrared (IR) and near-infrared (NIR) spectroscopy. The O-H stretching fundamentals and their first overtone bands were employed to explore the structural changes. In order to analyze the overlapping OH bands due to various H-bonds, perturbation-correlation moving-window two-dimensional (PCMW2D) correlation spectroscopy was applied to the IR and NIR data. Typical spectral variation temperatures were visualized by the PCMW2D correlation analysis. Structural changes in the strong H-bonds in MCC gradually occur in the temperature region of 25-130 degrees C, and they become greater above 130 degrees C. Both OH groups with H-bonds of intermediate strength and very weak H-bonds arise from the structural change of strong H-bonds in the temperature region of 40-90 degrees C, whereas the appearance of the latter OH groups with very weak H-bonds gradually becomes dominant above 90 degrees C. It is revealed from the present study that the glass transition at 184 degrees C induces the changes in the H-bonds in the Ibeta and the O3-H3...O5 intrachain H-bonds. Band assignments for the O-H stretching first overtone vibration region are proposed based on the results of the PCMW2D correlation analyses.     

Extended range near-infrared imaging of water and oil in facial skin

Recently, near-infrared (NIR) imaging has been applied to detecting changes in skin hydration using the water OH band centered near 1460 nm. However, assigning changes in the intensity of the OH band near 1460 nm to changes in the skin's water content is complicated. Consequently, detection of small changes in facial skin water content is difficult. For highly sensitive imaging of facial skin water and oil, a near-infrared unit with a large detection range that includes the CH(3) and CH(2) stretching vibration modes at 1700-1800 nm and the strongest water bands centered near 1920 nm is required. In this study, an extended range indium gallium arsenide near-infrared camera was combined with a diffuse-illumination unit specifically developed for facial skin analysis. Images of water and oil in facial skin were obtained in real time using a combination of interference filters, such as 1950 ± 56 nm for water OH, 1775 ± 50 nm for oil CH, and 1300 ± 40 nm for background reflections. Clear near-infrared images were obtained with little mirror reflection. The water and oil content of facial skin could be evaluated even around the eyes, nose, and sides of the cheeks, which are areas that are difficult to analyze using current commercial devices. Differences were detected in the time-dependent changes of water and oil content in facial skin images obtained after the application of different types of moisturizer. The distribution of both water and oil in the facial skin could be visualized at the same time, and the images could be used to evaluate skin type and skin conditions.     

Conductive SnO2/Sb powder: preparation and optical properties

Preparation of an SnO₂ semiconducting powder doped with antimony (x=2.38 mol%) was achieved by co-precipitation. The unit cell parameters of the doped SnO₂ powders were measured and their changes with dopant concentration were determined. Four-point sheet resistance measurements, together with optical and infrared spectra of the powder were taken in order to obtain a highly-conducting, low-emitting powder which could be used for antistatic paint preparation. Evolution of the phonon bands corresponding to Sn-O stretching modes as a function of dopant concentration were followed, and a model calculation based on an extended four-parametric Kurosawa relation was applied to the reflection spectra of differently doped powders. It was found that the frequency of the plasma oscillations shifts with dopant concentration, and the intensity of the reflectivity peaks was correlated with plasmon-phonon interactions. An additional negative reflection peak in the range 1100 to 1200 cm^–1 was found in the reflection spectra of highly doped powders and was attributed to the coupled modes between the plasma oscillations and one of the phonon combinational or overtone modes of SnO₂.     

Use of infrared spectroscopy for the determination of electronegativity of rare earth elements

Infrared spectroscopy has been used to study a series of synthetic agardite minerals. Four OH stretching bands are observed at around 3568, 3482, 3362, and 3296 cm(-1). The first band is assigned to zeolitic, non-hydrogen-bonded water. The band at 3296 cm(-1) is assigned to strongly hydrogen-bonded water with an H bond distance of 2.72 A. The water in agardites is better described as structured water and not as zeolitic water. Two bands at around 999 and 975 cm(-1) are assigned to OH deformation modes. Two sets of AsO symmetric stretching vibrations were found and assigned to the vibrational modes of AsO(4) and HAsO(4) units. Linear relationships between positions of infrared bands associated with bonding to the OH units and the electronegativity of the rare earth elements were derived, with correlation coefficients >0.92. These linear functions were then used to calculate the electronegativity of Eu, for which a value of 1.1808 on the Pauling scale was found.     

Ab initio calculations of proline vibrations with and without water: consequences on the infrared spectra of proline-rich proteins

The infrared spectra of proline-rich proteins display a strong band in the 1450 cm(-1) region. In the literature, this band has been assigned either to the deformation modes of the CH(2) and CH(3) groups or to the CN stretching mode of proline residues. In order to establish the correct assignment of this band, the impact of proline vibrations in a polypeptide chain is studied and ab initio calculations are performed for a model molecule (I) containing a repeat unit of polyproline. A strong band is effectively calculated in the 1450 cm(-1) region and mostly assigned to CN stretching, whereas, due to the absence of the N-H bond, there is no amide II band. These results are in good agreement with the spectral features observed in the Fourier transform infrared (FT-IR) spectra of gliadins. Moreover, the spectral shifts calculated when a water molecule is complexed with (I) are consistent with the hydration effect observed in the experimental data.     

Studies on the structure of water using two-dimensional near-infrared correlation spectroscopy and principal component analysis

The structure of water molecules in the pure liquid state has been subjected to extensive research for several decades. Questions still remain unanswered, however, and no single model has been found capable of explaining all the anomalies of water. In the present study, near-infrared spectra of water in the temperature region 6-80 degrees C have been analyzed by use of principal component analysis and two-dimensional correlation spectroscopy in order to study the dynamic behavior of a band centered around 1,450 nm at room temperature, which is due to the combination of symmetric and antisymmetric O-H stretching modes (first overtone) of water. It has been found that the wavelengths 1,412 and 1,491 nm account for more than 99% of the spectral variation, representing two major water species with weaker and stronger hydrogen bonds, respectively. A third species located at 1438 nm, whose concentration was relatively constant as a function of temperature, is also indicated. A somewhat distorted two-state structural model for water is suggested.     

Fourier transform infrared and inelastic neutron scattering study of HY zeolites

A combination ofFTi.r. and INS spectroscopy is used in a vibrational study of the bending and stretching vibrations of the acidic hydroxyl groups of Y zeolites. The influence of the number of acidic Bro¨nsted sites and theSi/Al ratio is discussed. Out-of-plane hydroxyl bending modes are assigned to vibrations centered around 419 cm⁻¹ and in-plane hydroxyl bending modes are assigned to vibrations centered around 1089 cm⁻¹. Upon dealumination, these bands are shifted by approximately 30 cm⁻¹ to lower values. The less intense bands at 319,470,565,765, and 1130 cm⁻¹ are assigned to proton-coupled framework vibrations. Upon dealumination, the mode at 319 cm⁻¹ is shifted to lower frequencies and the modes at 565 and 1130 cm⁻¹ are shifted to higher frequencies.     

Temperature-jump apparatus with Raman detection based on a solid-state tunable (1.80-2.05 microm) kHz optical parametric oscillator laser

The operating characteristics of a pulsed (10 ns) tunable near-infrared (NIR) laser source are described for temperature-jump (T-jump) applications. A Q-switched Nd:YLF laser (approximately 10 ns pulses) with a 1 kHz repetition rate is used to pump a potassium titanyl arsenate (KTA) crystal-based optical parametric oscillator (OPO), producing approximately 1 mJ NIR pulses that are tunable (1.80-2.05 microm) across the 1.9 microm vibrational overtone band of water. This T-jump source has been coupled to a deep ultraviolet (UV) probe laser for Raman studies of protein dynamics. T-jumps of up to 30 degrees C, as measured via the O-H stretching Raman band of water, are readily achieved. Application to cytochrome c unfolding is demonstrated.     

Near infrared and mid infrared investigations of adsorbed phenol on HDTMAB organoclays

X-ray diffraction patterns (XRD), infrared Spectroscopy (IR) and near infrared spectroscopy (NIR) have been used to measure the adsorption of phenol on untreated montmorillonite and on hexadecyltrimethylammonium bromide (HDTMAB) modified montmorillonite. The mid infrared spectra indicate that both the surfactant molecule and phenol enter the interlayer of organoclays, replacing the interlayer cations. The higher concentration surfactant leads to a decrease in wavenumber of the bands of organoclays and to increase in intensity. The near infrared spectra (9000–4000 cm^?1) show a prominent band 8260 cm^?1, assigned to the combination result of the CH stretching vibrations of high concentration surfactant and absorbed phenol. The main band observed at 7090 cm^?1 is assigned to the first fundamental overtone of the OH stretching vibrations at 3415 cm^?1 for organoclay. The organoclays are characterised by prominent bands situated between 5900 and 5700 cm^?1. Both the higher concentration of organic molecules and adsorbed phenol causing the near infrared spectra of organic clays to be more complex for spectra in the region from 4700 to 5500 cm^?1. The main band of 4535 cm^?1 for montmorillonite shifts towards the lower wavenumber sites for higher concentration organoclay. The intensity of near infrared spectra generally rises with the value of surfactant concentration increasing, showing certain regularity. It is concluded that phenol is adsorbed to significantly greater amounts on the higher concentration organoclays.     

Crystallization of polylactide and its stereocomplex investigated by two-dimensional fourier transform infrared correlation spectroscopy employing carbonyl overtones

The band origins and transitions of weak vibrational modes developed in the 3500 cm(-1) region of polylactide (PLA) spectra during crystallization are investigated. The band assignment to the OH stretching mode of terminal hydroxyls is unlikely because the trace amount of chain-ends is negligible considering the long chain of high molecular weight polymer. The band intensity can be enhanced for quantitative study by increasing the sample film thickness. The results show that the transition patterns of these bands mimic those of C=O stretching modes. Therefore, these are assigned to C=O overtones. Two bands associated with crystalline and amorphous characteristics are revealed during cold crystallization. The crystalline C=O bands of PDLA and its stereocomplex counterpart are located at 3510 cm(-1) and 3482 cm(-1), respectively, indicating a weaker C=O bond in the latter crystal structure. Two-dimensional Fourier transform infrared (2D-FT-IR) correlation spectroscopy is then applied to study the correlation between C=O overtones and the crystalline characteristic band located near 900 cm(-1). The transitions of the two vibrational modes observed in crystallization of the stereocomplex are in-phase with each other. This reflects an involvement of short-range hydrogen bonding in the stereocomplex crystal structure. In contrast, crystallization of PDLA shows that the C=O overtone varies prior to that of the C-H character, indicating that dipole-dipole force is a crystal-induced interaction.     

采用二维红外技术研究交联对碱溶胶原结构的影响

以N-羟基琥珀酰亚胺己二酸酯(NHS-AA)为交联剂,交联改性碱溶胶原,采用二维红外相关光谱法研究了交联对胶原二级结构的影响。研究发现,交联未影响胶原红外特征吸收峰的位置,但1672、1554和1241cm-1归属于胶原酰胺I带的CO伸缩振动、酰胺Ⅱ带的C—N伸缩与N—H弯曲振动和Ⅲ带的N—H面内变形振动峰之间存在同步正交叉峰,表明随交联共价键的增加,胶原的链段构象发生了变化。在NHS-AA用量增加的过程中,胶原二级结构变化的顺序为:酰胺Ⅲ带>酰胺Ⅰ带>酰胺Ⅱ带>—CH3>—CH—。由此可见,二维红外相关分析法能提供由交联引起的胶原构象动态变化的微观信息,为进一步研究改性胶原结构与功能之间的关系提供实验依据。     

Near-infrared study of the dealumination and water desorption from zeolites

Water desorption from alkali X-zeolites, from NaY and NaA, and deammonization of NaNH₄-Y and dealumination of NaHY are studied. From overtone and combination bands of hydroxyl groups and water important and additional results to the infrared fundamental vibrations are obtained.     

Optical absorption spectra studies for amorphous Cu2O-Bi2O3 glass system

Infrared absorption spectra were measured in the spectral range 4000–200 cm^–1 for the Cu₂O-Bi₂O₃ glass system. Strong bands were observed around 436–477, 600–632, 700–715, 810–875, 975–1000, 1550–1610 and 3225–3510 cm^–1 which are due to harmonics of the Bi-O-Bi stretching vibration, Cu-O stretching vibrations, O-Bi-O stretching vibrations, O-Bi-O bending vibrations, Bi-O stretching vibrations, free H₂O normal-mode bending vibrations and free H₂O molecules or OH^– ions, respectively. Quantitative justification of these absorption bands shows that the values of the experimental wave number for most recorded absorption bands agree well with the theoretical ones.The optical absorption spectra were recorded for the same glass system in the spectral range 300–700 Nm. These records show that the absorption edge has a tail extending towards lower energies. The edge shifts towards lower energies with increasing Cu₂O content. This shift is mostly related to the structural rearrangement and the relative concentrations of the glass basic units. By increasing the Cu₂O content, the optical energy gap decreases, while the width of the localized states increases.     

Estimation of crystallinity in isotropic isotactic polypropylene with Raman spectroscopy

The Raman spectrum of isotactic polypropylene (iPP) has been found to exhibit vibrational peaks in the region of 750 to 880 cm(-1) that are sensitive to the degree of crystallinity. These features are broadly assigned to various modes of methyl group rocking, rho(CH2), and there have been various attempts to assess crystallinity based on the integrated intensities of these bands. Various vibrational analyses performed in the past in combination with experimental studies have concluded that the presence of crystalline order with trans-gauche conformation gives rise to a peak at 809 cm(-1), which is assigned to a rho(CH2) mode coupled with the skeletal stretching mode. However, the presence of additional peaks at 830 cm(-1), 841 cm(-1), and 854 cm(-1), within the same envelope, have been the subject of controversy. In this work isotropic films of iPP derived from the same precursor of identical tacticity have been subjected to various degrees of annealing and the integrated intensities of the Raman bands were measured. The results showed that true 3d crystallinity in isotropic iPP can only be expressed by the 809 cm(-1) band whereas the band at 841 cm(-1) corresponds to an uncoupled rho(CH2) fundamental mode and thus is a measure of the amorphous content. The less intense satellite bands at 830 cm(-1) and 854 cm(-1) of solid iPP cannot be distinguished from the 841 cm(-1) band in the melt and are generally considered as intermediate phases possibly related to non-crystalline components with 3(1)-helical conformations. Independent differential scanning calorimetry (DSC) crystallinity measurements were in broad agreement with the Raman measurements based on the normalized intensity of the 809 cm(-1) Raman band. By comparing the Raman with the DSC data a new value for the theoretical heat of fusion for the 100% crystalline iPP has been proposed.     

Comparison of combination and first overtone spectral regions for near-infrared calibration models for glucose and other biomolecules in aqueous solutions

Partial least squares calibration models are compared for the measurement of glucose, lactate, urea, ascorbate, triacetin, and alanine in aqueous solutions from single-beam spectra collected over the first overtone (6500-5500 cm(-1)) and the combination (5000-4000 cm(-1)) regions of the near-infrared spectrum. Spectra are collected under two sets of conditions with one designed for combination spectra and the other designed for first overtone spectra. As part of the optimization of conditions, an exponential function is presented that accurately characterizes the strong dependency between spectral quality and sample thickness. Sample thickness set for the first overtone and combination spectra are 7.5 and 1.5 mm, respectively. Independent calibration models are established for each solute from both combination and first overtone spectra. Direct comparison reveals superior performance by models generated from combination spectra, particularly for glucose and urea. Standard error of prediction (SEP) values are 1.12 and 0.45 mM for glucose models generated from first overtone and combination spectra, respectively. SEP values for urea are 7.33 and 0.10 mM for first overtone and combination spectra, respectively. Such high SEP values for urea with first overtone spectra correspond to an inability to quantify urea from these spectra because of a lack urea-specific molecular absorption features in this spectral region. Net analyte signal (NAS) is used to quantify the degree of selectivity provided within the first overtone and combination spectral regions. The superior selectivity of combination spectra is confirmed by comparing the length of the NAS vectors for each matrix component.