Asynchronous Spectra Research Articles

Two-Dimensional Correlation Analysis of near Infrared Spectral Intensity Variations of Ground Wheat

Generalised two-dimensional (2D) correlation analysis was applied to characterise the NIR spectral intensity fluctuations among many spectra of ground wheat with multi-variable variations. Prior to 2D analysis, the spectra having neighbouring protein reference values were averaged and then the new spectral set was subjected to principal component analysis for cluster classification. This was repeated for sodium dodecyl sulphate sedimentation (SDSS) volume. Synchronous and asynchronous 2D correlation spectra enhanced spectral resolution and provided information about protein content- and SDSS index-dependent intensity changes not readily accessible from one-dimensional NIR spectra of wheat. The results revealed remarkable differences between the protein content- and SDSS index-induced NIR spectral response. Of interest were several unique protein bands around 1980 nm, 2040 nm, 2200 nm, 2260 nm and 2350 nm in high protein and SDSS wheat. At least one of these bands could be associated with gluten protein (a complex formed primarily from gliadin and glutenin) that influences the end-use quality of wheat flour.

An independent confirmation of the correlation of Uf4 primary peaks and satellite structures of UVI, UV and UIV in mixed valence uranium oxides by two-dimensional correlation spectroscopy

Two-dimensional (2D) correlation spectroscopy was used to resolve the positions and correlations among U4f primary peaks and satellite structures of UIV, UV and UVI components on a dry mica surface. These different species resulted from the reduction of UVI, initially sorbed/precipitated from solution, upon exposure to a high flux of monochromatic Al Kα X-rays during X-ray photoelectron spectroscopy. Synchronous and asynchronous 2D maps of these results are consistent with previous assignments to UIV, UV and UVI components of the solid. The synchronous spectra confirmed the negative correlation between UVI and UIV components and the asynchronous spectra confirmed the role of UV as a reactive intermediate in the reduction reaction of UVI to UIV. Simulations of 2D correlation maps using synthetic spectra of the primary peaks showed that the presence of highly overlapped peaks centered within 2 eV of each other cannot be distinguished without the presence of additional cross-peaks. The maps have therefore confirmed the existence of three dominant oxidation states, and identified positions of UIV, UV and UVI U4f primary peaks and satellite structures that are consistent with previous peak-fitting efforts. Satellite structures also showed out-of-phase correlations among the different oxidation states, further confirming their use as reliable indicators of oxidation state.

Details of thermal behavior of spin-coated film of biodegradable poly(3-hydroxybutyrate- co-3-hydroxyhexanoate) copolymer studied by principal component analysis-based two-dimensional (PCA2D) correlation spectroscopy

Principal component analysis-based two-dimensional (PCA2D) correlation spectroscopy was applied to the temperature-dependent infrared-reflection absorption (IRRAS) spectra of a spin-coated film of poly(3-hydroxybutyrate- co-3-hydroxyhexanoate) (P(HB- co-HHx)) (HHx = 7.2 mol%) copolymer. In asynchronous PCA2D correlation spectra, we clearly captured the existence of two components in the crystalline band of the C O stretching mode, well-ordered primary crystals observed at lower wavenumber and less ordered secondary crystals observed at higher wavenumber, which is not readily detectable in the original 1D spectra. Furthermore, the intensity changes of bands at 1298 and 1280 cm −1 are significantly different in the temperature ranges below and above the transition temperature around 140 °C identified by the 2D first derivatives plot. The result further confirms that the sequence of intensity changes with increasing temperature is such that bands for less ordered crystalline components of P(HB- co-HHx) (HHx = 7.2 mol%) are changing first at an earlier ( i.e., lower temperature) stage.

Analysis of the CO2 and NH3 Reaction in an Aqueous Solution by 2D IR COS: Formation of Bicarbonate and Carbamate

The two-dimensional (2D) infrared correlation spectra obtained from the reaction time- and concentration-dependent IR spectra elucidates the reaction of CO2 and NH3 in an aqueous solution for CO2 absorption. In the synchronous 2D correlation spectra, the interrelation of the proton with carbamate and bicarbonate indicates that the pH level affected the formation reactions of the two products. Furthermore, the interrelation of carbamate with bicarbonate confirmed the conversion of carbamate into bicarbonate with the release of protons (or the decrease of the pH). From the experimental results including the asynchronous 2D correlation spectra, the reaction of the CO2 and aqueous ammonia proceeded through the following steps: formation of carbamate, formation of bicarbonate, release of protons, and conversion of carbamate into bicarbonate. The analysis of the formation of carbamate and bicarbonate by 2D infrared correlation spectroscopy provides useful information on the reaction mechanism of CO2 and NH3 in aqueous solutions.

Two‐dimensional Fourier transform infrared correlation spectroscopy and evolving factor analysis in the study of cationic curing of DGEBA and γ‐valerolactone mixtures

AbstractGeneralized two‐dimensional (2D) correlation spectroscopy and evolving factor analysis (EFA) have been applied to the study of cationic curing reaction of mixtures of diglycidyl ether of bisphenol A (DGEBA) and γ‐valerolactone (γ‐VL). The reaction has been monitored by Fourier transform infrared spectroscopy. The reaction periods in which a chemical change takes place are identified using EFA and then the sequence of changes are established by means of the interpretation of the synchronous and asynchronous spectra obtained with 2D correlation spectroscopy. By combining this information, in the curing process, four reactions have been detected: (1) DGEBA and γ‐VL reaction to obtain a spiroorthoester intermediate, (2) homopolymerization of DGEBA, (3) copolymerization of DGEBA with the spiroorthoester intermediate, and (4) homopolymerization of the spiroorthoester. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3886–3899, 2008

Innovative spectral investigations on the thermal-induced poly(aspartic acid)

Two-dimensional (2D) correlation FTIR spectroscopy was used to investigate the dynamic mechanism of poly(aspartic acid) during the heating process. According to the 2D asynchronous correlation spectra, the CO vibration band of Amide I was separated into three peaks at 1637, 1645 and 1677cm−1, assigned to α helical, random coil and β antiparallel conformation, respectively. And α helical structure would transform into the more ordered and stable conformation of β antiparallel in heating. In the region of 3700–2700cm−1, the H-contained groups were analyzed; the loosening of hydroxyl is found to change prior to the NH-related hydrogen bonds and the conformational reorganization of hydrocarbon chains.

“Sequential Order” Rules in Generalized Two-Dimensional Correlation Spectroscopy

The widely used "sequential order" rules in the generalized two-dimensional (2D) correlation spectroscopy were adopted from the mechanical perturbation-based 2D infrared, where dynamic spectral intensity variation must be a simple sinusoid. 2D correlation analysis is fundamentally a form of parametrization of the integrated or overall relationship between two variable quantities. In generalized 2D correlation spectroscopy, however, the dynamic spectral intensity variations are generally nonperiodic and monotonic, and spectral intensity changes are largely instantaneous. The sequential orders in generalized situations are therefore localized. It is naturally necessary and important to testify whether the analysis result obtained by using the sequential order rules is consistent with the local sequential order of events, which reflects the real sequential order in generalized situations. Unfortunately, this test was not done yet. In this report, the sequential order rules have been tested in the generalized situations using simulated spectra with different local sequential orders and assuming the intensity changes of bands take the exponential forms. It has been found that the sequential order rules correctly identify the local sequential order of two events when spectral intensities of two bands increase or decrease at the same direction but fail when spectral intensities change at different directions. In addition, 2D correlation analysis cannot distinguish the local sequential order from the rate difference of events. A theoretical analysis demonstrates that the synchronous and asynchronous spectra in the generalized 2D correlation spectroscopy may also indicate the linear/nonlinear relationship, in addition to the integrated or overall sequential order of events. The synchronous and asynchronous spectra in the generalized 2D correlation spectroscopy do not necessarily provide the information on the local sequential order or rate difference of events.

Two-Dimensional Attenuated Total Reflection Infrared and Near-Infrared Correlation Study of the Structure of Butyl Alcohol/Water Mixtures

The effect of temperature on attenuated total reflection infrared (ATR-IR) and near-infrared (NIR) transmission spectra of pure butan-1-ol, butan-2-ol, 2-methyl-propan-1-ol, 2-methyl-propan-2-ol, and mixtures with a small water content (X(H2O) </= 0.1) have been examined. The spectra were analyzed using a two-dimensional (2D) correlation approach. Two kinds of correlation analysis were performed: IR-IR and NIR-NIR homo-correlation and IR-NIR hetero-correlation. Our results reveal that the addition of small to moderate amounts of water does not destroy the structure of alcohol. The presence of water stabilizes the structure of alcohols and this effect is more evident for sec-butanol and tert-butanol. The ATR-IR spectra provide information on the most associated species, whereas absorption of the smaller associates and the free OH group is hardly seen. On the contrary, in the NIR spectra the absorption of the free OH groups dominates. The ability of resolution enhancement in the hetero-correlation asynchronous spectra is reduced as compared to that in the homo-correlation spectra. On the other hand, peaks may appear in the hetero-correlation synchronous spectra that are not observed in the homo- correlation contour plots. The positions of the synchronous peaks were used for evaluation of anharmonicity constants. These values for the free OH group do not depend on the experimental conditions. In contrast, the anharmonicity constants for the bonded OH groups determined from the spectra of pure alcohols may significantly differ from those obtained from diluted solutions.

Application of two-dimensional near-infrared correlation spectroscopy to the discrimination of Chinese herbal medicine of different geographic regions

Fructus Lycii is a traditional Chinese medicinal herb. The objective of this paper was to apply two-dimensional (2D) near-infrared (NIR) correlation spectroscopy to the discrimination of Fructus Lycii of four different geographic regions. Generalized 2D-NIR correlation spectroscopy was able to enhance spectral resolution, simplify the spectrum with overlapped bands, and provide information about temperature-induced spectral intensity variations that was hard to obtain from one-dimensional NIR spectroscopy. The 2D synchronous and asynchronous spectra showed remarkable differences within the range of 4950–5700 cm −1 between samples of different geographic regions. Using NIR instead of IR made the 2D approach more convenient and fast, and it can be applied to more area like process control. This approach can also be applied analogously to the discrimination of other Chinese herbal medicine of different geographic regions.

Nano-TiO2 induced secondary structural transition of silk fibroin studied by two-dimensional Fourier-transform infrared correlation spectroscopy and Raman spectroscopy

By sol–gel processing, regenerated nano-TiO2/SF (silk fibroin) composite films were synthesized. The experimental results revealed that the nano-TiO2 particles were well dispersed in the regenerated silk fibroin. Using FT-IR and Raman spectroscopy, the secondary structures of these composite films with concentrations of 0, 0.2, 0.4, 0.8 and 1.6 wt% were characterized. Concentration-perturbed two-dimensional (2D) correlation spectra were calculated for the spectra in the 1800–1600 cm−1 region. To investigate nano-TiO2 particles induced changes in the secondary structure and hydration, the slice spectra were calculated from the synchronous and asynchronous spectra, respectively. The transmittance IR and Raman spectra measurement indicated that the secondary structure of the pure silk film was mostly random coil and α-helix, while the composite films were β-sheet. With increasing nano-TiO2 content, the secondary structure of composite films was changed from typical Silk I to typical Silk II. However, it was found that the transition of the SF's secondary structures would be restrained by excessive nano-TiO2 (over 0.8%) introduced into the composite SF films. Through the FT-IR absorbance and 2D correlation spectra, it was demonstrated that the formation of nano-TiO2 particles could induce the partial transformation of SF conformation from Silk I to Silk II.

Thermal Stability of Lysozyme Langmuir−Schaefer Films by FTIR Spectroscopy

Fourier transform infrared spectroscopy has been applied to study the thermal stability of multilayer Langmuir-Schaefer (LS) films of lysozyme deposited on silicon substrates. The study has confirmed previous structural findings that the LS protein films have a high thermal stability that is extended in a lysozyme multilayer up to 200 degrees C. 2D infrared analysis has been used here to identify the correlated molecular species during thermal denaturation. Asynchronous 2D spectra have shown that the two components of water, fully and not fully hydrogen bonded, in the high-wavenumber range (2800-3600 cm-1) are negatively correlated with the amine stretching band at 3300 cm-1. On the grounds of the 2D spectra the FTIR spectra have been deconvoluted using three main components, two for water and one for the amine. This analysis has shown that, at the first drying stage, up to 100 degrees C, only the water that is not fully hydrogen bonded is removed. Moreover, the amine intensity band does not change up to 200 degrees C, the temperature at which the structural stability of the multilayer lysozyme films ceases.

A study of water dehydration in nylon 6 as a function of temperature using two-dimensional (2D) correlation near-infrared (NIR) analysis

The dehydration progress of nylon 6 was investigated at two different temperatures, using near-infrared (NIR) spectroscopy. The two-dimensional (2D) correlation technique was applied to analyse the experimental data. In the region of the O–H combination band (5350–5000 cm −1), the asynchronous spectra of the two temperatures resolve the complex band into three component bands centered at 5280, 5230, and 5140 cm −1, respectively, indicating the existence of three species of water molecules in different states of hydrogen bonding. From the study of the 2D correlation analysis at two temperatures, we have suggested different dehydration mechanisms of the polyamide 6 soaked with water for 50 and 80 °C.

Perturbation-Correlation Moving-Window Two-Dimensional Correlation Spectroscopy

A new method of analysis, perturbation-correlation moving-window two-dimensional (PCMW2D) correlation spectroscopy, is proposed. For a spectral data set collected under an external perturbation, this method provides a pair of synchronous and asynchronous two-dimensional correlation spectra plotted on a plane between a spectral variable (e.g., wavenumber) axis and a perturbation variable (e.g., temperature) axis. One of the advantages of this new correlation analysis method is that complicated spectral variation along the perturbation direction can be monitored. It has been found that the synchronous and asynchronous PCMW2D correlation spectra are similar to the first perturbation derivative and negative second perturbation derivative spectra of the original data, respectively. To demonstrate the potential of PCMW2D correlation spectroscopy, it has been applied to temperature-dependent infrared (IR) spectra of a poly(vinyl alcohol) (PVA) film. The thermal behavior of the PVA film has been revealed by the PCMW2D correlation analysis. Two characteristic cross-peaks are observed in the synchronous PCMW2D correlation spectra generated from the temperature-dependent IR spectra between the crystalline phase C-O stretching band at 1141 cm-1 and the melting temperature of 209 degrees C and between the amorphous phase C-O stretching band at 1095 cm-1 and another specific temperature of 233 degrees C. This specific temperature of 233 degrees C corresponds to the thermal degradation temperature due to the elimination of the hydroxyl group attached to the main chain.

Novel Tool for Characterization of Noncrystalline Regions in Cellulose: A FTIR Deuteration Monitoring and Generalized Two-Dimensional Correlation Spectroscopy

Our previous results indicated that noncrystalline regions in a regenerated cellulose film comprised at least three domains engaged in different manners of molecular assembly [Kondo et al. In Cellulose Derivatives; Heinze, T. J., Glasser, W. G., Eds.; ACS Symposium Series 688; American Chemical Society: Washington, DC, 1998; Chapter 12]. In this article, we attempt to characterize each of the three noncrystalline domains in the film. The method used was a FTIR monitoring of deuteration from hydroxyl (OH) groups to OD, leading to the two-dimensional (2D) correlation analysis. The time-scan spectra in the OH-OD exchanging reaction were transformed into two kinds of 2D correlation spectra, the synchronous and the asynchronous spectra. Of the two, some cross-peaks were found in the latter spectrum. This suggests that the asynchronous 2D correlation spectrum could differentiate the contribution of OH groups due to different frequencies of hydrogen bonds in each domain. Here we will show the validity of this 2D correlation method as a powerful tool to predict hydrogen-bonding networks of the noncrystalline domains in cellulose.

Effect of Temperature and Concentration on the Structure of N-Methylacetamide−Water Complexes: Near-Infrared Spectroscopic Study

Generalized two-dimensional (2D) FT-NIR correlation spectroscopy and chemometric methods have been used to study temperature-dependent spectral changes in pure N-methylacetamide (NMA) and NMA-water mixtures. We also examined the effect of varying water content on the structure of the mixture. It has been found that the extent of self-association of NMA in CCl4 is very high; the association occurs even at concentration of 0.001 M. In the pure liquid NMA, the population of the monomers is negligible and the structure is dominated by the linear associates. An increase in temperature reduces the number of hydrogen bonds, but in contrast to alcohols their strength remains nearly the same. This reflects a difference in the mechanism of thermal breaking of the associates of NMA and alcohols. The present results reveal that the interaction between NMA and water in the NMA-rich region (X(H2O) < 0.1) does not have a significant effect on the intrinsic structure of NMA. The structure of NMA is dominant, and the molecules of water do not form separate clusters but are dispersed and incorporated into the structure of NMA. We did not observe the presence of the free OH groups in the mixture. This led to the suggestion that each molecule of water forms two hydrogen bonds to two different molecules of NMA. An analysis of the asynchronous spectra reveals that most of the peaks observed in the asynchronous spectra, constructed from the temperature-dependent data, simply result from the frequency shift. This assumption is supported by the simulation studies.

Crystallization behavior of poly(3-hydroxybutyrate- co-3-hydroxyhexanoate) studied by 2D IR correlation spectroscopy

Crystallization behavior of poly(3-hydroxybutyrate- co-3-hydroxyhexanoate) (P(HB- co-HHx)) (HHx=12 mol%) was studied by means of two-dimensional infrared (2D IR) correlation spectroscopy. Three types of crystallization; the gradual cooling from the melt, the isothermal crystallization of the supercooled melt, and the isothermal crystallization of the solution-cast film were investigated. The order of crystal growth steps taking place during the three different types of crystallization processes was analyzed in detail. It was revealed by the asynchronous 2D correlation spectra generated from the dynamic IR spectra in the C O stretching band region that the development of the highly ordered crystals occurs prior to that of the less ordered crystals for the gradual cooling crystallization. On the other hand, for the supercooled melt and solution-cast film crystallization, the formation of the less ordered crystals takes place before that of the highly ordered crystals. The transition from the amorphous phase to the less ordered crystals is a simultaneous process for all three types of crystallization.

Two‐dimensional correlation gel permeation chromatography study of aggregate–aggregate interactions during acid‐catalyzed polymerization of triethoxysilyl‐terminated polystyrene

AbstractThe three‐step polymerization of a well‐defined polymeric silane coupling agent, triethoxysilyl‐terminated polystyrene, catalyzed by acid (H3PO4), was traced as a function of the reaction time with gel permeation chromatography (GPC). Time‐resolved GPC traces collected during the polymerization process were then used to construct two‐dimensional (2D) correlation maps via generalized 2D correlation analysis. The results demonstrated that the synchronous and asynchronous 2D correlation GPC spectra directly reflected the dynamic variation of aggregate–aggregate interactions during each step of the polymerization. In particular, it was found that the formation of aggregates among the cyclic trimers (or tetramers) and monomers was critical for the preferential production of pentamers in the reaction system. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3447–3460, 2004

Characterization of Concentration-Dependent Infrared Spectral Variations of Urea Aqueous Solutions by Principal Component Analysis and Two-Dimensional Correlation Spectroscopy

The association behavior of urea as a function of urea concentration was elucidated by applying principal component analysis (PCA) and two-dimensional (2D) correlation spectroscopy to concentration-dependent FTIR spectra of aqueous urea solutions. The first principal component revealed changes that occurred during the initial increase in urea concentration, which led to the formation of dimers. The second principal component gave information on changes involving the formation of higher aggregates at higher urea concentration. By applying 2D correlation analysis to two sets of FTIR spectra collected above and below 2 M of urea, which were divided on the basis of the PCA, further details on the association process were extracted. Synchronous and asynchronous 2D correlation spectra constructed from the first group of spectra (urea concentration up to 2 M) identified intensity changes due to the formation of ribbon and chain dimers, while the 2D correlation analysis indicated that for urea concentrations above 2 M, urea undergoes further chain polymerization.

Fourier transform infrared studies on deblocking and crosslinking mechanisms of some fluorine containing monocomponent polyurethanes.

The thermal reactivity of a set of different blocked perfluoropolyether (PFPE) containing polyisocyanates and one monocomponent polyurethane containing a PFPE diol was investigated by Fourier transform infrared (FT-IR) spectroscopy. With the former series of products the deblocking kinetics at 90 degrees C and 120 degrees C were investigated with time-dependent spectral data, showing the highest thermal deblocking activity for 3,5 dimethylpyrazole blocking agent. The crosslinking reaction of the PFPE diol with ketoxime blocked isocyanurate at 150 degrees C was monitored by infrared (IR) spectroscopy and two-dimensional (2D) correlation analysis; the results suggested a prevailing direct condensation mechanism and the formation of urea byproducts in the later stages of reaction. Both synchronous and asynchronous spectra were considered and discussed, pointing out the time relation of the chemical functions during the crosslinking experiment.

Structure Changes during the Induction Period of Cold Crystallization of Isotactic Polystyrene Investigated by Infrared and Two-Dimensional Infrared Correlation Spectroscopy

The structural changes during the induction period of isotactic polystyrene (iPS) cold crystallization were investigated by using infrared (IR) spectroscopy together with 2D correlation analysis. It was found that the ordered orientation of the phenyl ring, local conformation change, and structural formation of 31 helix chain of iPS already appear during the induction period. Moreover, careful interpretation of the asynchronous 2D IR spectra generated from the time-dependent spectra enabled us to delineate the structural evolution during the induction period of iPS cold crystallization: Prior to the crystallization of iPS, the amorphous phase changes first, and then the ordering of the phenyl rings of iPS takes place. After that, the polymer chains adjust their local conformations to form the short 31 helix structure. The present study has also demonstrated that the generalized 2D IR correlation spectroscopy is powerful in studying small spectral changes in the induction period of polymer crystallization.