Perturbation-correlation Moving-window Two-dimensional Correlation Research Articles

Composition and structure analysis of different depths in the stratum corneum using confocal Raman microscopy combined with two-dimensional correlation spectroscopy

The chemical composition and structure of the stratum corneum (SC) play a crucial role in the skin barrier function. Therefore, accurately determining the SC thickness and studying the changes in lipid and keratin structure and distribution within it are key aspects of skin barrier research. Currently, there are limited analytical tools and data analysis methods available for real-time and online studies of SC composition and structural changes. In this study, we focus on depth as a perturbation and employ confocal Raman microscopy combined with moving-window two-dimensional correlation spectroscopy (MW2D) technique to investigate the SC thickness. Additionally, we employ confocal Raman microscopy combined with perturbation-correlation moving-window two-dimensional correlation spectroscopy (PCMW2D) to precisely characterize the stratification of the SC. Furthermore, the two-dimensional correlation spectroscopy (2DCOS) method is utilized to examine the content of various conformations in the keratin secondary structure within the SC, as well as the subtle interrelationships between lipid and keratin structures.

PCMW2D and 2D Raman correlation spectroscopy evidence for presence of spin-phonon coupling in hexagonal LuMnO3

Two-dimensional correlation spectroscopy (2D-COS) and perturbation-correlation moving window two-dimensional correlation spectroscopy (PCMW2D) analysis are performed on the temperature-dependent Raman spectra of hexagonal LuMnO3 single crystal. Under the resonance with the on-site Mn d-d transitions, the correlation between the phonons which are relate to the vibration of Mn ions’ bonds and spin-excitation peaks suggest a strong spin-phonon coupling in LuMnO3. The PCMW2D results clearly show that the significant change in phonons and spin-excitation peaks occurs around the Néel temperature and the spin reorientation transition. The multiple components in the broad spin-excitation peaks also suggest variations in spin symmetries in the ground state. Furthermore, we propose that the 2D-COS and PCMW2D Raman correlation spectroscopies provide a simple and powerful method for investigating the couplings and the transitions, which would be very important for understanding systematically the magnetoelectric properties of multiferroic materials.

Applying second derivative synchronous fluorescence spectroscopy combined with Gaussian band fitting to trace variations of DOM fractions along an urban river

Synchronous fluorescence spectroscopy (SFS) combined with Gaussian band fitting, two-dimensional correlation (2D-COS) and perturbation-correlation moving-window two-dimensional (PCMW2D) can provide an excellent mothed to extract fluorescent components of dissolved organic matter (DOM) and reveal its variations in an urban river. Fifteen water samples were collected from the Anyanghe River, which flew across the town, urban, and rural regions. Five peaks (peak1 tyrosine-like, peak2 tyrosine-like, peak3 tryptophan-like, peak4 microbial humic-like, peak5 fulvic-like) were extracted using the Gaussian Amp model from the SFS in the river, while the peak1 only occurred in the rural region. The microbial humic-like in the town region accounting for 50.02 % was the representative substance. The tyrosine-like dominated in the rural regions, for its percentage range was 62.26 %-75.78 %. The average percnetage of tyrosine-like (29.77 %) in the urban region was similar to that of the tryptophan-like (21.86 %), microbial humic-like (25.56 %), and fulvic-like (22.82 %). Based on the two-dimensional correlation, the variation order of DOM fractions in the town and urban regions was tryptophan → tyrosine → microbial humic → fulvic, and the variation order in the rural region was tyrosine → tryptophan → microbial humic → fulvic. This indicated that the changing trend of DOM fractions existed from the labile protein-like to the stable humus in the whole river. According to the perturbation-correlation moving-window two-dimensional correlation spectroscopy, the spectral intensity of tyrosine-like should be linear increase in the town and urban regions, and concave increase in the rural region. The spectral intensity trend of tryptophan-like mainly was linear increase in the whole river. And the intensity of microbial humic-like showed the rough convex increase in the whole river. The trend of the fulvic-like in the town and rural regions was similar to the microbial humic-like. However the fulvic-like intensity in the urban region exhibited a trend from the concave increase to the convex increase, which was obviously different from the tyrosine-like, tryptophan-like and microbial humic-like. This attribute that the untreated domestic sewage in the urban region could discharge into the river. Therefore, for small amounts of samples, the SFS combined with Gaussian band fitting, 2D-COS and PCMW2D can be used as a powerful tool to investigate fluorescent components of DOM, and reveal their variations along the river.

Experimental and theoretical study on the evolution of functional groups in cellulose char during oxidative pyrolysis

Oxidative pyrolysis of biomass is a promising substitute technology for conventional pyrolysis and is also crucial to the related degradation process of biomass materials such as aging, combustion, fire hazard, etc. The intertwining of heterogeneous oxidation and homogeneous oxidation of biomass and its derivative muffles the detailed mechanism of oxidative pyrolysis. To unravel the mechanism of heterogeneous oxidation in the cellulose condensed phase, the real-time evolution of functional groups in cellulose char during oxidative pyrolysis was probed by the in situ diffuse reflectance infrared Fourier transform technology, which is further analyzed by a homemade semi-quantitative analysis program based on the perturbation-correlation moving-window two-dimensional correlation spectroscopy and two-dimensional correlation spectroscopy. The experimental results show the obvious promotion effects of O2 on the direct oxidation of hydroxyls to unconjugated CO and the cleavage of COC in the development stage between the temperatures of the initiation and the maximum rate of weight loss, resulting in the lowered thermostability and devolatilization of cellulose. At elevated temperatures, the hydroxyls and CO were further oxidized by O2 into carboxyls, and released at around 450 °C in the last decline stage, performing the second peak of the derivative thermogravimetry curve for oxidative pyrolysis. Through density functional theory calculation of the hydroxyl oxidation, a low-temperature oxidation mechanism competitive with the transglycosylation and other dehydration reactions was proposed. Its rate is determined by the initiating H abstraction, which highly depends on the spin density (population) for the transition state and pyrolysis temperature.

Comprehensive utilization of agricultural wastes by combined wet torrefaction and pyrolysis

Wet torrefaction (WT) is promising to convert moist biomass into hydrophobic fuel with higher heating value and energy density. The current study investigated the comprehensive utilization of biomass with combined wet torrefaction and pyrolysis. Characterizations of both torrefied solid and liquid were achieved to understand the evolution of physicochemical properties during WT. The composition analysis showed that the torrefied liquid was a promising candidate for furfural and organic acid production, and could affect the WT solid properties as well. Torrefied solid products with less reactive ash, larger surface area, and higher crystallinity were obtained. And the AAEM removal by WT could be enhanced with corncob due to its hemicellulose abundance. Followed by WT, techniques including TGA, py-GC/MS and py-in-situ DRIFT were used for pyrolysis investigation of torrefied solids. It was found that WT could change the activation energy of cellulose decomposition mainly due to the removal of AAEMs. The energy required for levoglucosan production could be mildly reduced, resulted from enlarged pore structure and better cellulose accessibility. Because of the removal of reactive AAEMs and enhanced product transportation, levoglucosan yield reached 55 wt% based on cellulose content, even with some inert AAEMs left in torrefied solids. The yields of phenols without methoxyl groups were also enhanced by WT. The perturbation-correlation moving-window two-dimensional correlation spectroscopy (PCMW2D) analysis of the in-situ DRIFT results further proved that WT could significantly change the pyrolysis pathway of cellulose from dehydration and condensation to hydrogen bond dissociation and glycosidic bond cleavage.

In situ evolution of functional groups in char during cellulose pyrolysis under the catalysis of KCl and CaCl2

A combination of in situ diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy, perturbation-correlation moving-window two-dimensional correlation spectroscopy (PCMW2D) and two-dimensional correlation spectroscopy (2D-COS) was used to reveal the catalytic mechanism of KCl and CaCl2 on cellulose char evolution during slow pyrolysis. Pretreatments of the one-dimensional spectra ensure the semi-quantitative analysis of the evolution of functional groups in pyrolysis char, which invoked principal component analysis followed by a Butterworth filter for denoising and extended multiplicative scatter correction. Through the differential processing of the absolute changes, the char evolution product was divided into ‘char rearrangement’ and ‘char devolatilization’ processes containing a high contribution from chemical reactions and physical migration, respectively. The ‘char rearrangement’ of cellulose pyrolysis consists of four stages, i.e. the budding, development, climax and decline stages, which were dominated by H-bond network reconfiguration, the consumption of C–O–C and OH, homogeneous devolatilization and aromatization, respectively. The uppermost influence of the two salts on the pyrolysis is the relationship alteration of C–O–C cleavage, dehydration reactions and ‘char devolatilization’. For neat, KCl-loaded and CaCl2-loaded cellulose, the unsaturated bonds were formed in the light reaction intermediate, heavy reaction intermediates and cellulose chain, respectively. Especially, the cleavage of most C–O–C following dehydration reactions conduced a shoulder peak in the differential thermogravimetry curve before the maximum weight loss rate of CaCl2-loaded sample. Due to the alteration, the pyrolysis was advanced but slowed down by the high content of unsaturated bonds in char. This study provides a powerful tool for the in situ semi-quantitative analysis of char evolution during the non-catalytic and catalytic thermo-chemical conversion of solid fuels and waste, and the results benefit to both biomass pyrolysis mechanism revelation and industrial production of biochar.

The effects of pH on the structure of polystyrene-nano manganese dioxide composites

Loading nano manganese dioxide (NMO) on the surface of polymers change the pH of point zero charge (pHPZC) of the dioxide. In this work, a polystyrene-NMO composite was prepared and the effects of pH from 1 to 14 on its structural and morphological properties were investigated. Moving-window, and perturbation-correlation moving-window two-dimensional correlation spectroscopies were used to analyze the pH-dependent Fourier transform infrared spectra of the composite. The auto correlation showed a peak value around pH=4 corresponding to the pHPZC of the composite, and another peak value around pH=9, which was assigned to change in the NMO structures. X-ray diffraction patterns and scanning electron microscopy further confirmed the changes at both pH=4 and pH=9 that were accompanied by a change in the morphology and crystalline structures of the composite. Moving-window and perturbation-correlation moving-window two-dimensional correlation spectroscopies are powerful tools in finding overlapped, weak, and hidden peaks along the spectral direction and could be used to locate the pHPZC of solid materials.

Perturbation-correlation moving-window two-dimensional correlation spectroscopic studies on the heat treatment of poly(vinyl alcohol)/silver nitrate film

In this paper, poly(vinyl alcohol)/silver nitrate (PVA/AgNO3) films were annealed at 180 °C for 1 h to prepare highly electrically conductive poly(vinyl alcohol)/silver (PVA/Ag) nanohybrids. Ultraviolet (UV)-visible absorption spectra, X-ray diffraction (XRD) scans, and scanning electronic microscopy (SEM) were applied to investigate the structures and morphology of the PVA hybrids. Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) were employed to study the thermal property of PVA/AgNO3 films. Furthermore, perturbation-correlation moving-window two-dimensional (PCMW2D) correlation spectroscopy combined with temperature-dependent Fourier transform infrared (FTIR) spectroscopy was used to investigate the conversion of AgNO3 into Ag nanoparticles in PVA matrix. The results show that the chelates for AgNO3 coordinated with hydroxyl groups are primarily decomposed in the temperature regions of 39.7–72.6 °C and 182.7–199.6 °C. AgNO3 is reduced into Ag0 and the hydroxyl groups of PVA are oxidized into carbonyl groups. The PVA-AgNO3 chelates are very rapidly decomposed in the temperature region of 182.7–199.6 °C. Large amounts of Ag0 produced by the reduction of AgNO3 are aggregated into Ag nanoparticles which are homogeneously dispersed into the PVA matrix. When the temperature increases to 212.7 °C, the unhydrolyzed acetate groups in PVA chains are sharply decomposed.

Water Uptake of Poly(2-N-Alkyl-2-Oxazoline)s: Temperature-Dependent Fourier Transform Infrared (FT-IR) Spectroscopy and Two-Dimensional Correlation Analysis (2DCOS)

A library of poly(2-oxazoline)s with varying length of the alkyl side-chain has been investigated by variable-temperature Fourier transform infrared (FT-IR) spectroscopy. These polymers are suitable for studies of structure-property relationships as their cationic ring-opening polymerization and the relatively facile monomer synthesis enable a control of the molecular structure. In this contribution, the number of carbon atoms in the linear side-chain is systematically varied from a short methyl to a long nonyl group. Previous studies showed that the sample library can be split in two groups: poly(2-oxazoline)s with a short side-chain (methyl-, ethyl-, and isopropyl-) exhibit hygroscopic behavior, while those with longer side-groups (butyl- and longer) were found to be semi-crystalline. To gain further insight into the mechanisms of hydrogen bonding and crystallization, temperature-dependent infrared (IR) spectroscopy has been applied in the current study. The processes involved have been monitored by generalized two-dimensional correlation spectroscopy (2DCOS) and perturbation-correlation moving-window two-dimensional correlation spectroscopy (PCMW2D) in the C=O stretching region around 1645 cm(-1). These advanced analysis techniques provided valuable additional information on the material behavior during heating. As water is removed from the samples in the course of the heating process, it was possible to clearly distinguish between "loosely associated" and hydrogen-bonded water. Furthermore, the melting process of the semi-crystalline samples could be depicted. For the poly(2-isopropyl-2-oxazoline) even a crystallization process could be monitored in the temperature range between glass transition and melting.

Two-Step Curing Reaction of Epoxy Resin Studied by Thermal Analysis and Infrared Spectroscopy

A curing reaction of bisphenol A diglycidyl ether epoxy resin with 4,4'-diaminodicyclohexyl methane hardener was investigated by means of modulated differential scanning calorimetry (MDSC) and infrared (IR) spectroscopy. MDSC observation revealed that the curing process of the resin occurred in two steps. Mid-infrared and near-infrared spectra of the resin were measured as a function of temperature. The obtained spectra were analyzed by perturbation-correlation moving-window two-dimensional correlation spectroscopy (PCMW2D-COS). The first step was revealed as a polymerization reaction among the oxirane group and primary and secondary amine groups, followed by etherification; the second step of the curing process occurred in the vicinity of the gelation point and was characterized by the growth of a three-dimensional cross-linking structure with tertiary amine and etherification of the hydroxyl group.

Tracing the crystallization process of polyoxymethylene/poly(ethylene oxide) crystalline/crystalline blends by two-dimensional infrared correlation spectroscopy

A new perturbation-correlation moving-window two-dimensional correlation (PCMW2D) infrared spectroscopy was employed to study the complex crystallization of the polyoxymethylene/poly(ethylene oxide) (POM/PEO) crystalline/crystalline blends for the first time. The online polarizing microscope measurement found POM/PEO forms the crystalline/crystalline blends with a typical island structure. The PCMW2D IR spectra determined three processes of the POM/PEO crystallization. The first is the maximum crystallization temperature of POM (138°C). The second is the POM recrystallization process (72°C). The thickening speed of the lamellae (FCC), as well as the crystallization of the macrocyclic POM, is faster than the improvement of POM ECC. The existence of the PEO melts significantly decelerates the improvement speed of ECC in interface. The third is the maximum crystallization temperature of PEO (35°C). According to the results of the generalized 2D correlation analysis, it can be found the POM ECC plays a leading role during the POM/PEO crystallization.

NIR spectroscopic study of the dissolution process in pharmaceutical tablets

In this study, water penetration and the interaction between water and a pharmaceutical excipient in a tablet were investigated using near-infrared (NIR) spectroscopy and perturbation-correlation moving-window two-dimensional correlation spectroscopy (PCMW-2DCS). The penetration rate of water into a tablet was mainly dependent on the porosity of the tablet and was less dependent on the type of excipient. This behavior was well described by the Lucas–Washburn theory. The PCMW-2DCS technique revealed that there are two-staged interaction changes in NIR spectra of the water–powder interactions. The first and second changes corresponded to the water–solid interaction and the dissolution of the solid, respectively. The diffusion-controlled dissolution model by Nernst well explained these results.

Temperature-Dependent Changes in Hydrogen Bonds in Cellulose Iα Studied by Infrared Spectroscopy in Combination with Perturbation-Correlation Moving-Window Two-Dimensional Correlation Spectroscopy:  Comparison with Cellulose Iβ

Our recent IR study demonstrated that hydrogen-bond structure in cellulose Ibeta drastically changes around 220 degrees C (Watanabe et al. Biomacromolecules 2006, 7, 3164). In the present study, temperature-dependent IR spectra of cellulose Ialpha from 30 to 260 degrees C were analyzed by use of perturbation-correlation moving-window two-dimensional correlation spectroscopy. It was observed that as in the case of cellulose Ibeta abrupt changes in the hydrogen-bond structure occur around 220 degrees C in cellulose Ialpha. It was also revealed that although weakly hydrogen-bonded OH groups in Ibeta are stable below 230 degrees C thermal oxidation of those in Ialpha is accelerated around 220 degrees C. In this way, the present study has clarified a difference between the thermal behavior of Ialpha and that of Ibeta at the functional group level. Our result suggests that the drastic change in the hydrogen-bond structure around 220 degrees C makes cellulose Ialpha much more unstable than Ibeta.

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.