Recrystallization of water in a non-water-soluble polymer examined by Fourier transform infrared spectroscopy: poly(2-methoxyethylacrylate) with low water content

Crystallization of water during heating, the so-called "recrystallization of water", in poly(2-methoxyethylacrylate) (PMEA) was investigated by temperature-variable Fourier transform infrared spectroscopy. Recrystallization in a polymer-water system is generally understood to be a phase transition from glassy water (condensed water) to crystalline water. However, infrared spectral changes of the PMEA-water system with low water content indicated that the formation of ice I h during heating occurred by a vapor deposition process rather than by a crystallization process.     

Determination of the diffusion coefficient of water into atelocollagen type I thin films by attenuated total reflection Fourier transform infrared spectroscopy

 The diffusion coefficient of water into thin polymer layers of glutar aldehyde cross-linked atelocollagen type I matrix (sample 1, the typical layer thickness was about 0.065 × 10⁻³ m) at 23 °C was 1.142 × 10⁻¹⁰ m² s⁻¹. At twice the concentration of the cross-linking agent (sample 2) the diffusion coefficient was 2.795 × 10⁻¹⁰ m² s⁻¹. This increase was attributed to the more ordered morphology and the creation of ordered microvoids in the film. A larger surface area is then available for the transport of diffusing molecules, allowing a higher penetration rate of the solvent. Received: 11 January 2000/Accepted: 6 May 2000     

Diffuse reflectance infrared Fourier transform spectroscopy as a tool to characterise water in adsorption/confinement situations

We present experimental data acquired by diffuse reflectance infrared spectroscopy in the mid-IR (4000-400 cm(-1)), on micrometric-sized mineral grain powders. The spectral evolution of the OH-stretching band is followed when the adsorbed water film is thinned under dry conditions, from high to low hydration states. The IR bands are found to be characteristic of the degree of adsorption/confinement of the liquid water. The OH-stretching band is shifted toward shorter wavenumbers than in bulk water, showing that a significant portion of adsorbed water has a higher intermolecular bonding energy. Complementary treatment of the kinetics of water desorption, varying with the surface forces in the water film, confirms the relationships of these bands with the constrained water state. We distinguish different water types obeying liquid-liquid interactions (free and capillary water) or dominated by solid-water interactions (confined and adsorbed water). Part of this study is devoted to mesoporous silica MCM-41, of interest due to the restricted geometries of its mesopores (4.7 nm) favouring the confined water state. The methodology allows us to distinguish bulk and adsorbed/confined water, using spectral analysis coupled with an understanding of the dynamic behaviour of the desorption process.     

Fourier transform infrared spectroscopy with a sample deposition interface as a quantitative detector in size-exclusion chromatography

Micellar electrokinetic capillary chromatography was developed to analyze plant hormones including gibberellic acid, abscisic acid, indole-3-acetic acid, alpha-naphthaleneacetic acid, 2,4-dichlorophenoxyacetic acid, kinetin-6-furfurylaminopurine and N6-benzyladenine. The influences of some crucial parameters including buffer concentration, pH value, micelle concentration and applied voltage on electrophoretic separation were investigated. Under optimum conditions (50 mM borate as the running buffer containing 50 mM sodium dodecylsulfate, pH 8.0; separation voltage: -15 kV; injection: hydrodynamic injection, 5 s at 50 mbar; temperature: 25 degrees C), a complete separation of seven plant hormones was accomplished within 30 min. Emphasis was placed on improving detection sensitivity in order to detect small amounts of hormones in plant tissue. Multiple wavelength detection and expanded bubble cell capillary were used with enrichment factors of 2 and 3, respectively. In addition, an on-line concentration method of large volume sample stacking was designed. Enrichment factors of up to approximately 10-600 were achieved for these hormones with detection limits down to 0.306 ng/ml. The method was successfully applied to analyzing abscisic acid in flowers of transgenic tobacco.     

Conformational order of n-alkyl modified silica gels as evaluated by Fourier transform infrared spectroscopy

The conformational behaviour of non-deuterated and selectively deuterated alkyl modified silica gels in the dry state is examined by variable temperature FT IR spectroscopy. In the present study, three systems are considered, which are distinguished by the length of the tethered alkyl chains (C9Hl9-, C18H37-, C22H45-). The desired information is obtained by the analysis of various conformational-sensitive IR bands, including CH2 wagging, CD2 stretching and CD2 rocking bands. The analysis of the CH2 wagging bands provides the relative amounts (i.e., integral numbers over the whole chain) of the kink/gauche-trans-gauche, double-gauche and end-gauche conformers in the tethered alkyl chains. From the analysis of the CD2 stretching and CD2 rocking bands information about the conformational order at a specific deuterated methylene segment is available. Here, the CD2 rocking band data are used to determine the amount of gauche conformers at the deuterated carbon positions C-4 and C-6, and C-12. It is found that the conformational order critically depends on the actual alkyl chain length, chain position and sample temperature. Particular emphasis is given to the impact of the external pressure during sample preparation on the alkyl chain conformations, about which so far no information is available. It is observed that the samples prepared as KBr pellets, which experienced a pressure of about 10 kbar, are characterised by a lower amount of gauche conformers. This substantial increase of conformational order is attributed to better alkyl chain packing along with a gain of intermolecular chain interactions.     

Detection of trace materials with Fourier transform infrared spectroscopy using a multi-channel detector

FTIR spectroscopy is one of the most powerful methods for material characterization. However, the sensitivity of this analytical tool is often very limited especially for materials with weak infrared absorption or when spectral bands of the targeted trace material overlap with the spectral bands of major components. Fortunately, for heterogeneous samples, there is an opportunity to improve the sensitivity of detection by using an imaging approach. This paper explores the opportunity of enhancing the sensitivity of FTIR spectroscopy to detect trace amounts of materials using the FTIR imaging approach based on a focal plane array (FPA) detector. Model sample tablets of ibuprofen in hydroxypropyl methylcellulose (HPMC) have been used to exemplify the detection limits of FTIR spectroscopy using: (a) a conventional mercury cadmium telluride (MCT) detector and (b) a FPA detector. The sensitivity level was compared and it has been found that for this particular set of samples, the lowest concentration of ibuprofen in HPMC that can be detected using attenuated total reflection (ATR) measuring mode with the single element MCT detector was 0.35 wt% while using the FPA detector, the presence of drug has been detected in a sample that contains as little as 0.075 wt% of drug. The application of using this enhanced sensitivity offered by the multi-channel detector to probe trace amounts of drug particles left on the surface of a finger after handling a small amount of the drug has also been demonstrated. These results have broad implications for forensic, biomedical and pharmaceutical research.     

Surface hydration of aqueous calcium minerals as studied by Fourier transform Raman and infrared spectroscopy

Rapid hydration reactions of several calcium minerals are studied using Fourier transform (FT) Raman and infrared (IR) spectroscopy. Oleate adsorption over aqueous synthetic fluorite, calcite and gypsum (pH 9) is investigated and adsorption mechanisms are discussed.     

Determination of chlorinated hydrocarbons introduced into air/acetylene flames by Fourier transform infrared emission spectroscopy

A Fourier transform spectrometer is used to record the infrared emission from chlorinated hydrocarbons combusted in an air/acetylene flame. In this manner, the chlorinated hydrocarbons are determined by monitoring the infrared emission of hydrogen chloride at 2653 cm(-1). Discussion is presented of the air/acetylene flame background, and the potential spectral interference from the emission of deuterated species. Practical detection limits for chloroform, carbon tetrachloride and methylene chloride in acetone, methanol, and ethanol are solvent independent and are found to be 1.1, 0.80, and 1.0%, respectively. Calibration curves for these three analytes are linear from their detection limits to approximately 55% (v/v). In addition, evidence is presented that flame flicker-noise does not lead to a multiplex disadvantage when the Fourier transform instrument is used for data acquisition.     

Fourier transform infrared spectroscopy as a tool for the study of rare earths carbohydrates complexes

FT-IR spectra of the mixtures of praseodymium chloride and glucose in glassy state were investigated. From the changes of relative intensity and shifts of the characteristic frequency of glucose and water, it is concluded that the coordinated water molecules of the praseodymium ions are partially substituted by glucose through O-H groups which coordinated with praseodymium ions to form chelate ions.     

State of irremovable water in solid polymer films examined by fourier transform infrared spectroscopy I: poly(ethylene glycol) dimethyl ether

The state of the sorbed water, including the water that cannot be removed by the reduced pressure and water-sorption processes, into poly(ethylene glycol) dimethyl ether (PEG-DME) film was examined by Fourier transform infrared (FT-IR) spectroscopy. The spectrum of the irremovable water could be obtained without a thermal treatment frequently used as the dehydration procedure. It was found that the irremovable water mainly existed in the crystalline region of PEG-DME film, and that its hydrogen-bonding (HB) structure differed from that of the water sorbed from the air. Moreover, the amount of water having the same HB structure as the irremovable water increased with the water contents. These findings could not be revealed by the spectrum of the sorbed water obtained by the conventional dehydration procedure. The experimental procedure examined here allowed us to investigate the true aspects of the irremovable water and the water-sorption processes.     

Fourier transform infrared spectroscopy supported by multivariate statistics in compatibility study of atenolol with excipients

The objective of this study was to use Fourier transform infrared spectroscopy (FTIR) and multivariate statistics to investigate compatibility/incompatibility of atenolol as a representative of active pharmaceutical ingredients and excipients, such as β-cyclodextrin, methylcellulose, starch and chitosan, when used in solid dosage formulations. Two-component physical mixtures consisting of atenolol and selected excipients were studied by FTIR spectroscopy and two methods of multivariate statistical analysis – principal component analysis (PCA) and cluster analysis (CA), which were used as a supplementary tool for interpretation of the FTIR spectra. Taking into account variability explained by the first two principal components, the results of PCA were visualized in the form of a bi-dimensional scatterplot. A lack of interaction was confirmed by two distinct clusters created by both atenolol and a particular excipient with their mixtures. In the case of CA, lack of interaction between both ingredients was also indicated by two large clusters at a level of 33 or 66% of the maximum distance. The results of the investigations show that with the exception of β-cyclodextrin, the remaining excipients are compatible with atenolol. These findings were confirmed by complementary methods, such as differential scanning calorimetry, thermogravimetry and X-ray powder diffraction.     

Fourier transform infrared spectroscopic study of water-in-supercritical CO2 microemulsion as a function of water content

Fourier transform infrared (FT-IR) spectrum of water-in-supercritical CO(2) microemulsion was measured at 60 degrees C and 30.0 MPa over a wide range of water/CO(2) ratio from 0.0 to 1.2 wt % to study the distribution of water into CO(2), interfacial area around surfactant headgroup, and core water pool. The microemulsion was stabilized by sodium bis(1H,1H,2H, 2H-heptadecafluorodecyl)-2-sulfosuccinate [8FS(EO)(2)] equimolarly mixed with sodium 1-oxo-1-[4-(tridecafluorohexyl)phenyl]-2-hexanesulfonate [FC6HC4] or with poly(ethylene glycol) 2,6,8-trimethyl-4-nonyl ether [TMN-6]. The signal area of the O-H stretching band of water suggested that the number of water molecules in the microemulsion increases linearly with the water/CO(2) ratio, except for a slow initial increase below 0.4 wt % due to a part of water dissolved in CO(2). The amount of water in CO(2) was evaluated by decomposing the bending band of water into two components, one at lower frequency ascribed to water in CO(2) and the other at higher frequency to water in the microemulsion. The decomposition confirmed that CO(2) is saturated with water at the water content of 0.4 wt %. It was also revealed, from the symmetric SO stretching frequency of the surfactant, that the sulfonate headgroup is completely hydrated at the water/CO(2) ratio of 0.4-0.5 wt %. The results demonstrated that water is introduced preferentially into CO(2) and the interfacial area at small water content, and then is loaded into the micelle core after the saturation of CO(2) with water and the full hydration of the surfactant headgroup.     

Fourier transform infrared spectroscopy as a tool to study structural properties of cytochromes P450 (CYPs)

Cytochrome P450 proteins (CYPs) are a big class of heme proteins which are involved in various metabolic processes of living organisms. CYPs are the terminal catalytically active components of monooxygenase systems where the substrate binds and is hydroxylated. In order to be functionally competent, the protein structures of CYPs possess specific properties that must be explored in order to understand structure–function relationships and mechanistic aspects. Fourier transform infrared spectroscopy (FTIR) is one tool that is used to study these structural properties. The application of FTIR spectroscopy to the secondary structures of CYP proteins, protein unfolding, protein–protein interactions and the structure and dynamics of the CYP heme pocket is reviewed. A comparison with other thiolate heme proteins (nitric oxide synthase and chloroperoxidase) is also included. Figure The protein secondary structure, protein unfolding, redox-partner protein–protein interaction, structural changes induced by the reduction of the heme iron, and the structure and dynamics of the active site of cytochromes P450 (CYP) can be studied using Fourier transform infrared spectroscopy (FTIR). FTIR spectroscopy is a good approach for gaining a deeper insight into structure–function relationships in CYPs. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Detection of volatile organic compounds by temperature-programmed desorption combined with mass spectrometry and Fourier transform infrared spectroscopy

A temperature-programmed desorption (TPD) device connected to a mass spectrometer was used to detect volatile organic compounds from air samples. The main aim was to develop an analytical method, by which both non-polar and polar organic components can be detected in the same run. In TPD, the adsorbed compounds are desorbed from the resin more slowly than in the conventional trapping techniques, such as purge-and-trap technique, in which the resin is flash-heated and the compounds are desorbed at the same time to a cryogenic trap or an analytical column. In TPD, the adsorbent resin acts also as an analytical column. In this way it is possible to obtain more rapid analysis, and also a more simple instrumentation, which can be used on-line and on-site. In this work, a new version of TPD device, which uses a resistor for heating and a Peltier element for rapid cooling, was designed and constructed. Various adsorbent resins were tested for their adsorption and desorption properties of both polar and non-polar compounds. When using a mixture of adsorbent resins, Tenax TA and HayeSep D, it was possible to analyze both polar, low-molecular weight compounds, such as methanol and ethanol, and non-polar volatile organic compounds, such as benzene and toluene, in the same run within 15 min including sampling. The same TPD principle was also tested using a Fourier transform infrared spectrometer as an analytical instrument, and the results showed that it was possible to obtain a separation of similar compounds, such as hexane and heptane, and still retaining the same sensitivity as the original on-line FTIR instrument.     

Molecular recognition of 7-(2-octadecyloxycarbonylethyl)guanine to cytidine at the air/water interface and LB film studied by Fourier transform infrared spectroscopy

Monolayer behavior of a nucleolipid amphiphile, 7-(2-octadecyloxycarbonylethyl)guanine (ODCG), on aqueous cytidine solution was investigated by means of surface-molecular area (pi-A) isotherms. It indicates that molecular recognition by hydrogen bonding is present between ODCG monolayer and the cytidine in subphase. The Fourier transform infrared (FTIR) transmission spectroscopic result indicates that the cytidine molecules in the subphase can be transferred onto solid substrates by Langmuir-Blodgett (LB) technique as a result of the formation of Watson-Crick base-pairing at the air/water interface. Investigation by rotating polarized FTIR transmission also suggests that the headgroup recognition of this amphiphile to the dissolved cytidine influence the orientation of the tailchains.     

Investigation of water diffusion process in ethyl cellulose-based films by attenuated total reflectance Fourier transform infrared spectroscopy and two-dimensional correlation analysis

Two-dimensional correlation spectroscopy (2Dcos) analysis on the time-resolved attenuated total reflectance Fourier transform infrared spectroscopy has been employed to investigate the diffusion behavior of water in ethyl cellulose/triethyl citrate (EC/TEC) films with varied TEC content. The diffusion coefficients of water in the EC-based films are calculated from the diffusion curves according to the Fickian Diffusion Model. And they are observed to increase with TEC content, possibly caused by the increased free volume in the film matrix. In the 2Dcos analysis, the broad O–H stretching vibration region is split into at least four bands, which can be assigned to four different states of water molecules, that is, bulk water, cluster water, relatively free water and free water. Moreover, it is found that as water molecules disperse into the EC-based films, cluster water with moderate hydrogen bonds diffuses faster than bulk water with strong hydrogen bonds. The relatively free water and free water are formed during the diffusion process due to their interactions with the films matrix, which makes water molecules confined and restricted in limited space.     

Studies on charge transfer properties from mixture of Schiff base and zinc complex in Langmuir-Blodgett film by UV-vis absorption and Fourier transform infrared spectroscopy

A novel mixed Langmuir Blodgett (LB) film based on a 1:1 (molar ratio) mixture of a non-amphiphile complex (Et4N)2[Zn(dmit)2] (H2dmit = 4,5-dimercapto-1,3-dithiole-2-thione) and Schiff base amphiphile 2,4-dihydroxy-N-octadecylbenzylideneamine (SBC18) was constructed and characterized by Fourier transform infrared (FTIR) spectra and UV-vis electronic absorption spectra. After iodine was doped in situ, magnitude of charge transfer increases, which was demonstrated by FTIR and UV-vis absorption spectral analysis.     

Adulteration of diesel/biodiesel blends by vegetable oil as determined by Fourier transform (FT) near infrared spectrometry and FT-Raman spectroscopy

In this work it has been shown that the routine ASTM methods (ASTM 4052, ASTM D 445, ASTM D 4737, ASTM D 93, and ASTM D 86) recommended by the ANP (the Brazilian National Agency for Petroleum, Natural Gas and Biofuels) to determine the quality of diesel/biodiesel blends are not suitable to prevent the adulteration of B2 or B5 blends with vegetable oils. Considering the previous and actual problems with fuel adulterations in Brazil, we have investigated the application of vibrational spectroscopy (Fourier transform (FT) near infrared spectrometry and FT-Raman) to identify adulterations of B2 and B5 blends with vegetable oils. Partial least square regression (PLS), principal component regression (PCR), and artificial neural network (ANN) calibration models were designed and their relative performances were evaluated by external validation using the F-test. The PCR, PLS, and ANN calibration models based on the Fourier transform (FT) near infrared spectrometry and FT-Raman spectroscopy were designed using 120 samples. Other 62 samples were used in the validation and external validation, for a total of 182 samples. The results have shown that among the designed calibration models, the ANN/FT-Raman presented the best accuracy (0.028%, w/w) for samples used in the external validation.     

The effect of pressure on the phase transition behavior of tridecane, pentadecane, and heptadecane: a Fourier transform infrared spectroscopy study

The effect of pressure on the phase transition behavior of tridecane (C(13)), pentadecane (C(15)), and heptadecane (C(17)) has been investigated up to 489, 220, and 387 MPa, respectively, using Fourier transform infrared spectroscopy at 25 °C. The transition between the high pressure ordered (HPO) and high pressure rotator (HPR) phases has been observed in the pressure ranges of 270-220, 106-95, and 152-181 MPa for C(13), C(15), and C(17), respectively, and the transition between the HPR and liquid phases was observed in the pressure ranges of 171-112, 73-47, and 43-70 MPa for C(13), C(15), and C(17), respectively. The P(1)+P(3) band of the methylene rocking mode exhibits factor group splitting caused by intermolecular vibrational coupling. This was observed in both the HPO and HPR phases, while the P(1)+P(3) band did not split in the liquid phase. The separation of the peaks in the P(1)+P(3) band changed discontinuously at the HPO-HPR and HPR-liquid phase transitions, even though the separation is known to change continuously in the transition from the liquid to the high temperature rotator (HTR) phase. In the HPR phase, the ratio of the intensities of the higher and lower frequency components in the P(1)+P(3) doublet is roughly unity independent of pressure, while it is known to be much less than unity in the HTR phase. The separation of the P(1)+P(3) doublet in the HPR phase is found to be larger for longer alkanes. From the intensity ratio, a large proportion of alkane molecules is believed to participate in intermolecular vibrational coupling and possess herringbone-type short-range positional order in the HPR phase. Conversely, in the HTR phase only small proportion of alkane molecules participate in intermolecular vibrational coupling. From the pressure dependence of the separation of the doublet, intermolecular vibrational coupling and herringbone-type short-range positional order is considered to change discontinuously at the HPR-liquid phase transition, while they are reported to change continuously at the HTR-liquid phase transition. The HPR-liquid phase transition is governed by the effect of molecular packing while the HTR-liquid phase transition is predominantly governed by the difference in entropy between the herringbone-type and parallel-type packing.     

Structural coupling of an arginine side chain with the oxygen-evolving Mn4Ca cluster in photosystem II as revealed by isotope-edited Fourier transform infrared spectroscopy

Photosynthetic oxygen evolution by plants, algae, and cyanobacteria is performed at the Mn(4)Ca cluster in photosystem II (PSII) by light-driven water oxidation. It has been proposed that CP43-Arg357, which is located in the vicinity of the Mn(4)Ca cluster, plays a key role in the O(2) evolution mechanism; however, direct evidence for its involvement in the reaction has not yet been obtained. In this study, we have for the first time detected the structural coupling of CP43-Arg357 with the Mn(4)Ca cluster by means of isotope-edited Fourier transform infrared (FTIR) spectroscopy. Light-induced FTIR difference spectra upon the S(1)→S(2) transition (S(2)/S(1) difference spectra) of the Mn(4)Ca cluster were measured using isolated PSII core complexes from Synechocystis sp. PCC 6803 cells, where the Arg side chains were labeled with either [η(1,2)-(15)N(2)]Arg or [ζ-(13)C]Arg. Bands due to Arg side chain vibrations, which were extracted by taking a double difference between the S(2)/S(1) spectra of isotope-labeled and unlabeled samples, were found at 1700-1600 and 1700-1550 cm(-1) for [η(1,2)-(15)N(2)]Arg- and [ζ-(13)C]Arg-labeled PSII, respectively. These frequency regions are in good agreement with those of the CN/NH(2) vibrations of a guanidinium group in difference spectra between isotope-labeled and unlabeled Arg in aqueous solutions. The detected Arg bands in the S(2)/S(1) difference spectra were attributed to CP43-Arg357, which is the only Arg residue located near the Mn(4)Ca cluster. The presence of relatively high frequency bands arising from unlabeled Arg suggested that the guanidinium N(η)H(2) is engaged in strong hydrogen bonding. These results indicate that CP43-Arg357 interacts with the Mn(4)Ca cluster probably through direct hydrogen bonding to a first coordination shell ligand of a redox-active Mn ion. This structural coupling of CP43-Arg357 may play a crucial role in the water oxidation reactions.