At the solid/liquid interface: FTIR/ATR--the tool of choice

For the last 7 years, we have been researching various aspects of the Bayer process. Predominant among these has been the surface chemistry of Bayer process solids. To this end, we have been using Fourier transform infrared (FTIR) attenuated total reflection (ATR) spectroscopy for in situ studies of the surfaces of the Bayer process solids sodium oxalate and aluminium trihydroxide under extreme (high ionic strength, high pH), Bayer-like conditions. FTIR/ATR is one of the few techniques currently available to scientists wishing to explore solid/liquid interfacial phenomena in situ. Using this investigative technique, information regarding the nature of adsorbed species can be readily acquired, with details concerning adsorbate orientation and adsorption/desorption equilibria, speciation, mechanisms and kinetics obtainable. Not surprisingly, FTIR/ATR has become one of the tools of choice for those wishing to explore the solid/liquid interface, and the body of literature available on the subject has been steadily growing over the last 10-15 years. This review addresses the current state of knowledge in the area of FTIR/ATR with respect to interfacial spectroscopy, as well as introducing some of the more fundamental theoretical and practical aspects of the technique. Particular emphasis is placed upon applied interfacial research. In writing this review, we draw on a considerable amount of expertise in the use of FTIR/ATR in interfacial studies (in particular, the practical considerations involved), as well as a large and comprehensive literature database focussing primarily on the investigation of interfacial processes using the FTIR/ATR technique.     

Vibration Spectroscopy Stability Investigation of 12-Tungstosilicic Acid Solution

Heteropoly acids (HPA) attract the attention of large variety of scientists, due to HPA’s extraordinary interesting properties and possible application fields. 12-tungstosilicic acid (WSiA), the Keggin type HPA, has some promising characteristic to be used in catalytic processes, but with not well-defined stability. Raman spectroscopy was used for in situ analysis of WSiA hydrolysis in detail in a wide pH range of 1–12. Raman spectroscopy is able to give an almost immediate response/spectrum as a representation of the exact profile/composition of the solution. This method and FTIR spectroscopy, as a complementary technique, enabled recording of the solid and liquid phases of the same sample under different conditions. Our results confirm that the decomposition pathways of WSiA in solution proceed via the formation of the lacunary monovacant anion at pH > 6.4. This anion is a major constituent in pH range up to 9.5. With further increases in pH this species convert to the trivacant lacunary anion. The total decomposition of the Keggin anion to silicate and tungstate occurs at pH > 11.0. The results of the performed study contribute to understand the behavior of WSiA in the water–methanol solution, as the model system of aqueous-organic system. It is concluded that addition of methanol in aqueous solution of WSiA leads to expansion of the pH region where Keggin anion is stable up to 8.1 and above this pH value, precipitation occurs. The obtained data clarify the stability range of WSiA in both water and water–methanol solutions, as well.     

The determination of salivary oxypurines before and after exercise by combined liquid chromatography-field asymmetric waveform ion mobility spectrometry-time-of-flight mass spectrometry

A method combining field asymmetric waveform ion mobility spectrometry with liquid chromatography-mass spectrometry (LC-FAIMS-MS) has been developed for the analysis of the oxypurine compounds hypoxanthine (HX) and xanthine (XA) in saliva. Separation of the oxypurines from interfering matrix components was investigated using FAIMS-MS. The selected FAIMS parameters were then applied to the rapid LC-FAIMS-MS analysis of HX and XA using a short chromatographic separation method (7 min). A comparison of the LC-MS method with and without FAIMS applied, resulted in improved discrimination from saliva matrix interferences and improved chromatographic peak integration for both HX and XA using a FAIMS separation. A quantitative evaluation of the LC-FAIMS-MS method was performed giving limits of detection of 2.0 ng mL^?1 for HX and 1.8 ng mL^?1 for XA, and limits of quantification of 6.6 ng mL^?1 for HX and 6.0 ng mL^?1 for XA. The developed LC-FAIMS-MS method was applied to the targeted analysis of the oxypurine metabolites in saliva collected from healthy male athletes (n =?11) before and after exercise designed to induce oxidative stress; post-exercise collection time-points included immediately after exercise, one hour and twenty-four hours’ post-exercise. The salivary concentrations of both HX and XA were lower after physical exercise, compared to the pre-exercise (rest) concentrations and returned to approximately pre-exercise levels after twenty-four hours. The method reported has the potential for monitoring the salivary oxypurines, HX and XA, as biomarkers of oxidative stress and in other clinical applications.     

FTIR ATR SPECTRAL AND THEORETICAL VIBRATIONAL STUDIES OF URACIL IN DIMETHYLSULFOXIDE OR DIETHYLSULFOXIDE SOLUTIONS

Journal of Structural Chemistry - In this work the solutions of uracil in pure dimethylsulfoxide (DMSO) and diethylsulfoxide (DESO) have been studied by both FTIR ATR spectroscopy and...     

An FTIR study of the surface chemistry of the dynamic Si(100) surface during etching in alkaline solution

In situ FTIR spectroscopy has been used in the attenuated total reflectance (ATR) mode to investigate the surface chemistry of etching Si(100) surfaces in aqueous KOH. The effect of solution concentration and electrode potential on the Si-H vibrations has been explored and the experimental results compared with density functional theory calculations. In addition. the kinetics of surface passivation of n-Si(100) has been investigated using FTIR spectroscopy.     

Determination of Chlorinated Hydrocarbon Species in Aqueous Solution Using Teflon Coated ATR Waveguide/FTIR Spectroscopy

The potential of an optical sensor based on mid-infrared spectroscopy, utilising a zinc selenide (ZnSe) attenuated total reflectance (ATR) element coated with an amorphous Teflon polymer, to determine chlorinated hydrocarbon species (CHC) in an aqueous environment is examined. The polymer coating concentrates the analytes within the penetration depth of the Fourier transform infrared (FTIR) evanescent wave and excludes water from the region. Teflon AF (Amorphous Fluoropolymer) is a family of amorphous copolymers based on polytetrafluoroethylene (PTFE), and is commercially available in two polymeric grades. Teflon AF is highly amorphous in nature with a large 'void volume', exhibits excellent chemical resistance and low water absorption. Such properties identify it as an excellent candidate for enrichment coating on an ATR/FTIR sensor. The potential of both polymeric grades of Teflon AF as enrichment membranes for ATR/FTIR analysis of CHC species was examined and contrasted. A rapid, repeatable, reversible response was observed with both grades to a range of CHC species. Linear responses in the mg/L region, with detection limits in the low mg/L region were achieved with the system used.     

ATR and transmission analysis of pigments by means of far infrared spectroscopy

In the field of FTIR spectroscopy, the far infrared (FIR) spectral region has been so far less investigated than the mid-infrared (MIR), even though it presents great advantages in the characterization of those inorganic compounds, which are inactive in the MIR, such as some art pigments, corrosion products, etc. Furthermore, FIR spectroscopy is complementary to Raman spectroscopy if the fluorescence effects caused by the latter analytical technique are considered. In this paper, ATR in the FIR region is proposed as an alternative method to transmission for the analyses of pigments. This methodology was selected in order to reduce the sample amount needed for analysis, which is a must when examining cultural heritage materials. A selection of pigments have been analyzed in both ATR and transmission mode, and the resulting spectra were compared with each other. To better perform this comparison, an evaluation of the possible effect induced by the thermal treatment needed for the preparation of the polyethylene pellets on the transmission spectra of the samples has been carried out. Therefore, pigments have been analyzed in ATR mode before and after heating them at the same temperature employed for the polyethylene pellet preparation. The results showed that while the heating treatment causes only small changes in the intensity of some bands, the ATR spectra were characterized by differences in both intensity and band shifts towards lower frequencies if compared with those recorded in transmission mode. All pigments' transmission and ATR spectra are presented and discussed, and the ATR method was validated on a real case study. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Grafting copolymerization of polyethylene glycol methacrylate (PEGMA) onto preirradiated PP films

Polyethylene glycol methacrylate (PEGMA) with different polyethylene oxide units were grafted onto polypropylene (PP) films by a preirradiation grafting method. The effect of co-solvent system on the degree of grafting and water contact angle were determined, respectively. The grafted sample films were verified by Fourier Transform Infrared (FTIR) spectroscopy in the attenuated total reflectance mode (ATR). The biocompatibility and blood compatibility of the grafted PP films were evaluated by the determination of protein adsorption, platelet adsorption and thrombus.     

Development of an analytical method using microchip capillary electrophoresis for the measurement of fluorescein-labeled salivary components in response to exercise stress

We have developed an analytical method using microchip capillary electrophoresis (microchip CE) for the high-speed separation of fluorescein-labeled salivary components in response to exercise stress. Optimal separation was obtained using a borate buffer at pH 9.5 containing 10 mM beta-cyclodextrin and 1.0% (w/v) methylcellulose. To minimize individual differences in human saliva, such as viscosity, conductivity, and contaminants, the concentration of methylcellulose in the analytical conditions played a key factor. The optimized separation conditions produced identical electropherograms successfully despite of the use of different microchips made from quartz glass or poly-methylmethacrylate (PMMA). In addition, a practical application of bicycle ergometer stress was performed. Some components in human saliva showed a marked decrease after exercise stress.     

Infrared study of HDTMA+ intercalated montmorillonite

In this paper, FTIR spectroscopy using attenuated total reflection (ATR) and KBr pressed disk techniques has been used to characterize sorbed water and HDTMA+ in organo-clay. Sorbed water content decreases with the intercalation of HDTMA+. With the decrease of the sorbed water content, the position of the nu2 mode shifts to higher frequency dramatically while the stretching vibration shifts to lower frequency slightly, indicating that H2O is less strongly hydrogen bonded. This might be resulted from the polarization of H2O molecules by the changeable cations and HDTMA+. FTIR spectra show that both antisymmetric and symmetric CH2 stretching absorption bands shift to low frequencies with increase of amine concentration within the galleries of montmorillonite, elucidating the increase of ordered conformation. Furthermore, the present study demonstrates that the antisymmetric CH2 stretching mode is more sensitive to the conformational ordering than the symmetric stretching mode. When KBr pressed disk technique used, two well resolved absorption bands at 730 and 720 cm(-1), and at 1473 and 1463 cm(-1), corresponding to the methylene scissoring and rocking modes, respectively, could be observed in FTIR spectra of organo-clays with relative higher concentration of surfactant. However, the FTIR spectra using ATR technique only display singlets and they are independent of amine concentration and chain conformation. Our present study demonstrates that FTIR spectroscopy using KBr pressed disk technique is more suitable to probe the conformational ordering of surfactant in organo-clays than that suing ATR technique does.     

Reversible Immobilization of Peptides: Surface Modification and In Situ Detection by Attenuated Total Reflection FTIR Spectroscopy

A generic method is described for the reversible immobilization of polyhistidine‐bearing polypeptides and proteins on attenuated total reflecting (ATR) sensor surfaces for the detection of biomolecular interactions by FTIR spectroscopy. Nitrilotriacetic acid (NTA) groups are covalently attached to self‐assembled monolayers of either thioalkanes on gold films or mercaptosilanes on silicon dioxide films deposited on germanium internal reflection elements. Complex formation between Ni²⁺ ions and NTA groups activates the ATR sensor surface for the selective binding of polyhistidine sequences. This approach not only allows a stable and reversible immobilization of histidine‐tagged peptides (His–peptides) but also simultaneously allows the direct in situ quantification of surface‐adsorbed molecules from their specific FTIR spectral bands. The surface concentrations of both NTA and His–peptide on silanized surfaces were determined to be 1.1 and 0.4 molecules nm^?2, respectively, which means that the surface is densely covered. A comparison of experimental FTIR spectra with simulated spectra reveals a surface‐enhancement effect of one order of magnitude for the gold surfaces. With the presented sensor surfaces, new ways are opened up to investigate, in situ and with high sensitivity and reproducibility, protein–ligand, protein–protein, protein–DNA interactions, and DNA hybridization by ATR–FTIR spectroscopy.     

FTIR characterization of Candida species: a study on some reference strains and pathogenic C. albicans isolates from HIV+ patients

ATR–FTIR has been used together with principal components analysis to study some reference strains belonging to five different Candida species and 20 Candida albicans isolates from three HIV⁺ patients under different fluconazole regimens. The five reference strains were easily differentiated by using first derivative spectra of the carbohydrate region comprising the spectral range 900–1200 cm⁻¹. For the C. albicans clinical isolates, classification obtained by Fourier-transform infrared (FTIR) spectroscopy was compared with data from the genotypic method, PFGE. Results show a good correlation between the two methods for one patient who presented a partially conserved immune system with no previous fluconazole treatment, where all C. albicans strains isolated were susceptible to this antifungal agent. Divergences in the two methods appear for the two immuno-compromised patients receiving long-term fluconazole treatment. It is very probable that such iterative antifungal treatment can cause strong alterations in the yeast cell wall membrane and that the mismatch of the two techniques highlights the complex situation of strain-level identification and differentiation of clinical isolates originating from patients under prolonged treatment.     

Hydroxyapatite coating on porous polyurethane facilitated by tetraethoxysilane

Biomimetic growth of calcium phosphate compounds on porous polyurethane (PU) treated with tetraethoxysilane (TEOS) and soaked in simulated body fluid (SBF) solution was studied using scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDAX), and Fourier transformed infrared spectroscopy–attenuated total reflectance (FTIR–ATR). Polyurethane was treated with TEOS in order to produce silanol groups which stimulated the growth of hydroxyapatite when immersed in SBF solution. Polyurethanes that were not treated with TEOS did not show calcium phosphate growth upon immersion in SBF solution. The Ca and P determined by EDAX and inductively coupled plasma spectroscopy (ICP) analysis revealed that the surface layer was not stoichiometric hydroxyapatite, but carbonated, containing hydroxyapatite with a Ca/P ratio of 1.5–1.6. This was confirmed by FTIR–ATR.     

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

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

Determination of carbonate in marine solid samples by FTIR-ATR spectroscopy

A method for detecting carbonate in marine solid samples (sediments, corals) by Fourier transform infrared spectroscopy (FTIR) coupled to the total attenuated reflectance (ATR) technique is described. Compared to other techniques, the proposed method is not based on the measurement of CO2 evolved by combustion or acidification of the sample, but on the direct measurement of carbonate present in the sample. For this reason, the method by FTIR-ATR spectroscopy does not require any chemical pre-treatment. The proposed method allows determination of carbonate in the range 6-100% (w/w) as Na2CO3 and gives comparable results with the determination of inorganic carbon by elemental analysis.     

Spectroscopic evaluation of living murine macrophage cells before and after activation using attenuated total reflectance infrared spectroscopy

Infection activates immune response pathways in host macrophages and lymphocytes that might be of sufficient magnitude to facilitate early diagnoses of infections through a host immune biosignature. Attenuated total reflectance (ATR) infrared spectroscopy was used to examine the spectroscopic signatures of living mouse macrophage cells before and after activation. Cells were prepared as control samples, or activated with a combination of lipopolysaccharide and interferon-gamma (IFN-γ) and analyzed 21 h after treatment. Resulting ATR/IR spectra collected from the living cells were analyzed using principal components analysis (PCA) and other classification methods. Plotting the scores from the first two principal components against one another provides good separation between activated and control samples. Interpretation of the loadings plots indicated that cellular activation was associated with changes in nucleic acid, protein and lipid infrared bands. Spectral samples were used to develop classification models based on activation status. Linear discriminant analysis (LDA) and K-nearest neighbor (K-NN) models were developed with 100% classification rates, using leave-one-out cross-validation procedures. Activated macrophages can be distinguished from macrophages in the resting state by their ATR spectroscopy biosignatures.     

Modification of surface properties of polyethylene by perfluoropolyether blending

The preparation of a stabile blend from thermoplastic polymer and lubricating additive was studied with high density polyethylene (HDPE) and perfluoropolyether (PFPE). PFPE was melt blended within HDPE by injection molding. The chemical composition of the mixtures, the relative amount of PFPE on the surface, and the nature of the surface were studied by three surface sensitive methods: attenuated total reflectance infrared (ATR‐IR) spectroscopy, secondary ion mass spectroscopy (SIMS), and contact angle (CA) measurement. All the blends exhibited improved hydrophobicity. CA and SIMS gave a maximum response when about 2.0 wt % PFPE was added, whereas ATR‐IR spectroscopy gave maximum response for an addition of about 3.0 wt %. No changes in surface properties were observed when samples were reanalyzed about 1–4 months after preparation. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2252–2258, 2005     

A critical comparison of solid sample preparation techniques in infrared spectroscopy

The growing capabilities of FTIR spectrometers and computers have opened the use of new sample preparation techniques in infrared spectroscopy. In addition to the established KBr pellet technique and ATR spectroscopy, diffuse reflectance and photoacoustic spectroscopy are increasing in importance. A systematic experimental comparison of these techniques has been made in order to make proper use of their mutual advantages.     

Grafting copolymerization of N,N-dimethyacrylaminoethylmethacrylate (DMAEMA) onto preirradiated polypropylene films

Grafting copolymerization of dimethylaminoethylmethacrylate (DMAEMA) onto preirradiated polypropylene (PP) films was studied. PP samples were irradiated by electron beam in air. The effects of co-solvent system of ethanol/water (EtOH/H₂O), absorbed dose, monomer concentration, reaction time, and reaction temperature on the degree of grafting were determined. The grafted sample films were investigated by Fourier transform infrared (FTIR) spectroscopy in the attenuated total reflectance mode (ATR).     

表面接枝含氟苯乙烯共聚物的聚酯薄膜制备与表征

利用表面引发原子转移自由基聚合(SI-ATRP)在聚对苯二甲酸乙二醇酯(PET)薄膜表面接枝苯乙烯和4-氟苯乙烯的共聚物.研究不同反应时间和不同配比下接枝共聚物对聚酯薄膜表面组成、结构和性能的影响.通过傅利叶变换红外光谱仪(ATR/FTIR),X-射线光电子能谱仪(XPS),凝胶渗透色谱(GPC)和扫描电子显微镜(SEM)对接枝改性前后PET薄膜的表面组成,结构和形貌进行分析;利用接触角测试和表面能计算对比研究接枝改性前后PET薄膜的表面性能.结果表明反应时间和单体百分含量对接枝百分率及接触角有一定的影响,随着反应时间的增长,聚酯薄膜表面接枝百分率增大,接触角增加,表面自由能下降.