Determination of chlorinated hydrocarbons in water by fiber-optic evanescent wave spectroscopy and partial least-squares regression

An application of the multivariate calibration technique of partial least-squares (PLS) regression to near-infrared spectra of a fiber-optic sensor based on the evanescent wave principle is presented. The sensing element consists of a quartz glass fiber with a silicone cladding which enriches nonpolar water contaminants. Due to the interaction of the extracted molecules with the part of the light which is transmitted in the evanescent wave zone of the cladding, absorbance spectra of the contaminants can be collected. In view of a sensor application for in-situ environmental analysis, aqueous solutions of chlorinated hydrocarbon solvents (CHS), which often can be found as major water contaminants, have been measured. PLS regression was applied to three sets of CHS samples, representing typical features of NIR evanescent wave spectral data. These are, e.g., strong overlapping of the absorption bands of different CHS components, peak distortions due to temperature variations between reference and sample measurement and noisy data at analyte concentrations near to the limit of detection, respectively. For trichloroethene and 1,1-dichloroethene, where the calibration model was built for samples within a small concentration range of 1–9 mg l^–1, satisfactory prediction results could be obtained with a relatively small root-mean-square error of 0.3 mg l^–1 compared to analytical reference measurements. In contrast to this, for a three component system of dichloromethane, trichloromethane and trichloroethene with strongly overlapping absorption bands, where samples over a very broad concentration range from 3–4940 mg l^–1 were included in the PLS model, the prediction accuracy decreased enormously and for some samples strong deviations between real and predicted data occurred. Nevertheless, applying multivariate calibration to this difficult system with similar spectral features and huge differences in the concentration of the species allowed an acceptable spectral distinction and at least a semi-quantitative determination of the CHS species.     

Detection of endotoxin using an evanescent wave fiber-optic biosensor

The lipopolysaccharide endotoxin is the most powerful immune stimulant known and a causative agent in the clinical syndrome known as sepsis. Sepsis is responsible for more than 100,000 deaths annually, in large part due to the lack of a rapid, reliable, and sensitive diagnostic technique. This study describes the detection of LPS fromE. coli at concentrations as low as 10 ng/mL, in 30 s using an evanescent wave fiber-optic biosensor. Polymyxin B, covalently immobilized onto the surface of the fiber-optic probe, selectively bound fluorescently labeled LPS. Unlabeled LPS was detected in a competitive assay format using labeled LPS for signal generation. The competitive assay format worked in both buffer and plasma with similar sensitivities. This method can be used with other LPS capture molecules such as antibodies, lectins, or antibiotics, to simultaneously detect LPS and to determine the LPS serotype. The LPS assay using the fiber-optic biosensor is applicable to both clinical and environmental testing.     

Determination of hydrocarbons in water by evanescent wave absorption spectroscopy in the near-infrared region

An home-made EFA (evanescent field absorbance)-sensor has been tested for the determination of hydrocarbons in water. The investigations have been performed both with crude oil emulsions and petrol solutions. Cuvette and evanescent wave spectra of crude oil and petrol in the near-infrared region are presented and discussed. The concentration of aromatic compounds in crude oil can be determined semiquantitatively by the standard addition method. The sorption behaviour of the hydrocarbons in the cladding of the fiberoptic sensor has been investigated and a correlation between the sensor signal and the concentration of the aqueous hydrocarbon emulsion/solution could be shown. The desorption of the enriched molecules after the measurements is also presented. The petrol molecules evaporate in ambient air so that the sensor is easily regenerated. In case of oil measurements the hydrocarbon molecules cannot be removed by rinsing the sensor with clear water or by evaporating them in ambient air. It has to be regenerated by washing it with a high volatile solvent instead.     

Determination of hydrocarbons in water by evanescent wave absorption spectroscopy in the near-infrared region

An home-made EFA (Evanescent Field Absorbance)-sensor has been tested for the determination of hydrocarbons in water. The investigations have been performed both with crude oil emulsions and petrol solutions. Cuvette and evanescent wave spectra of crude oil and petrol in the near-infrared region are presented and discussed. The concentration of aromatic compounds in crude oil can be determined semiquantitatively by the standard addition method. The sorption behaviour of the hydrocarbons in the cladding of the fiberoptic sensor has been investigated and a correlation between the sensor signal and the concentration of the aqueous hydrocarbon emulsion/solution could be shown. The desorption of the enriched molecules after the measurements is also presented. The petrol molecules evaporate in ambient air so that the sensor is easily regenerated. In case of oil measurements the hydrocarbon molecules cannot be removed by rinsing the sensor with clear water or by evaporating them in ambient air. It has to be regenerated by washing it with a high volatile solvent instead.     

The automated sample preparation system MixMaster for investigation of volatile organic compounds with mid-infrared evanescent wave spectroscopy

For efficient development assessment, and calibration of new chemical analyzers a large number of independently prepared samples of target analytes is necessary. Whereas mixing units for gas analysis are readily available, there is a lack of instrumentation for accurate preparation of liquid samples containing volatile organic compounds (VOCs). Manual preparation of liquid samples containing VOCs at trace concentration levels is a particularly challenging and time consuming task. Furthermore, regularly scheduled calibration of sensors and analyzer systems demands for computer controlled automated sample preparation systems. In this paper we present a novel liquid mixing device enabling extensive measurement series with focus on volatile organic compounds, facilitating analysis of water polluted by traces of volatile hydrocarbons. After discussing the mixing system and control software, first results obtained by coupling with an FT-IR spectrometer are reported. Properties of the mixing system are assessed by mid-infrared attenuated total reflection (ATR) spectroscopy of methanol-acetone mixtures and by investigation of multicomponent samples containing volatile hydrocarbons such as 1,2,4-trichlorobenzene and tetrachloroethylene. Obtained ATR spectra are evaluated by principal component regression (PCR) algorithms. It is demonstrated that the presented sample mixing device provides reliable multicomponent mixtures with sufficient accuracy and reproducibility at trace concentration levels.     

DNA interaction probed by evanescent wave cavity ring-down absorption spectroscopy via functionalized gold nanoparticles

Evanescent wave cavity ring-down absorption spectroscopy (EW-CRDS) is employed to study interaction and binding kinetics of DNA strands by using gold nanoparticles (Au NPs) as sensitive reporters. These Au NPs are connected to target DNA of study that hybridizes with the complementary DNA fixed on the silica surface. By the absorbance of Au NPs, the interaction between two DNA strands may be examined to yield an adsorption equilibrium constant of 2.2 × 10¹⁰ M⁻¹ using Langmuir fit. The binding efficiency that is affected by ion concentration, buffer pH and temperature is also examined. This approach is then applied to the label-free detection of the DNA mutation diseases using the sandwich hybridization assay. For monitoring a gene associated with sickle-cell anemia, the detection limit and the adsorption equilibrium constant is determined to be 1.2 pM and (3.7 ± 0.8) × 10¹⁰ M⁻¹, distinct difference from the perfectly matched DNA sequence that yields the corresponding 0.5 pM and (1.1 ± 0.2) × 10¹¹ M⁻¹. The EW-CRDS method appears to have great potential for the investigation of the kinetics of a wide range of biological reactions.     

The structure of water in polymer systems as revealed by Raman spectroscopy

A review on the structure of water in aqueous polymer systems as revealed by Raman spectroscopy is presented. Various interpretations and analysis procedures for Raman bands of liquid water which have been proposed are introduced. The structure and hydrogen-bonding properties of water which exist in aqueous polymer solutions and gels are described. Effects of chemical properties of polymer chains and size of water domains surrounded by polymer chains on the structure of water are discussed.     

Positioning of bound electron wave packets in molecules revealed by high-harmonic spectroscopy

By solution of the time-dependent two-electron Schr?dinger equation, we demonstrate that strong-field ionization in combination with electron correlation can localize bound electron wave packets in molecules. The wave packet creation is revealed by the emission spectrum in high-order harmonic generation, which is sensitive to the ionization and recombination phase difference between different ionization channels. For hydrogen molecules at stretched internuclear distance, we find that the ionization phase difference between the gerade and ungerade channels is in the range from π and 1.5π, indicating that the bound wave packet either is initially on the same side as the outgoing electron or is delocalized.     

Spectral diffusion at the water/lipid interface revealed by two-dimensional fourth-order optical spectroscopy: a classical simulation study

Using a classical simulation protocol for nonlinear optical signals, we predict the two-dimensional (2D) spectra of water near a monolayer of [1,2-dimytristoyl-sn-glycero-3-phosphatidylcholine] (DMPC) generated by three IR probe pulses followed by one visible probe pulse. Sum-frequency-generation 1D spectra show two peaks of the OH stretch representing two environments: near-bulk water nonadjacent to DMPC and top-layer water adjacent to DMPC. These peaks create a 2D pattern in the fourth-order signal. The asymmetric cross-peak pattern with respect to the diagonal line is a signature of coherence transfer from the higher- to the lower-frequency modes. The nodal lines in the imaginary part of the 2D spectrum show that the near-bulk water has fast spectral diffusion resembling that of bulk water despite the orientation by the strong electrostatic field of DMPC. The top-layer water has slower spectral diffusion.     

Fiber-optic evanescent wave fourier transform infrared (FEW-FTIR) spectroscopy of polymer surfaces and living tissue

The new method of fiber-optic evanescent wave Fourier transform infrared (FEW-FTIR) spectroscopy has been applied to studies of polymer surfaces and the diagnostics of normal, precancerous and cancerous tissue. This technique using optical fibers and fiber-optic sensors operating in the attenuated total reflection (ATR) mode in the mid-infrared (IR) region of the spectrum (850 – 1850 cm⁻¹) has found recently application in the area of tissue diagnostics. The method is suitable for noninvasive and rapid (seconds) direct measurements of the spectra of normal and pathological tissues in vitro, ex vivo, and in vivo. The FEW-FTIR technique is an ideal diagnostic tool for different types of soft, porous, foam, and rough polymer surfaces. Inhomogeneous coatings and defects on polymer surfaces as well as layer structures have also been detected by this method. It is convenient to apply this method to analyze large pieces of soft plastics and/or surfaces covered by plastics, since these types of surfaces are comparatively hard to analyze by traditional absorption spectroscopy. The FEW-FTIR technique is non-destructive, fast (15 seconds), and remote (up to a fiber length of 3m). In addition, it is sensitive enough to detect any changes in the vibrational spectra of a polymer surface, without heating and damaging it. The surfaces of polyethylene crumpled bags and rumpled films have been investigated in the range of 2000 – 1000 cm⁻¹. The distinct spectra of these surfaces as well as spectra of polytetrafluoroethylene have been recorded. The spectra of white and colored foams and different plastics have also been studied. Weak but distinct spectra have been recorded for carbon fibers (black, narrow fibers with a diameter of about 10 μm). Using the FEW-FTIR technique, measurements can be taken without preparing the sample. High quality spectra have also been obtained for the bulk and surfaces of apple, banana, grapefruit, and other food products. The method is expected to be further developed for geological and microelectronic applications.     

Determination of copolymer composition by Raman spectroscopy

The application of laser-Raman spectroscopy to the analysis of copolymers of glycidyl methacrylate (GMA) with methyl methacrylate (MMA) and styrene is discussed. For both copolymer systems the line near 1451 cm^?1, assigned to the methylene bending mode, was found to be a useful reference. Lines characteristic of each monomer were identified. The intensities of these lines were found to be linearly related to the composition of the copolymers when normalized against the 1451 cm^?1 reference. The line near 1730 cm^?1, assigned to the carbonyl stretching mode, was also found to be a useful reference for the copolymers of methyl methacrylate and glycidyl methacrylate.     

Water penetration into protein secondary structure revealed by hydrogen-deuterium exchange two-dimensional infrared spectroscopy

Two-dimensional infrared spectroscopy in conjunction with hydrogen-deuterium exchange experiments provides detailed information about solvent penetration into protein structure. Correlating the secondary-structure sensitivity of the amide I vibration and the solvent-exposure sensitivity of amide II provides a direct probe of solvent-inaccessible residues of proteins embedded in the hydrophobic core or those involved in strong hydrogen bonds in secondary structures. Distinct spectral signatures of the cross-peak region arising from the coupling of the amide I and II modes imply a significant degree of structural stability of hydrogen-bonded contacts in alpha-helices and beta-sheets in a series of proteins. Ubiquitin, an alpha/beta-protein, exhibits strong alpha-helical signatures and lacks those of the beta-sheet in the cross-peak region, demonstrating that ubiquitin's beta-sheet exchanges protons with the surrounding solvent and is conformationally unstable.     

Insights into reaction mechanisms in heterogeneous catalysis revealed by in situ NMR spectroscopy

This tutorial review intends to show the possibilities of in situ solid state NMR spectroscopy in the elucidation of reaction mechanisms and the nature of the active sites in heterogeneous catalysis. After a brief overview of the more usual experimental devices used for in situ solid state NMR spectroscopy measurements, some examples of applications taken from the recent literature will be presented. It will be shown that in situ NMR spectroscopy allows: (i) the identification of stable intermediates and transient species using indirect methods, (ii) to prove shape selectivity in zeolites, (iii) the study of reaction kinetics, and (iv) the determination of the nature and the role played by the active sites in a catalytic reaction. The approaches and methodology used to get this information will be illustrated here summarizing the most relevant contributions on the investigation of the mechanisms of a series of reactions of industrial interest: aromatization of alkanes on bifunctional catalysts, carbonylation reaction of methanol with carbon monoxide, ethylbenzene disproportionation, and the Beckmann rearrangement reaction. Special attention is paid to the research carried out on the role played by carbenium ions and alkoxy as intermediate species in the transformation of hydrocarbon molecules on solid acid catalysts.     

The diffusion of alcohols and water in polyamide 11: A study by fourier-transform near-infrared spectroscopy

The diffusion of different deuterium-labeled (OD) low-molecular-weight alcohols and D₂O in polyamide 11 (PA11) has been investigated by monitoring the NH/ND-exchange in the polymer by Fourier-Transform near-infrared (FTNIR) spectroscopy. The results demonstrate that the diffusion process of the different penetrants is strongly controlled by their molecular structure and geometry. To characterize this phenomenon quantitatively, the diffusion coefficients for the different deuteration agents have been determined for PA11. Furthermore, it could be shown that with this technique the less ordered regions of the polymer can be separated spectroscopically from the crystalline domains which are not accessible for the isotopically labeled diffusants.     

Structural inhomogeneity of interfacial water at lipid monolayers revealed by surface-specific vibrational pump-probe spectroscopy

We report vibrational lifetime measurements of the OH stretch vibration of interfacial water in contact with lipid monolayers, using time-resolved vibrational sum frequency (VSF) spectroscopy. The dynamics of water in contact with four different lipids are reported and are characterized by vibrational relaxation rates measured at 3200, 3300, 3400, and 3500 cm(-1). We observe that the water molecules with an OH frequency ranging from 3300 to 3500 cm(-1) all show vibrational relaxation with a time constant of T(1) = 180 ± 35 fs, similar to what is found for bulk water. Water molecules with OH groups near 3200 cm(-1) show distinctly faster relaxation dynamics, with T(1) < 80 fs. We successfully model the data by describing the interfacial water containing two distinct subensembles in which spectral diffusion is, respectively, rapid (3300-3500 cm(-1)) and absent (3200 cm(-1)). We discuss the potential biological implications of the presence of the strongly hydrogen-bonded, rapidly relaxing water molecules at 3200 cm(-1) that are decoupled from the bulk water system.     

Structure of water incorporated in amphoteric polymer thin films as revealed by FT-IR spectroscopy

The structure and hydrogen bonding of water incorporated in a thin film of amphoteric terpolymers composed of various ratios of MA, DMAPMA, and BMA were analyzed using the band shapes of the O--H stretching in the IR spectra. At an early stage of sorption of water, the IR spectrum for the water incorporated in the film with comparative contents of MA and DMAPMA residues was similar to that for free water. This is consistent with the tendency for zwitterionic polymers, but is in contrast with the drastic change in the IR spectrum of water incorporated in non-ionic polymer films such as polyBMA. These results suggest a correlation between the mildness of the charge-balanced polymers to the structure of incorporated water and their blood compatibilities.     

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     

The role of water H-bond imbalances in B-DNA substate transitions and peptide recognition revealed by time-resolved FTIR spectroscopy

The conformational substates B(I) and B(II) of the phosphodiester backbone in B-DNA are thought to contribute to DNA flexibility and protein recognition. We have studied by rapid scan FTIR spectroscopy the isothermal B(I)-B(II) transition on its intrinsic time scale. Correlation analysis of IR absorption changes occurring within seconds after a reversible incremental growth of the DNA hydration shell identifies water populations w(1) (PO(2)(-)-bound) and w(2) (non-PO(2)(-)-bound) exhibiting weaker and stronger H-bonds, respectively, than those dominating in bulk water. The B(II) substate is stabilized by w(2). The water H-bond imbalance of 3-4 kJ mol(-1) is equalized at little enthalpic cost upon formation of a contiguous water network (at 12-14 H(2)O molecules per DNA phosphate) of reduced ν(OH) bandwidth. In this state, hydration water cooperatively stabilizes the B(I) conformer via the entropically favored replacement of w(2)-DNA interactions by additional w(2)-water contacts, rather than binding to B(I)-specific hydration sites. Such water rearrangements contribute to the recognition of DNA by indolicidin, an antimicrobial 13-mer peptide from bovine neutrophils which, despite little intrinsic structure, preferentially binds to the B(I) conformer in a water-mediated induced fit. The FTIR spectra resolve sequential steps leading from PO(2)(-)-solvation to substate transition and eventually to base stacking changes in the complex. In combination with CD-spectral titrations, the data indicate that, in the absence of a bulk aqueous phase, as in molecular crowded environments, water relocation within the DNA hydration shell allows for entropic contributions similar to those assigned to water upon DNA ligand recognition in solution.