We report a liquid-liquid extraction system based on perfluorocarbon (fluorous-solvent extraction) that allows selective extraction of metal ions from aqueous and organic phases to a perfluorocarbon phase (FC-72) with perfluorinated β-diketone (1,1,1,5,5,6,6,6-octafluoro-2,4-hexanedione), which can be followed by backward extraction using 1 M nitric acid.

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The present review describes a new enhancement technique for Raman scattering in aqueous solutions. Raman scattering spectroscopy has an inherent ability to distinguish between molecules with great similarity and provides useful information on local physical and chemical environments at their functional groups' level. Since the Raman scattering signals from water molecules are quite weak, Raman spectroscopy has great advantage for detection or discrimination of a trace amount of analytes in aqueous environments. However, Raman scattering cross-sections are inherently small and it generally requires high power excitation and long acquisition times to obtain high-quality Raman spectra. These conditions create disadvantages for the analyses for living cells and real-time monitoring for environmental analyses. Here, I describe a new Raman enhancement technique, namely “electron enhanced Raman scattering (EERS)”, where artificially generated electrons additionally affect the polarizability of target molecular systems and enhance their inherent Raman cross-section. Principles of the EERS and its applications to aqueous solutions are presented.

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Langmuir-Blodgett films and cast films of a ferroelectric liquid crystal of sec-butyl-6-(4-(nonyloxy)benzoyloxy)-2-naphthoate have been fabricated. Their thermal behavior was investigated using infrared spectroscopy at elevated temperature combined with principal component analysis. The result shows a new phase transition from smectic A to nematic phase, compared to the phase sequence obtained by polarizing optical microscopy. Another solid transition of different isomeric crystals was also found, which was confirmed by calorimetric measurement.

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A curve fitting technique for optical spectra based on a robust estimator, least median squares (LMedS), is introduced in this study. For the effective calculation of LMedS, particle swarm optimization (PSO) is also introduced. Unlike a standard curve fitting method using least squares (LS) estimator, the method based on LMedS estimator is less influenced by outliers in experimental data. Two kinds of data sets, simulated data with outliers and temperature-dependent near-infrared (NIR) spectra of oleic acid (OA) are applied for the demonstration of the proposed method. The results clearly reveal that, compared with the LS estimator, the proposed method can effectively reduce undesirable effects of low SN ratio and can yield more accurate fitting results.

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We report on the application of Raman scattering as a probe to study 4-mercaptopyridine (4-Mpy) surface-modified CuO nanocrystals. Enhanced Raman scattering from 4-Mpy adsorbed on CuO nanocrystals was observed. The Raman signals displayed 10² enhancement compared with those of 4-Mpy in solution. We compared the Raman spectra of 4-Mpy molecules adsorbed on CuO nanocrystals and Ag, Cu substrate. A particular feature of the semiconductor substrate that was different from the metal substrate was revealed. The excitation wavelength-dependent behavior was clearly observed.

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In the present study, a dry film-based Fourier transformed-infrared (FT-IR) spectroscopic technique, coupled with boosting support vector regression (BSVR), was employed for a blood glucose assay. Potassium thiocyanate (KSCN) was taken in the dry-film method as an internal standard to compensate for any film thickness variation. This technique circumvents interference from water absorption, and requires only 5 µl of a sample. Moving window partial least-squares regression (MWPLSR) was used for wavenumber interval selection before multivariate modeling. By using the BSVR modeling technique, glucose in plasma could be determined over a 0.4 - 20 mmol/l concentration range with satisfactory accuracy. The performance of the BSVR methodology was compared with that of conventional support vector regression (SVR) as well as partial-least squares (PLS). The results demonstrated that BSVR is an effective multivariate calibration tool, providing better performance than conventional PLS and SVR.

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A fluoroionophore sensor, N-[4-(1-pyrene)butyroyl]-L-tryptophan (PLT), has been reported. It can distinguish lead ion from other 12 metal ions via forming a pyrene dimer and it exhibits a very high sensitivity (0.15 µM) in aqueous solution (Chem. Commun., 2006, 2702). When the indole moiety in PLT was changed to benzene, in forming a new fluoroionophore of N-[4-(1-pyrene)butyroyl]-L-phenylalanine (PLP), it could not form a pyrene dimer in response to Pb²⁺ in water. The present study describes the spectroscopic clarification of the intrinsic differences of the binding model between PLP and PLT in binding with Pb²⁺. The model shows identical chelating bidentate coordination between COO^- and Pb²⁺ both in PLP-Pb and PLT-Pb; however, there is no indication of the interaction between the phenyl ring and the metal ion or the hydrogen bonding between amide groups in PLP-Pb. These differences in the binding model between PLP-Pb and PLT-Pb illustrate that the indole ring in PLT appears to play a crucial role in the high selectivity and sensitivity of PLT to lead(II) ion.

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Terahertz time-domain spectroscopy (THz-TDS) is used to study the intra- and intermolecular vibrational modes of aromatic carboxylic acids, for example, o-phthalic acid, benzoic acid, and salicylic acid, which form either intra- or intermolecular hydrogen bond(s) in different ways. Incorporating the target molecules in nano-sized spaces in mesoporous silicate (SBA-16) is found to be effective for the separate detection of intramolecular hydrogen bonding modes and intermolecular modes. The results are supported by an analysis of the differences in the peak shifts, which depend on temperature, caused by the different nature of the THz absorption. Raman spectra revealed that incorporating the molecules in the nano-sized pores of SBA-16 slightly changes the molecular structures. In the future, THz-TDS using nanoporous materials will be used to analyze the intra- and intermolecular vibrational modes of molecules with larger hydrogen bonding networks such as proteins or DNA.

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Twenty Thai commercial fish sauces were characterized by sensory descriptive analysis and near-infrared (NIR) spectroscopy. The main objectives were i) to investigate the relationships between sensory attributes and NIR spectra of samples and ii) to characterize the sensory characteristics of fish sauces based on NIR data. A generic descriptive analysis with 12 trained panels was used to characterize the sensory attributes. These attributes consisted of 15 descriptors: brown color, 5 aromatics (sweet, caramelized, fermented, fishy, and musty), 4 tastes (sweet, salty, bitter, and umami), 3 aftertastes (sweet, salty and bitter) and 2 flavors (caramelized and fishy). The results showed that Thai fish sauce samples exhibited significant differences in all of sensory attribute values (p < 0.05). NIR transflectance spectra were obtained from 1100 to 2500 nm. Prior to investigation of the relationships between sensory attributes and NIR spectra, principal component analysis (PCA) was applied to reduce the dimensionality of the spectral data from 622 wavelengths to two uncorrelated components (NIR1 and NIR2) which explained 92 and 7% of the total variation, respectively. NIR1 was highly correlated with the wavelength regions of 1100 - 1544, 1774 - 2062, 2092 - 2308, and 2358 - 2440 nm, while NIR2 was highly correlated with the wavelength regions of 1742 - 1764, 2066 - 2088, and 2312 - 2354 nm. Subsequently, the relationships among these two components and all sensory attributes were also investigated by PCA. The results showed that the first three principal components (PCs) named as fishy flavor component (PC1), sweet component (PC2) and bitterness component (PC3), respectively, explained a total of 66.86% of the variation. NIR1 was mainly correlated to the sensory attributes of fishy aromatic, fishy flavor and sweet aftertaste on PC1. In addition, the PCA using only the factor loadings of NIR1 and NIR2 could be used to classify samples into three groups which showed high, medium and low degrees of fishy aromatic, fishy flavor and sweet aftertaste.

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This paper reports on a simultaneous prediction method for ethylene (C₂) content and the melt temperature in melt state random polypropylene (RPP) and block polypropylene (BPP) by near-infrared (NIR) spectroscopy and chemometrics. The NIR spectra of RPP and BPP in melt states were measured by a FT-NIR on-line monitoring system. The predicted values of the C₂ content from the RPP or BPP spectra measured at 190 and 250°C were investigated using a calibration model for the C₂ content developed by using each RPP or BPP spectra set measured at 230°C. The errors in the predicted values of the C₂ content depended on the pretreatment methods for each calibration model. It was found that a multiplicative signal correction (MSC) is very effective to compensate for the influence of the change of the RPP or BPP sample temperature on the predicted C₂ content. By using modified MSC, it was demonstrated that simultaneous predictions of the C₂ contents and the relative temperature of the melt RPP and BPP from the NIR spectra could be realized.

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Thermosensitive phase transition behavior of poly(vinyl methyl ether) (PVME) in an aqueous solution and the effect of inorganic ions on the coil-globule transition have been investigated by Fourier transform infrared (FT-IR) spectroscopy with attenuated total reflection (ATR) accessory. ATR-IR spectra of PVME aqueous solution indicate that in water-PVME-inorganic salts system, the phase separation temperature of PVME aqueous solution decreased with the increase of ion concentration and the increase of anion electronegativity. Meanwhile, two-dimensional infrared (2D-IR) measurements have been made to clarify the microcosmic conformational changes of PVME during the coil-globule transition. Results show that the conformation changes of main chains occur earlier than those of ether groups during heating. Furthermore, the 2D correlation spectroscopy of PVME aqueous solution during heating and the increase of concentration of potassium chloride have been studied. The features of 2D-IR spectra during heating did not change compared to the features of PVME aqueous solution during the increase of concentration of potassium chloride. This result implies that, although the addition of inorganic ions shifts the phase separation temperature, it does not alter the internal mechanism of the coil-globule transition of PVME.

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We have demonstrated surface-enhanced Raman spectroscopy (SERS) on arrays of Au nanorods aligned in line by a dynamic oblique deposition technique. For light polarized along the major axes of the nanorods, the plasma resonance of the Au nanorods has been tuned to a wavelength suitable for Raman spectroscopy. Raman scattering on the discrete nanorods is significantly enhanced compared with that on semicontinuous Au films. Since the preparation process is physically bottom-up, it is robust in its selection of the materials and is useful for providing SERS sensors at low cost.

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The solvation number and conformation of N,N-dimethylacrylamide (DMAA) in the coordination sphere of the cobalt(II) ion in solution were studied, and compared with those of N,N-dimethylpropionamide (DMPA) by means of FT-Raman and FT-IR spectroscopy. Both solvents are present as either the planar cis or nonplanar staggered conformer in equilibrium, and the former is more stable in the bulk. As these solvents solvate the metal ion through the carbonyl O atom of the acryl (DMAA) or propionyl (DMPA) group, the solvation structure around the metal ion is highly congested to reduce the solvation number and/or to lead to a conformational geometry change of solvent. It turns out that the solvation number of the cobalt(II) ion is 4 for both DMAA and DMPA at 298 K, and that DMPA changes its conformation upon solvation, whereas DMAA hardly changes. The enthalpy of conformational change ΔH° for DMPA is 5 kJ mol^-1 in the bulk, and is -9 kJ mol^-1 in the coordination sphere of the cobalt(II) ion. On the other hand, the ΔH° value for DMAA is 9 kJ mol^-1 in the bulk.

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Resonance Raman spectroscopy assisted by centrifugal liquid membrane/circular dichroism (CLM-CD) and UV/Vis absorption spectroscopies was applied to measure the binding state of bilirubin (BR) in the complex with bovine serum albumin (BSA) formed at a heptane/water interface. The bisignate Cotton effects in the interfacial CD spectra and the red shift and linewidth increase of the BR absorption band around 450 nm indicated the formation of the BR-BSA complex at the interface and the chiral conversion of BR molecules in the aggregates. The resonance Raman spectra of BR observed at the interface suggested that the interfacial BR-BSA complex formed during the initial 15 min after the contact of the two phases had a similar structure with that in solution, but after 15 min were forming aggregates coexisting with solid micro-particles. These experimental results strongly suggested that the chiral interconversion of BR from (P+) conformation to (M-) conformation in the interfacial complex was accompanied by aggregation of the BR-BSA complexes. In the present study, resonance Raman microscopic spectrometry was proved to be highly useful for characterizing the solid like aggregate formed at the liquid/liquid interface.

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A simple, yet very powerful technique for the spectral acquisition of an extremely thin film with enhanced absorption was explored. An infrared absorption of an extremely thin film confined between media of high refractive indices was greater than that of its bulk when the spectrum was acquired under the attenuated total reflection (ATR) condition with parallel (p) polarized radiation. The absorption enhancement was not observed under perpendicular (s) polarized radiation. Theoretical investigations indicated that the absorption enhancement was proportional to the integration of the mean square evanescent field within the film. The field integration under p-polarized radiation increased, while that under s-polarized radiation decreased as the thickness of the confined film became thinner. The maximum enhancement was observed when the film was sufficiently thinner than the penetration depth. The phenomena were experimentally investigated, and the results agreed very well with theoretical predictions.

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An exploration was made to develop a determination method of a low-concentration analyte by NIR spectroscopy. An absorber, silica gel was employed to extract and enrich a low-concentration analyte of ethyl carbamate. The solid absorber with the enriched analyte was measured by NIR spectroscopy in the range of 800 - 2500 nm. Afterwards, PLS regression was performed between the NIR spectra and the concentrations of the analyte for quantitative analysis of the low-concentration analyte. The spectra of 20 solid samples of analyte-absorbed silica gel showed a good correlation with the concentrations of ethyl carbamate in the samples. A leave-one-out cross validation was applied to evaluate the prediction ability of PLS models built with the full spectra, spectra in the region of 1920 - 1970 nm and the region of 2250 - 2430 nm, respectively. The values of the root-mean-square error of the cross validation (RMSECV) were about 0.1 mg L^-1 (0.1 ppm).

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In order to clarify the theoretical basis of the variability in the measurement of tablet hardness by compression pressure, NIR spectroscopic methods were used to predict tablet hardness of the formulations. Tablets (200 mg, 8 mm in diameter) consisting of berberine chloride, lactose, and potato starch were formed at various compression pressures (59, 78, 98, 127, 195 MPa). The hardness and the distribution of micropores were measured. The reflectance NIR spectra of various compressed tablets were used as a calibration set to establish a calibration model to predict tablet hardness by principal component regression (PCR) analysis. The distribution of micropores was shifted to a smaller pore size with increasing compression pressure. The total pore volume of tablets decreased as the compression pressure increased. The hardness increased as the compression pressure increased. The hardness could be predicted using a calibration model consisting of 7 principal components (PCs) obtained by PCR. The relationship between the predicted and the actual hardness values exhibited a straight line, an R² of 0.925. In order to understand the theoretical analysis (scientific background) of calibration models used to evaluate tablet hardness, the standard error of cross validation (SEV) values, the loading vectors of each PC and the regression vector were investigated. The result obtained with the calibration models for hardness suggested that the regression vector might involve physical and chemical factors. In contrast, the porosity could be predicted using a calibration model composed of 2 PCs. The relationship between the predicted and the actual total pore volume showed a straight line with R² = 0.801. The regression vector of the total pore volume might be due to physical factors.

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Surface contaminants, such as powder and thin film on various solid surfaces, were analyzed by ATR FT-IR microspectroscopy. An ATR accessory consisting of a miniature-Ge IRE with contact area smaller than 50 µm, in diameter was fabricated and employed for a non-destructive characterization. The IRE was pre-aligned and fixed onto a 15 × Schwarzschild-Cassegrain infrared objective. Easy maneuvering of the microscope stage enabled an accumulative collection of the contaminant at the tip of a miniature-Ge IRE, where the contaminants were analyzed under the ATR condition. By making a gentle contact between the Ge tip and selected area on the surface, any removable contaminants were transferred onto the Ge tip where its molecular information was acquired without any interference from the solid substrate. A thin organic film (i.e., mineral oil or fluorolube) was coated at the tip of the IRE in order to enhance the collecting efficiency of the removable contaminants.

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Herein we report a new method to collect a qualified infrared spectrum of a solute in solution by two solvent cells with different thickness during background single-beam spectrum scanning. By collecting the background spectrum with two cells (two stages), we successfully achieved accurate solvent compensation between a sample and a reference, namely, the solvent amounts in the sample and background measurements could become congruent. Therefore, the solvent bands were thoroughly suppressed in the infrared spectrum and a qualified spectrum of the solute was obtained.

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The homogeneity of blends of poly((R)-3-hydroxybutyrate) (PHB) and poly(L-lactic acid) (PLLA) was evaluated by the near infrared chemical imaging (NIRCI) technique. NIRCI can nondestructively investigate a sample over a wide field of view within a few minutes to acquire a large number of spatially resolved NIR spectral data. NIRCI may be combined with multivariate analysis not only for qualitative analysis but also for statistically based quantitative analysis. The score images derived from the partial least squares regression (PLSR) analysis directly show that PHB/PLLA blends are highly homogeneous. The standard deviations (STD) of the histograms, indicating the distribution of the score values, show small values for the blends. These results qualitatively and quantitatively show the high level of homogeneity of PHB/PLLA blends. The predictions of the spatially averaged concentrations of the blend components obtained from PLSR results show values similar to the actual contents for the blends. The small errors of the predictions are also explained by STD values.

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FTIR microscopic imaging was used to investigate the miscibility behavior of ethylene/vinyl acetate copolymer (EVA) and C5 petroleum resin. Images with an area of 500 × 500 µm² were collected in the reflection mode. The miscibility was characterized by probing the spatial distribution of the carbonyl group (C=O) of EVA in the whole images. It was found that a 1:1 hot-melt mixture of EVA and C5 resin showed a good miscibility behavior. For two different EVA copolymers, one with 18% vinyl acetate (VAc) content showed a better miscibility behavior than that with 28% VAc content. Our results demonstrated that this method allowed a direct, convenient and nondestructive visualization. This developed technique promises to become a powerful tool for studying the miscibility behavior of composite materials.

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Principal component analysis-based two-dimensional (PCA2D) correlation spectroscopy, combined with the eigenvalue manipulating transformation (EMT) of a spectral data set, was applied to the temperature-dependent IR spectra of poly(hydroxybutylate) (PHB). In asynchronous PCA2D correlation spectrum, we clearly captured the existence of two components in the crystalline band of the C=O stretching mode, well-ordered primary crystals observed at lower wavenumber and less ordered secondary crystals observed at higher wavenumber, which is not readily detectable in the 1D spectra. By lowering the power of a set of eigenvalues associated with the original data, subtle differences in the thermal responses of PHB, which are difficult to observe even by conventional 2D correlation analysis, are revealed. When the contributions from minor factors are enhanced by eigenvalue manipulating transformation, intensities of bands assignable to the amorphous component of PHB are accentuated more in the C-O-C stretching region, while the intensities of bands assignable to the crystalline component become most prominent in the CH stretching region. However, the 2D correlation between CH and C=O stretching region reveals that the spectral intensity change of the CH₃ stretching bands at 2975 cm^-1 contains a component due to the amorphous contribution.

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The effects of a magnetic force on magnetic particles linked by cysteamine to a silver colloid plate were analyzed with surface-enhanced Raman scattering spectroscopy. Cysteamine molecules were stretched by a force exerted on the magnetic particles with the external magnetic field gradients generated by two Nd-Fe-B magnets. The spectra showed that the relative intensity ratio of C-S (trans) to C-S (gauche) of cysteamine was increased 2 - 3 times within 30 min under the application of magnetic field gradients. Also, the shift of C-S (T) was observed up to 4 cm^-1 to higher frequency. These results suggested that an extension of the distance between a magnetic particle and a silver colloid induced isomerization from the gauche conformation to the trans conformation, accompanied by probable thiolate migration on the silver colloid surface.

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The utility of infrared (IR) spectroscopy for the determination of strawberry ripeness has been successfully demonstrated. Transmission IR spectra were collected using dried liquid extracts from strawberry flesh. The overall IR feature provided fairly noticeable differences, and the ripeness stage was clearly identified using principal component analysis (PCA). Although all of the extracted components contributed to the resulting spectral features for discrimination, the variation of carbohydrate and amide residues played a major role for providing the selective spectral feature. Additionally, NMR spectra were also collected to quantify the concentrations of three small sugars (α-glucose, β-glucose and sucrose) as well as to evaluate the NMR spectral features at each ripeness step. The concentrations of three sugars increased from early to late growth stages. Both IR and NMR spectroscopies were valuable to elucidate the metabolic signatures for the determining of ripeness stage; however, IR spectroscopy could be more advantageous when fast and high throughput analysis is essential.

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Multivariate regression based on partial least squares (PLS2) was applied to estimating one spectral dataset from another set having an intrinsic relationship with each other. An estimation was successfully carried out between mid-infrared (IR) spectra in the range of 2980 - 3800 cm^-1 and that of near-infrared (NIR) spectra in the range of 6000 - 7500 cm^-1 for hexafluoroisopropanol (HFIP)-water mixtures. The result demonstrates that, after building a suitable regression model, not only NIR spectra, but also well-resolved IR spectra of HFIP-water mixture can be estimated properly in this way. The use of IR and NIR spectroscopy together with PLS2 regression will not only alleviate laborious and costly measurements, but also open a way to provide easier assignments of generally weak and highly overlapped NIR spectral bands.

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Cow milk adulteration involves the dilution of milk with a less-expensive component, such as water or whey. Near-infrared spectroscopy (NIRS) was employed to detect the adulterations of milk, non-destructively. Two adulteration types of cow milk with water and whey were prepared, respectively. NIR spectra of milk adulterations and natural milk samples in the region of 1100 - 2500 nm were collected. The classification of milk adulterations and natural milk were conducted by using discriminant partial least squares (DPLS) and soft independent modelling of class analogy (SIMCA) methods. PLS calibration models for the determination of water and whey contents in milk adulteration were also developed, individually. Comparisons of the classification methods, wavelength regions and data pretreatments were investigated, and are reported in this study. This study showed that NIR spectroscopy can be used to detect water or whey adulterants and their contents in milk samples.

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The application of chemometrics to analyze the information of the cis/trans structure of alkenes in infrared spectra (IR) is introduced. For data from the OMNIC IR spectral database, two feature selection methods, Fisher ratios and genetic algorithm-partial least squares (GA-PLS), and two classification methods, support vector machine (SVM) and probabilistic neural network (PNN), have been used to obtain optimization classifiers. At last, some spectra from other IR databases are used to evaluate the optimization classifiers. It has been demonstrated that both the SVM and PNN optimization classifiers could give preferable predictive results about the cis and trans structures of alkene.

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The hydrogen bond resonance of a sodium chloride (NaCl) ion pair trapped in aqueous ice has been observed by transmission terahertz time-domain spectroscopy. The absorption peak of a sodium chloride ion pair in ice is 1.65 THz at 83 K. By investigating the interaction of the cation and anion with other chemical compounds, we deduce that the absorption peak originates from the hydrogen bond resonance of sodium chloride and water molecules. The charge redistribution that occurs when other ion pairs are added to aqueous salt solution changes the absorption spectrum. Furthermore, the results also indicate that simple molecules such as sodium halides have fingerprints in the terahertz region when the ions are trapped in ice. NaCl ion pairs in seawater and in Ringer's solution were examined.

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A systematic classification method for polymers is not yet available in case of using near infrared spectra (NIR). That is why we have been searching for a systematic method. Because raw NIR spectra usually have few obvious peaks, NIR spectra have been pretreated by 2nd derivation for taking well modulated spectra. After the pretreatment, we applied classification and regression trees (CART) to the discrimination between the spectra and the species of polymers. As a result, we obtained a relatively simple classification tree. Judging from the obtained splitting conditions and the classified polymers, we concluded that obtained knowledge on the chemical function groups estimated by the important wavelength regions is not always applicable to this classification tree. However, we clarified the splitting rules for polymer species from the NIR spectral point of view.

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