Applied Spectroscopy

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Surface-enhanced Raman scattering (SERS) and surface-enhanced resonance Raman scattering (SERRS) can provide positive identification of an analyte or an analyte mixture with high sensitivity and selectivity. Better understanding of the theory and advances in the understanding of the practice have led to the development of practical applications in which the unique advantages of SERS/SERRS have been used to provide effective solutions to difficult analytical problems. This review presents a basic theory and illustrates the way in which SERS/SERRS has been developed for practical use.

Coated silver (Ag) colloids synthesized with D-glucose permit the observation of surface-enhanced fluorescence (SEF) and surface-enhanced resonance Raman scattering (SERRS) of the rhodamine B (RhB) molecule. The organic coating formed during the synthesis of the Ag nanostructures was identified by its surface-enhanced Raman scattering (SERS) spectrum as D-gluconic acid. The RhB molecule is used to exemplify the distance dependence of SEF and SERRS on the coated Ag nanostructures. The fluorescence enhancement factor for RhB on D-gluconic acid coated silver nanoparticles was determined experimentally and estimated using a simple model. Further support for the plasmon enhancement is obtained from the fact that the measured fluorescence lifetime of RhB on the silver coated with D-gluconic acid is shorter than that found on a glass surface. A very modest enhancement factor is obtained, as expected for very short distance between RhB and the metal surface. Given the very thin metal–fluorophore separation, estimated from the size of the D-gluconic acid, the energy transfer or fluorescence quenching is still efficient and the SEF enhancement is just overcoming the energy transfer. Therefore, both SEF and SERRS are observed. Notably, the aggregation of coated nanoparticles also increases the enhancement factor for SEF.

This study describes a basic theory for reconstructing pure Raman signals of materials composing a multilayer sample from Raman spectra obtained using two types of miniaturized Raman probes. An illustrative example is demonstrated using a multilayer system of samples composed of the transparent plastics polymethylmethacrylate (PMMA) and polyethylene (PE) as a model of thin-layered biomedical tissues. When the same region of an object is measured using Raman probes with different focal properties, the Raman spectra provide different depth profile information depending on the level of light penetration. Thus, a detailed comparison of the spectra can provide an interesting opportunity to probe the differences between the layers. A simple analytic form is presented for reconstructing the pure Raman spectra of the embedded layer. The method applies an understanding of the Raman sampling volume in layered transparent materials to the interpretation of Raman spectra experimentally measured by multiple probes. The basic theory described here is necessary for the expansion of the technique to turbid media, such as biological samples, where light-scattering effects must be considered. The potential applications of the proposed method include material and catalyst subsurface probing through different embedded materials, such as assessment of silicon wafers, effective noninvasive screening for catalyst synthesis, and biomedical tissue research.

The use of a spatial heterodyne interferometer-based spectrometer (SHS) for Raman spectroscopy is described. The motivation for this work is to develop a small, rugged, high-resolution ultraviolet (UV) Raman spectrometer that is compatible with pulsed laser sources and that is suitable for planetary space missions. UV Raman is a particular technical challenge for space applications because dispersive (grating) approaches require large spectrographs and very narrow slits to achieve the spectral resolution required to maximize the potential of Raman spectroscopy. The heterodyne approach of the SHS has only a weak coupling of resolution and throughput, so a high-resolution UV SHS can both be small and employ a wide slit to maximize throughput. The SHS measures all optical path differences in its interferogram simultaneously with a detector array, so the technique is compatible with gated detection using pulsed lasers, important to reject ambient background and mitigate fluorescence (already low in the UV) that might be encountered on a planetary surface where samples are uncontrolled. The SHS has no moving parts, and as the spectrum is heterodyned around the laser wavelength, it is particularly suitable for Raman measurements. In this preliminary report we demonstrate the ability to measure visible wavelength Raman spectra of liquid and solid materials using an SHS Raman spectrometer and a visible laser. Spectral resolution and bandpass are also discussed. Separation of anti-Stokes and Stokes Raman bands is demonstrated using two different approaches. Finally spectral bandpass doubling is demonstrated by forming an interference pattern in both directions on the ICCD detector followed by analysis using a two-dimensional Fourier transform.

Real-time Raman spectroscopy was successfully utilized to monitor solvent evaporation and molecular orientation during electrospinning of atactic polystyrene (a-PS). The use of a binary solvent system of N,N-dimethyl formamide (DMF) and tetrahydrofuran (THF) provided a stable, straight jet during the experiment. The prominent Raman bands centered at 866 cm⁻¹, 914 cm⁻¹, and 1004 cm⁻¹, unique to DMF, THF, and a-PS, respectively, were used to monitor solvent concentration changes along the electrospinning jet for two different a-PS solutions. In addition, the changes in relative intensity for the radial skeletal ring vibration of the aromatic group of a-PS at 623 cm⁻¹ in two different polarization geometries, ZZ and YY, were monitored for orientation information. This study reports the first quantitative vibrational spectroscopic measurement during the electrospinning process. A significant change in concentration and orientation was observed during the process. The changes are explained in relation to the electrospinning process.

A basic approach was optimized for the synthesis of highly selective and sensitive in situ mesoporous (MCM) type imprinted silica polymers for the detection of dipicolinic acid (DPA) using europium as a reporter. DPA is a ubiquitous biochemical marker available during the germination event of endospore-forming bacteria such as Bacillus. Additionally, an MCM-MIP (molecularly imprinted polymeric phenomena) detector and a companion MCM–non-surface–MIP detector were synthesized using europium reporters for the sensing of DPA under optimized laboratory conditions. Our results showed that the in situ molecular imprinting process enabled rapid, selective detection of DPA with high sensitivity compared to MCM-MIP (imprinted for DPA; no DPA present), MCM-Non-MIP (no imprint present), and MCM-SR-MIP (imprinted with DPA present) detectors. The lower detection limit observed for DPA concentration is 5.49 × 10⁻¹⁰ mol dm⁻³ for MCM-MIP. The performance of the sensor in high-salt-water conditions, under photo-bleaching, and its reusability were also evaluated. The synthesized in situ MCM-MIP material should permit the detection of DPA for field assays related to suspect bacterial sporulation events.

Polymer films of varying thicknesses were deposited onto cotton and polyester fabric samples by dip-coating from solution. Scanning electron microscopy (SEM) images of the coated fabric samples were used to evaluate the quality of the polymer coating. The samples were analyzed by infrared diffuse reflection spectroscopy to determine the relationship between film thickness and the effect of the coating on the spectroscopy of the two fabrics. Effects observed in four limiting cases are examined: (Case I) weak coating absorption on a fabric with weak absorption at the same frequency; (Case II) strong coating absorption in a spectral region of weak fabric absorption; (Case III) weak coating absorption in a spectral region of strong fabric absorption; and (Case IV) strong coating absorption in a spectral region of strong fabric absorption. In the first case, effects were dominated by reduced scattering as the coating is added. In the second case, the strong coating absorption that was observed at low coverages plateaus at higher coverage due to depth of penetration effects. In the third and fourth cases, reduced Fresnel diffuse reflection is measured as the coating is added, consistent with the reduction of scattering observed in the first case.

A new continuous flow method using attenuated total reflection infrared (ATR-IR) spectroscopy has been developed for monitoring phase transitions in multicomponent fluids at high pressures and temperatures. Our approach uses Fourier transform infrared (FT-IR) and a modified Golden Gate attenuated total reflection (ATR) cell and exploits the fact that the absorbance of a vapor is much lower than that of the corresponding liquid to monitor the phase transition between vapor and liquid. We demonstrate that this method can provide quantitative measurements on both the dew point and the bubble point. We have validated our approach using three single-component systems (EtOH, MeOH, and H₂O) and a binary system of EtOH + H₂O, monitoring phase transitions at temperature up to 300 °C and pressure up to 10 MPa.

The interaction of N,N-dimethyl formamide (DMF) and N,N-dimethyl acetamide (DMA) with methanol in solution mixtures was studied using Fourier transform infrared–attenuated total reflection (FT-IR/ATR) spectroscopy. The concentration-dependent FT-IR/ATR spectra of DMF/methanol and DMA/methanol mixtures were recorded in the wavenumber range 4000–650 cm⁻¹ to investigate wavenumber shifts as a consequence of hydrogen bonding interactions. In combination with two-dimensional correlation spectroscopy (2D-COS), the positional fluctuations observed in the v(C=O) and v(O–H) regions of DMF/DMA and methanol, respectively, have been discussed in terms of changing populations of differently hydrogen-bonded and interacting species of the same and different component molecules.

This paper introduces a new approach to analysis of spectra called asynchronous orthogonal sample design (AOSD). Specifically designed concentration series are selected according to mathematical analysis of orthogonal vectors. Based on the AOSD approach, the interfering portion of the spectra arising strictly from the concentration effect can be completely removed from the asynchronous spectra. Thus, two-dimensional (2D) asynchronous spectra can be used as an effective tool to characterize intermolecular interactions that lead to apparent deviations from the Beer–Lambert law, even if the characteristic peaks of two compounds are substantially overlapped. A model solution with two solutes is used to investigate the behavior of the 2D asynchronous spectra under different extents of overlap of the characteristic peaks. Simulation results demonstrate that the resulting spectral patterns can reflect subtle spectral variations in bandwidths, peak positions, and absorptivities brought about by intermolecular interaction, which are barely visualized in the conventional one-dimensional (1D) spectra. Intermolecular interactions between butanone and dimethyl formamide (DMF) in CCl₄ solutions were investigated using the proposed AOSD approach to prove the applicability of the AOSD method in real chemical systems.

A new method of spectral subtraction for gas-phase Fourier transform infrared (FT-IR) spectra was developed for long-path gas measurements. The method is based on minimization of the length of the spectrum that results from subtracting the spectrum of an individual component of a gas mixture (water, CO₂, etc.) from the experimental spectrum of the mixture. For this purpose a subtraction coefficient (k_min) is found for which the length of the resulting spectrum is minimized. A mathematical simulation with two Lorentzian absorption bands was conducted and the limits of application for the proposed method were determined. Two experimental examples demonstrate that a successful result could be achieved in the case when the subtrahend spectrum contains a number of narrow absorption bands (such as the spectrum of water vapor).

Recently, near-infrared (NIR) imaging has been applied to detecting changes in skin hydration using the water OH band centered near 1460 nm. However, assigning changes in the intensity of the OH band near 1460 nm to changes in the skin's water content is complicated. Consequently, detection of small changes in facial skin water content is difficult. For highly sensitive imaging of facial skin water and oil, a near-infrared unit with a large detection range that includes the CH₃ and CH₂ stretching vibration modes at 1700–1800 nm and the strongest water bands centered near 1920 nm is required. In this study, an extended range indium gallium arsenide near-infrared camera was combined with a diffuse-illumination unit specifically developed for facial skin analysis. Images of water and oil in facial skin were obtained in real time using a combination of interference filters, such as 1950 ± 56 nm for water OH, 1775 ± 50 nm for oil CH, and 1300 ± 40 nm for background reflections. Clear near-infrared images were obtained with little mirror reflection. The water and oil content of facial skin could be evaluated even around the eyes, nose, and sides of the cheeks, which are areas that are difficult to analyze using current commercial devices. Differences were detected in the time-dependent changes of water and oil content in facial skin images obtained after the application of different types of moisturizer. The distribution of both water and oil in the facial skin could be visualized at the same time, and the images could be used to evaluate skin type and skin conditions.

Nondestructive in situ measurement of tomato fruits is essential to determine growing stages and to assist in automatic picking of fruits. This study evaluates the applicability of visible and near-infrared (Vis-NIR) spectroscopy for in situ determination of growing stages and harvest time of three cultivars of tomato fruits. A mobile fiber-type AgroSpec Vis-NIR spectrophotometer (Tec5 Co., Germany) with a spectral range of 350–2200 nm was used to measure tomato spectra in reflection mode. A new growing stage (GS) index defined as the ratio of the current growing age in days to the on-vine duration before harvest in days was proposed. After dividing spectra into a calibration set (70%) and an independent prediction set (30%), spectra in the calibration set were subjected to a partial least squares regression (PLSR) with leave-one-out cross-validation to establish calibration models relating GS to the spectra of tomato fruits. Separate models were developed for each tomato cultivar and compared with a general model that used combined spectra of all three cultivars. The results show that PLSR based on the new GS is successful and robust in predicting the growing stages and harvest time of tomato fruits. Validation of calibration models on the independent prediction set indicates that successful prediction of GS can be achieved using the three models developed separately for each cultivar with a coefficient of determination (R²) of 0.91–0.92, root mean square error of prediction (RMSEP) of 0.081–0.097, and residual prediction deviation (RPD) of 3.29–3.70. General calibration using the combined spectra produces good prediction performance, although less accurate than that for the three individual cultivar models. The analysis of regression coefficient plots resulting from PLSR analysis indicates consistent assignment of important wavelengths for individual cultivar spectra and combined spectra. It is concluded that the Vis-NIR PLSR based on GS index can be adopted successfully for in situ determination of growing stages and harvest time of on-vine tomato fruits, which allows for automatic picking of fruits by a horticultural robot.

A comprehensive study of the luminescence properties of cadmium pigments was undertaken to determine whether these properties could be used for in situ identification and mapping of the pigments in paintings. Cadmium pigments are semiconductors that show band edge luminescence in the visible range and deep trap luminescence in the red/infrared range. Emission maxima, quantum yields, and excitation spectra from the band edge and deep trap emissions were studied for sixty commercial cadmium pigments that span the color range from yellow to red (reflectance transition 470 to 660 nm). For paints containing cadmium pigments, luminescence from deep traps was more readily observable than that from the band edge, although the yield varied widely from zero to around 4.5%. Optimal excitation for emission is found to be in the visible for both pigments in powder form and mixed with a medium. The maxima of the deep trap emission shift with the band gap energy, providing a potentially useful way to assign pigment type even when used in pigment mixtures. The usefulness of the results of the study on mockups was demonstrated by the mapping of cadmium pigments of different hues with the aid of calibrated luminescence imaging spectroscopy in a painting by Edward Steichen, entitled Study for ‘Le Tournesol’ (1920). Analysis of the luminescence image cube reveals at least six unique spectral components, associated with emission from white pigments, paint binder, and cadmium red and yellow pigments. The results were compared with those from X-ray fluorescence spectrometry (XRF) and fiber-optic reflection spectroscopy (FORS) and the results obtained on paint samples containing cadmium pigments. These results show that, when present, the emission from traps can be used as an analytical tool to identify cadmium pigments, to distinguish among cadmium sulfide, cadmium zinc sulfide, and cadmium sulfoselenide, and to map cadmium pigments, even in mixtures.

A short laser pulse is irradiated on a sample to create a highly energetic plasma that emits light of a specific peak wavelength according to the material. By identifying different peaks for the analyzed samples, their chemical composition can be rapidly determined. The characteristics of the laser-induced breakdown spectroscopy (LIBS) plasma are strongly dependent on the ambient conditions. Research aimed at enhancing LIBS intensity is of great benefit in advancing LIBS for the exploration of harsh environments. By using double-pulse LIBS, the signal intensity of Al and Ca lines was enhanced by five times compared to the single-pulse signal. Also, the angles of the target and detector are adjusted to simulate samples of arbitrary shape. We verified that there exists an optimal angle at which specific elements of a test sample may be detected with stronger signal intensity. We provide several optimum configurations for the LIBS system for maximizing the signal intensity for the analysis of a nonstandard aluminum sample.