A rapid,non‐destructive method of detecting diagenetic alteration in fossil bone using Raman spectroscopy

Biogenic isotopes of analytical interest may be stripped from bone during burial, reducing the utility of fossil specimens for paleobiological and paleoenvironmental reconstruction. Denudation of the bone lattice coupled with the addition of exotic ions can influence the Raman spectra of fossil bone. Modern bone samples (n = 43) were used to establish an unaltered bone standard, and a suite of synthetic apatite samples were produced to simulate the addition of various ions into the bone mineral lattice. Diagenetic alteration produces distinct spectral characters, providing qualifications for major ionic substitution, ionic heterogeneity, the abundance of structural carbonate, the presence of calcium carbonate and the presence of luminescent ions. Spectral indicators (proxies) provide the means of rapidly and nondestructively evaluating the degree of alteration and thus the analytical utility of fossil bones, potentially avoiding exhaustive and destructive analysis on finite material. Copyright © 2007 John Wiley & Sons, Ltd.     

Drop‐coating deposition Raman spectroscopy of liposomes

Drop‐coating deposition Raman (DCDR) spectroscopy was tested as a potential technique for studying liposomes at very low sample concentrations. We used model liposomes prepared either from 1,2‐distearoyl‐sn‐glycero‐3‐phospocholine or from soybean asolectin, which is composed of various lipids and thus represents a good model of natural membranes. In both cases, deposited samples formed a dried drop with a circular shape with a ring of concentrated liposomes at the edge. Spectral mapping showed that maximum Raman intensity originated from the inner part of the edge ring, while Raman signal gradually decreased in both radial directions. The Raman spectra exhibited excellent reproducibility of spectral characteristics at different locations in the drop, indicating similar conformation and ordering of hydrocarbon lipid chains in the sample. Our results suggest that DCDR spectroscopy can be used for studying lipids in situ, and sensitivity of this technique is at least two orders of magnitude higher than that of conventional Raman microscopy. Copyright © 2011 John Wiley & Sons, Ltd.     

Drop‐coating deposition Raman spectroscopy of porphyrins

We report an improvement of the Raman detection sensitivity of porphyrins by factor of 10⁵ using drop‐coating deposition Raman spectroscopy (DCDR). We were able to obtain Raman spectra from ~20 nM initial (deposited) concentrations of cationic and anionic porphyrin. This detection limit is comparable with or even better than that of surface‐enhanced Raman scattering spectroscopy using Ag nanoparticles. Moreover, DCDR spectrum of protoporphyrin IX, which is known as a marker in clinical diagnostics of cancer, was also obtained from 10 nM deposited concentration. To our knowledge, it is the first demonstration of the resonance DCDR spectroscopy. Copyright © 2015 John Wiley & Sons, Ltd.     

Drop coating deposition Raman spectroscopy as a potential tool for identification and determination of fructose in seminal plasma

The detection of fructose in the seminal plasma has significant value to evaluate the function of seminal vesicles and evaluate male fertility. In this study, drop coating deposition Raman (DCDR) method was utilized to quantitative determination of fructose in seminal plasma. Optimization of experimental parameters to achieve reagent‐free and rapid detection of fructose was also investigated. Different fructose concentrations within physiological level demonstrated a linear relationship with the band intensity of 627 cm⁻¹ (assigned to fructose), and the relative error of predicted fructose concentration was 10.23%. Our results show that DCDR method has the potential for the determination of fructose concentration. Copyright © 2014 John Wiley & Sons, Ltd.     

Rapid outdoor non‐destructive detection of organic minerals using a portable Raman spectrometer

Raman spectral signatures have been obtained for a series of organic minerals using a compact portable Raman instrument equipped with 785‐nm laser excitation. Well‐resolved Raman spectra of crystalline salts of carboxylic acids, whewellite and mellite, as well as of the aromatic mineral idrialite were recorded. For comparative purposes, an amorphous fossil resin, baltic amber, was also investigated. The results obtained confirm that portable Raman instruments can be considered as excellent tools for field geological applications, including the detection of organic minerals in the frame of outcrops of sedimentary rocks or coal beds. Organic minerals can be added to the list of established biomarkers, including porphyrins, hydrocarbons and organic acids, which are important for the study with regard to future exobiological missions such as the ESA ExoMars mission to detect the presence of extinct or extant life on Mars. Copyright © 2009 John Wiley & Sons, Ltd.     

On the quantification of ciprofloxacin in proprietary Ciproxin tablets and generic ciprofloxacin tablets using handheld Raman spectroscopy

Quantification of ciprofloxacin in proprietary Ciproxin tablets and generic ciprofloxacin tablets was made using handheld Raman spectroscopy. Powder dilutions of ciprofloxacin or crushed Ciproxin tablets with excipient(s) were made. The spectra were taken either from the powder dilutions or from pellets compressed from these dilutions and were stored in the instrument library. Methods were created from these powder dilutions: each representing a separate model. The spectra of the tablets were identified within each method using the inbuilt algorithm of the instrument. The results showed that only the models made with the crushed Ciproxin tablets were semi‐quantitative for the analysis of Ciproxin tablets. On the other hand, none of the models could identify generic ciprofloxacin tablets. Thus, the spectra were exported to MATLAB for off‐line quantification. Whereas, univariate regression models were hardly linear, partial least square regression models gave linear calibrations with correlation coefficients above 0.99 and root mean square error of calibration below 3.75% m/m. For the prediction of tablets, the models varied in their results with the one created with ciprofloxacin and lactose giving the most satisfactory results. However, in total the method did not give the pharmacopoeial accuracy of ±5% and stays a semi‐quantitative approach although a satisfactory identity of the constituents was achieved. Copyright © 2011 John Wiley & Sons, Ltd.     

A novel method for quantification of ethanol and methanol in distilled alcoholic beverages using Raman spectroscopy

In this study, direct quantification of ethanol and methanol in distilled alcoholic beverages using Raman spectroscopy was performed. Raman spectra of varying ethanol–methanol mixtures were obtained, baseline corrections were made, and the data were normalized using Raman scattering intensity of an internal standard (acetonitrile, 921 cm^–1). Then, calibration graphs were produced for ethanol and methanol concentrations in the ranges of 0–7 M and 0–10 M, respectively. Accurate R² values of the calibration graphs proved the notable linear correlations (0.998 for ethanol and 0.998 for methanol). The method was validated based on linearity, sensitivity, intraday and interday repeatability, and recovery tests. The limit of detection and limit of quantification values of the validated method were determined for ethanol concentration as 1.2 and 3.7 mM, and for methanol concentration as 3.4 and 10.3 mM, respectively. The ability of the developed method to detect ethanol and methanol concentrations in real samples was also investigated. The results of the developed method were compared with the experimental results from traditional method and high correlation value (R² = 0.926) was obtained. Besides being sensitive and cheap, the developed method is rapid with the analysis time of less than 30 s. Furthermore, it eliminates labor‐consuming operations, chromatographic separation, and measurement error due to the high number of experiment steps in the standard method. Copyright © 2012 John Wiley & Sons, Ltd.     

Polarized Raman spectroscopy for enhanced quantification of protein concentrations in an aqueous mixture

Raman spectroscopy (RS) for selective quantification of protein species in mixed solutions holds enormous potential for advancing protein detection technology to significantly faster, cheaper, and less technically demanding platforms. However, even with powerful computational methods such as nonlinear least squares regression, protein quantification in such complex systems suffers from relatively poor accuracy, especially in comparison with established methods. In this work, a combination of the expanded set of spectral information provided by polarized Raman spectroscopy (PRS) that is otherwise unavailable in conventional RS was, to our knowledge, explored to enhance the quantitative accuracy and robustness of protein quantification for the first time. A mixture containing two proteins, lysozyme and α‐amylase, was used as a model system to demonstrate enhanced quantitative accuracy and robustness of selective protein quantification using PRS. The concentrations of lysozyme and α‐amylase in mixtures were estimated using data obtained from both traditional RS and PRS. A new method was developed to select highly sensitive peaks for accurate concentration estimation to take advantage of additional spectra offered by PRS. The root‐mean squared errors (RMSE) of estimation using traditional RS and PRS were compared. A drastic improvement in RMSE was observed from traditional RS to PRS, where the RMSEs of α‐amylase and lysozyme concentrations decreased by 11 and 7 times, respectively. Therefore, this technique is a successful demonstration in achieving greater accuracy and reproducibility in the estimation of protein concentration in a mixture, and it could play a significant role in future multiplexed protein quantification platforms. Copyright © 2015 John Wiley & Sons, Ltd.     

Recent advances in linear and non‐linear Raman spectroscopy. Part IX

This annual review is published to provide an overview of advances in the field of Raman spectroscopy as reflected in papers published each year in the Journal of Raman Spectroscopy (JRS) as well as in trends across related journals that have published papers in the broad field of Raman spectroscopy. The content is obtained from statistical data on article counts obtained from Thomson Reuters ISI Web of Science Core Collection by year and by subfield of Raman spectroscopy. Additional information is gleaned from presentations at the VIII International Conference on Advanced Vibrational Spectroscopy (ICAVS‐8) in Vienna, Austria in July 2015 and those featuring Raman scattering at SCIX 2015 organized by the Federation of Analytical Chemistry and Spectroscopy Societies (FACSS) in Providence, Rhode Island, USA, in September/October 2015. Coverage is also provided for topics from the conference ECONOS 2015 held in April in Leuven, Belgium. Finally, papers published in JRS in 2014 are highlighted and arranged by topics at the frontier of Raman spectroscopy. Taken from these various viewpoints, it is clear that Raman spectroscopy continues to be a rapidly expanding field that provides sensitive photonic information of matter at the molecular level in an ever‐widening arena of novel applications. Copyright © 2015 John Wiley & Sons, Ltd.     

Recent advances in linear and non‐linear Raman spectroscopy. Part III

Following the first two reviews on recent advances in linear and non‐linear Raman spectroscopy, the present review summarises papers mainly published in the Journal of Raman Spectroscopy during 2008. This again serves to give a brief overview of recent advances in this research field and to provide readers of this journal a quick introduction to the various sub‐fields of Raman spectroscopy. It also reflects the current research interests and trends in the Raman community. Copyright © 2009 John Wiley & Sons, Ltd.     

A non‐destructive approach for doping profiles characterization by micro‐Raman spectroscopy: the case of B‐implanted Ge

B‐implanted Ge samples have been investigated by micro‐Raman spectroscopy under different excitation wavelengths, with the aim of gaining insights about the B distribution at different depths beneath the sample surface. The intensities, observed under the different excitation wavelengths, of the B–Ge Raman peak at about 545 cm⁻¹, which is due to the local vibrational mode of the substitutional B atoms in the Ge matrix, have been used to calibrate the optical absorption lengths in B‐implanted Ge. Then, by using these calibrated values, a very sharp correlation between the spectral features of the Ge–Ge Raman peak at ~300 cm⁻¹ and the content of substitutional B atoms has been derived. Accordingly, a non‐destructive approach, based on micro‐Raman spectroscopy under different excitation wavelengths, is presented to estimate, at least at the lowest depths, the carrier concentration profiles from the spectral features of the Ge–Ge Raman peak. Copyright © 2014 John Wiley & Sons, Ltd.     

FT‐Raman spectroscopy—a rapid and reliable quantification protocol for the determination of natural indigo dye in Polygonum tinctorium

In the recent years, Raman and IR spectroscopies have attracted increasing attention as fast, non‐invasive and widely applicable alternative analytical approaches for a variety of materials. Vibrational spectroscopy has been used in the analysis of herbal products, dyes and sensitive art objects, besides complex and aqueous biomaterials such as biopolymers or mammalian tissue. Compared to conventional analytical methods based on high‐performance liquid chromatography (HPLC) or gas chromatography, which often involves extensive and time‐consuming sample preparation, Raman or IR spectroscopy can avoid these procedures. The present work introduces a fast and reliable quantification method for the determination of naturally occurring indigo dye in dyer's knotweed (Polygonum tinctorium) based on Fourier transform (FT) Raman spectroscopy. The results were validated by HPLC‐UV, and the merits and drawbacks of the present method are elaborated. Besides the qualitative aspects of signal assignment and comparison to appropriate attenuated total reflectance Fourier transform infrared (ATR‐FT‐IR) measurements, the Raman spectrum of dihydro indigo, an important intermediate in the indigo dying process, is presented for the first time and discussed with regard to its spectroscopic behaviour. Copyright © 2010 John Wiley & Sons, Ltd.     

Measurement and calculation of the Q‐branch spectrum of nitrogen using inverse Raman spectroscopy and cw Raman‐induced polarization spectroscopy

The techniques of inverse Raman spectroscopy, Raman‐induced polarization spectroscopy (RIPS), and optical heterodyne RIPS (OHD‐RIPS) are compared by probing the Q‐branch of the nitrogen molecule. The signal is measured employing either a photomultiplier tube (low background level–RIPS) or a photodetector (high background level–IRS and OHD‐RIPS). The measurements are performed using atmospheric mixtures of N₂ Ar with concentrations varying from 0 to 79% N₂. This strategy permits estimation of detection limits using the different techniques. Pump and probe energy levels are varied independently to study signal dependence on laser irradiance. A theoretical treatment is presented on the basis of the Raman susceptibility equations, which permits the calculation of spectra for all three techniques. Calculated Q‐branch spectra are compared with the measured spectra for the interactions of a linearly polarized probe beam with a linearly or circularly polarized pump beam. The polarizer angle in the detection path for OHD‐RIPS has a dramatic effect on the shape of the spectrum. The calculated and experimental OHD‐RIPS spectra are in good agreement over the entire range of investigated polarizer angles. Detection limits using these techniques are analyzed to suggest their applicability for measuring other species of importance in combustion and plasma systems. Copyright © 2007 John Wiley & Sons, Ltd.     

Non‐invasive probing of pharmaceutical capsules using transmission Raman spectroscopy

We demonstrate how transmission Raman geometry can be effectively used for non‐invasive probing of the content of pharmaceutical capsules. This approach is particularly beneficial in situations where the conventional Raman backscattering method is hampered or fails because of excessive surface Raman or fluorescence signals emanating from the capsule shell material, which pollute the much weaker subsurface Raman signals with undesired noise. It is demonstrated that such interfering signals can be effectively suppressed by the transmission geometry. The ability to avoid surface fluorescence and Raman signals in conjunction with the superior, bulk‐probing properties of the transmission Raman geometry provides an analytical technique ideally suited for fast on‐line process control monitoring applications in pharmaceutical industry where rapid, chemically specific bulk analysis is required. Copyright © 2007 John Wiley & Sons, Ltd.     

A novel method for urinary tract infection diagnosis and antibiogram using Raman spectroscopy

Urinary tract infection (UTI) diagnosis and antibiogram require a 48‐h waiting period using the standard conventional clinical methods. This long waiting period results in ineffective treatments, increased costs and, most importantly, in increased resistance to antibiotics. In this work, a novel method for classifying bacteria and determining their sensitivity to an antibiotic using Raman spectroscopy is described. Raman spectra belonging to three species of gram‐negative enterobacteria, which are most commonly responsible for UTIs, are classified with over 94% accuracy using novel feature extraction and discriminant analysis. Sensitivity to ciprofloxacin is also clearly evident as early as 2 h after treatment by differences in the Raman spectra of bacteria treated or not treated with this antibiotic. The proposed technique can become the basis for the development of new technology for UTI diagnosis and antibiogram with same day results, thus avoiding urine cultures and all undesirable consequences of current practice. Copyright © 2009 John Wiley & Sons, Ltd.     

Surface‐enhanced Raman spectroscopy for trace‐level detection of explosives

The detection of explosives and their associated compounds for security screening is an active area of research and a wide variety of detection methods are involved in this very challenging area. Surface‐enhanced Raman scattering (SERS) spectroscopy is one of the most sensitive tools for the detection of molecules adsorbed on nano‐scale roughened metal surface. Moreover, SERS combines high sensitivity with the observation of vibrational spectra of species, giving complete information on the molecular structure of material under study. In this paper, SERS was applied to the detection of very small quantities of explosives adsorbed on industrially made substrates. The spectra were acquired with a compact Raman spectrometer. Usually, a high signal‐to‐noise (S/N) spectrum, suitable for identification of explosive molecules down to few hundreds of picograms, was achieved within 30 s. Our measurements suggest that it is possible to exploit SERS using a practical detection instrument for routine analysis. Copyright © 2010 John Wiley & Sons, Ltd.     

Experimental and statistical analysis methods for peptide detection using surface‐enhanced Raman spectroscopy

Surface‐enhanced Raman spectroscopy (SERS) has the potential to make a significant impact in biology research due to its ability to provide information orthogonal to that obtained by traditional techniques such as mass spectrometry (MS). While SERS has been well studied for its use in chemical applications, detailed investigations with biological molecules are less common. In addition, a clear understanding of how methodology and molecular characteristics impact the intensity, the number of peaks, and the signal‐to‐noise of SERS spectra is largely missing. By varying the concentration and order of addition of the SERS‐enhancer salt (LiCl) with colloidal silver, we were able to evaluate the impact of these variables on peptide spectra using a quantitative measure of spectra quality based on the number of peaks and peak intensity. The LiCl concentration and order of addition that produced the best SERS spectra were applied to a panel of synthetic peptides with a range of charges and isoelectric points (pIs) where the pI was directly correlated with higher spectral quality. Those peptides with moderate to high pIs and spectra quality scores were differentiated from each other using the improved method and a hierarchical clustering algorithm. In addition, the same method and algorithm was applied to a set of highly similar phosphorylated peptides, and it was possible to successfully classify the majority of peptides on the basis of species‐specific peak differences. Copyright © 2008 John Wiley & Sons, Ltd.     

Characterization of polycyclic aromatic hydrocarbons using Raman and surface‐enhanced Raman spectroscopy

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous atmospheric pollutants and food contaminants, which exhibit potent carcinogenicity, mutagenicity, and teratogenicity. Vibrational spectroscopy techniques, especially Raman spectroscopy and surface‐enhanced Raman spectroscopy (SERS), can be potentially used as an alternative technique to liquid and gas chromatography in PAH analysis. However, there is limited information on the intrinsic Raman and SERS fingerprints of PAHs. In this study, we have acquired the Raman and SERS spectra of seven PAH compounds and compared their experimental spectra with theoretical Raman spectra calculated by density function theory (DFT). The vibrational modes corresponding to the Raman peaks have also been assigned using DFT. Characteristic Raman and SERS peaks have been identified for five PAH compounds, and the limits of detection were estimated. Such information could be useful for developing SERS assays for simple and rapid PAH identification. Copyright © 2014 John Wiley & Sons, Ltd.