Breaking the diffraction barrier using coherent anti-Stokes Raman scattering difference microscopy.

PubMed

Wang, Dong; Liu, Shuanglong; Chen, Yue; Song, Jun; Liu, Wei; Xiong, Maozhen; Wang, Guangsheng; Peng, Xiao; Qu, Junle

2017-05-01

We propose a method to improve the resolution of coherent anti-Stokes Raman scattering microscopy (CARS), and present a theoretical model. The proposed method, coherent anti-Stokes Raman scattering difference microscopy (CARS-D), is based on the intensity difference between two differently acquired images. One being the conventional CARS image, and the other obtained when the sample is illuminated by a doughnut shaped spot. The final super-resolution CARS-D image is constructed by intensity subtraction of these two images. However, there is a subtractive factor between them, and the theoretical model sets this factor to obtain the best imaging effect.

Coherent anti-Stokes Raman scattering microscopy: overcoming technical barriers for clinical translation

PubMed Central

Tu, Haohua; Boppart, Stephen A.

2015-01-01

Clinical translation of coherent anti-Stokes Raman scattering microscopy is of great interest because of the advantages of noninvasive label-free imaging, high sensitivity, and chemical specificity. For this to happen, we have identified and review the technical barriers that must be overcome. Prior investigations have developed advanced techniques (features), each of which can be used to effectively overcome one particular technical barrier. However, the implementation of one or a small number of these advanced features in previous attempts for clinical translation has often introduced more tradeoffs than benefits. In this review, we outline a strategy that would integrate multiple advanced features to overcome all the technical barriers simultaneously, effectively reduce tradeoffs, and synergistically optimize CARS microscopy for clinical translation. The operation of the envisioned system incorporates coherent Raman micro-spectroscopy for identifying vibrational biomolecular markers of disease and single-frequency (or hyperspectral) Raman imaging of these specific biomarkers for real-time in vivo diagnostics and monitoring. An optimal scheme of clinical CARS micro-spectroscopy for thin ex vivo tissues. PMID:23674234

Polarization Sensitive Coherent Anti-Stokes Raman Spectroscopy of DCVJ in Doped Polymer

NASA Astrophysics Data System (ADS)

Ujj, Laszlo

2014-05-01

Coherent Raman Microscopy is an emerging technic and method to image biological samples such as living cells by recording vibrational fingerprints of molecules with high spatial resolution. The race is on to record the entire image during the shortest time possible in order to increase the time resolution of the recorded cellular events. The electronically enhanced polarization sensitive version of Coherent anti-Stokes Raman scattering is one of the method which can shorten the recording time and increase the sharpness of an image by enhancing the signal level of special molecular vibrational modes. In order to show the effectiveness of the method a model system, a highly fluorescence sample, DCVJ in a polymer matrix is investigated. Polarization sensitive resonance CARS spectra are recorded and analyzed. Vibrational signatures are extracted with model independent methods. Details of the measurements and data analysis will be presented. The author gratefully acknowledge the UWF for financial support.

What are the intensities and line-shapes of the twenty four polarization terms in coherent anti-Stokes Raman spectroscopy?

DOE Office of Scientific and Technical Information (OSTI.GOV)

Niu, Kai; Lee, Soo-Y., E-mail: sooying@ntu.edu.sg

Coherent anti-Stokes Raman spectroscopy (CARS) is conventionally described by just one diagram/term where the three electric field interactions act on the ket side in a Feynman dual time-line diagram in a specific time order of pump, Stokes and probe pulses. In theory, however, any third-order nonlinear spectroscopy with three different electric fields interacting with a molecule can be described by forty eight diagrams/terms. They reduce to just 24 diagrams/terms if we treat the time ordering of the electric field interactions on the ket independently of those on the bra, i.e. the ket and bra wave packets evolve independently. The twentymore » four polarization terms can be calculated in the multidimensional, separable harmonic oscillator model to obtain the intensities and line-shapes. It is shown that in fs/ps CARS, for the two cases of off-resonance CARS in toluene and resonance CARS in rhodamine 6G, where we use a fs pump pulse, a fs Stokes pulse and a ps probe pulse, we obtain sharp vibrational lines in four of the polarization terms where the pump and Stokes pulses can create a vibrational coherence on the ground electronic state, while the spectral line-shapes of the other twenty terms are broad and featureless. The conventional CARS term with sharp vibrational lines is the dominant term, with intensity at least one order of magnitude larger than the other terms.« less

What are the intensities and line-shapes of the twenty four polarization terms in coherent anti-Stokes Raman spectroscopy?

NASA Astrophysics Data System (ADS)

Niu, Kai; Lee, Soo-Y.

2015-12-01

Coherent anti-Stokes Raman spectroscopy (CARS) is conventionally described by just one diagram/term where the three electric field interactions act on the ket side in a Feynman dual time-line diagram in a specific time order of pump, Stokes and probe pulses. In theory, however, any third-order nonlinear spectroscopy with three different electric fields interacting with a molecule can be described by forty eight diagrams/terms. They reduce to just 24 diagrams/terms if we treat the time ordering of the electric field interactions on the ket independently of those on the bra, i.e. the ket and bra wave packets evolve independently. The twenty four polarization terms can be calculated in the multidimensional, separable harmonic oscillator model to obtain the intensities and line-shapes. It is shown that in fs/ps CARS, for the two cases of off-resonance CARS in toluene and resonance CARS in rhodamine 6G, where we use a fs pump pulse, a fs Stokes pulse and a ps probe pulse, we obtain sharp vibrational lines in four of the polarization terms where the pump and Stokes pulses can create a vibrational coherence on the ground electronic state, while the spectral line-shapes of the other twenty terms are broad and featureless. The conventional CARS term with sharp vibrational lines is the dominant term, with intensity at least one order of magnitude larger than the other terms.

Effective suppression of stray light in rotational coherent anti-stokes Raman spectroscopy using an angle-tuned short-wave-pass filter.

PubMed

Bohlin, Alexis; Bengtsson, Per-Erik

2010-08-01

Stray light interference is a common problem in spontaneous rotational Raman spectroscopy and rotational coherent anti-Stokes Raman spectropscopy (CARS). The reason is that the detected spectrum appears in the spectral vicinity of the probe beam wavelength, and stray light at this wavelength from optics and surfaces is hard to suppress. In this Note, efficient suppression of stray light is demonstrated for rotational CARS measurements using a commercially available short-wave-pass filter. By angle-tuning this filter with a specified cut-off wavelength at 561 nm, the cut-off wavelength could be tuned to a desired spectral position so that more than 80% transmission is achieved as close as 15 cm(-1) (approximately 0.4 nm) from the probe beam wavelength of 532.0 nm, while the intensity at this wavelength is suppressed by two orders of magnitude.

Pure-rotational H2 thermometry by ultrabroadband coherent anti-Stokes Raman spectroscopy.

PubMed

Courtney, Trevor L; Bohlin, Alexis; Patterson, Brian D; Kliewer, Christopher J

2017-06-14

Coherent anti-Stokes Raman spectroscopy (CARS) is a sensitive technique for probing highly luminous flames in combustion applications to determine temperatures and species concentrations. CARS thermometry has been demonstrated for the vibrational Q-branch and pure-rotational S-branch of several small molecules. Practical advantages of pure-rotational CARS, such as multi-species detection, reduction of coherent line mixing and collisional narrowing even at high pressures, and the potential for more precise thermometry, have motivated experimental and theoretical advances in S-branch CARS of nitrogen (N 2 ), for example, which is a dominant species in air-fed combustion processes. Although hydrogen (H 2 ) is of interest given its prevalence as a reactant and product in many gas-phase reactions, laser bandwidth limitations have precluded the extension of CARS thermometry to the H 2 S-branch. We demonstrate H 2 thermometry using hybrid femtosecond/picosecond pure-rotational CARS, in which a broadband pump/Stokes pulse enables simultaneous excitation of the set of H 2 S-branch transitions populated at flame temperatures over the spectral region of 0-2200 cm -1 . We present a pure-rotational H 2 CARS spectral model for data fitting and compare extracted temperatures to those from simultaneously collected N 2 spectra in two systems of study: a heated flow and a diffusion flame on a Wolfhard-Parker slot burner. From 300 to 650 K in the heated flow, the H 2 and N 2 CARS extracted temperatures are, on average, within 2% of the set temperature. For flame measurements, the fitted H 2 and N 2 temperatures are, on average, within 5% of each other from 300 to 1600 K. Our results confirm the viability of pure-rotational H 2 CARS thermometry for probing combustion reactions.

Pure-rotational H2 thermometry by ultrabroadband coherent anti-Stokes Raman spectroscopy

NASA Astrophysics Data System (ADS)

Courtney, Trevor L.; Bohlin, Alexis; Patterson, Brian D.; Kliewer, Christopher J.

2017-06-01

Coherent anti-Stokes Raman spectroscopy (CARS) is a sensitive technique for probing highly luminous flames in combustion applications to determine temperatures and species concentrations. CARS thermometry has been demonstrated for the vibrational Q-branch and pure-rotational S-branch of several small molecules. Practical advantages of pure-rotational CARS, such as multi-species detection, reduction of coherent line mixing and collisional narrowing even at high pressures, and the potential for more precise thermometry, have motivated experimental and theoretical advances in S-branch CARS of nitrogen (N2), for example, which is a dominant species in air-fed combustion processes. Although hydrogen (H2) is of interest given its prevalence as a reactant and product in many gas-phase reactions, laser bandwidth limitations have precluded the extension of CARS thermometry to the H2 S-branch. We demonstrate H2 thermometry using hybrid femtosecond/picosecond pure-rotational CARS, in which a broadband pump/Stokes pulse enables simultaneous excitation of the set of H2 S-branch transitions populated at flame temperatures over the spectral region of 0-2200 cm-1. We present a pure-rotational H2 CARS spectral model for data fitting and compare extracted temperatures to those from simultaneously collected N2 spectra in two systems of study: a heated flow and a diffusion flame on a Wolfhard-Parker slot burner. From 300 to 650 K in the heated flow, the H2 and N2 CARS extracted temperatures are, on average, within 2% of the set temperature. For flame measurements, the fitted H2 and N2 temperatures are, on average, within 5% of each other from 300 to 1600 K. Our results confirm the viability of pure-rotational H2 CARS thermometry for probing combustion reactions.

Temperature of shocked plastic bonded explosive PBX 9502 measured with spontaneous Stokes/anti-Stokes Raman

NASA Astrophysics Data System (ADS)

McGrane, Shawn D.; Aslam, Tariq D.; Pierce, Timothy H.; Hare, Steven J.; Byers, Mark E.

2018-01-01

Raman spectra and velocimetry of shocked PBX 9502 (plastic bonded explosive composed of 95% triaminotrinitrobenzene (TATB) and 5% 3M Company Kel F-800 polymer binder) are reported with the Stokes/anti-Stokes ratio used to determine temperature after the shock reflects from a lithium fluoride window. Final pressures up to 14.5 GPa were tested, but the pressure induced absorption of TATB caused the Raman signal to decrease exponentially with pressure. The reflected shock temperature could be determined to 7 GPa, with an average increase of 14.9 K/GPa. Suggestions to adapt the technique to permit thermometry at higher temperatures are discussed, as are comparisons to a recently proposed equation of state for PBX 9502.

Investigation of enhanced forward and backward anti-stokes Raman signals in lithium niobate waveguides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Da; Hong, Pengda; Ding, Yujie J., E-mail: yding300@gmail.com

2015-07-07

We have observed enhancements of the anti-Stokes Raman signals generated in lithium niobate waveguides in the forward and backward configurations by at least one order of magnitude under the pump power of the microwatt level. These output signals were measured using a single photon detector. The forward and backward propagating anti-Stokes signals exhibited different spectral features.

Coherent anti-Stokes Raman scattering under electric field stimulation

NASA Astrophysics Data System (ADS)

Capitaine, Erwan; Ould Moussa, Nawel; Louot, Christophe; Lefort, Claire; Pagnoux, Dominique; Duclère, Jean-René; Kaneyasu, Junya F.; Kano, Hideaki; Duponchel, Ludovic; Couderc, Vincent; Leproux, Philippe

2016-12-01

We introduce an experiment using electro-CARS, an electro-optical method based on the combination of ultrabroadband multiplex coherent anti-Stokes Raman scattering (M-CARS) spectroscopy and electric field stimulation. We demonstrate that this method can effectively discriminate the resonant CARS signal from the nonresonant background owing to a phenomenon of molecular orientation in the sample medium. Such molecular orientation is intrinsically related to the induction of an electric dipole moment by the applied static electric field. Evidence of the electro-CARS effect is obtained with a solution of n -alkanes (CnH2 n +2 , 15 ≤n ≤40 ), for which an enhancement of the CARS signal-to-noise ratio is achieved in the case of CH2 and CH3 symmetric/asymmetric stretching vibrations. Additionally, an electric-field-induced second-harmonic generation experiment is performed in order to corroborate the orientational organization of molecules due to the electric field excitation. Finally, we use a simple mathematical approach to compare the vibrational information extracted from electro-CARS measurements with spontaneous Raman data and to highlight the impact of electric stimulation on the vibrational signal.

Coherent Anti-Stokes Raman Spectroscopy (CARS) Measurements in Supersonic Combustors at NASA Langley Research Center

NASA Technical Reports Server (NTRS)

Danehy, Paul M.; OByrne, Sean B.; Tedder, Sarah A.; Cutler, Andrew D.

2005-01-01

This paper describes the recent use of coherent anti-Stokes Raman spectroscopy (CARS) to study supersonic combustion at NASA Langley Research Center. CARS is a nonlinear optical measurement technique used to measure temperature and species mole fractions remotely in harsh environments. A CARS system has been applied to two different combustor geometries at NASA Langley. Both experiments used the same vitiated wind-tunnel facility to create an air flow that simulates flight at Mach numbers of 6 and 7 for the combustor inlet and both experiments used hydrogen fuel. In the first experiment, the hydrogen was injected supersonically at a 30-degree angle with respect to the incoming flow. In the second experiment, the hydrogen was injected sonically at normal incidence. While these injection schemes produced significantly different flow features, the CARS method provided mean temperature, N2, O2 and H2 maps at multiple downstream locations for both. The primary aim of these measurements was to provide detailed flowfield information for computational fluid dynamics (CFD) code validation.

Dispersive Fourier transformation for megahertz detection of coherent stokes and anti-stokes Raman spectra

NASA Astrophysics Data System (ADS)

Bohlin, Alexis; Patterson, Brian D.; Kliewer, Christopher J.

2017-11-01

In many fields of study, from coherent Raman microscopy on living cells to time-resolved coherent Raman spectroscopy of gas-phase turbulence and combustion reaction dynamics, the need for the capability to time-resolve fast dynamical and nonrepetitive processes has led to the continued development of high-speed coherent Raman methods and new high-repetition rate laser sources, such as pulse-burst laser systems. However, much less emphasis has been placed on our ability to detect shot to shot coherent Raman spectra at equivalently high scan rates, across the kilohertz to megahertz regime. This is beyond the capability of modern scientific charge coupled device (CCD) cameras, for instance, as would be employed with a Czerny-Turner type spectrograph. As an alternative detection strategy with megahertz spectral detection rate, we demonstrate dispersive Fourier transformation detection of pulsed (∼90 ps) coherent Raman signals in the time-domain. Instead of reading the frequency domain signal out using a spectrometer and CCD, the signal is transformed into a time-domain waveform through dispersive Fourier transformation in a long single-mode fiber and read-out with a fast sampling photodiode and oscilloscope. Molecular O- and S-branch rotational sideband spectra from both N2 and H2 were acquired employing this scheme, and the waveform is fitted to show highly quantitative agreement with a molecular model. The total detection time for the rotational spectrum was 20 ns, indicating an upper limit to the detection frequency of ∼50 MHz, significantly faster than any other reported spectrally-resolved coherent anti-Stokes Raman detection strategy to date.

Broadband plasmonic-enhanced forward and backward multiplex coherent anti-Stokes Raman scattering microscopy

NASA Astrophysics Data System (ADS)

Guo, Baoshan; Jiang, Lan; Hua, Yanhong; Li, Xin; Cui, Tianhong; Lu, Yongfeng

2018-03-01

Coherent anti-Stokes Raman scattering (CARS) microscopy is an attractive technique for label-free biochemical-specific characterization of biological specimens. However, it has very low sensitivity in monitoring and imaging molecules present in extremely low concentrations or at fast speeds. To improve this sensitivity, especially for multiplex CARS, the intensity of the pump beam and broadband Stokes beam should be enhanced simultaneously. Therefore, the gold shell particle and gold surface are demonstrated to enhance the forward and backward CARS, respectively. Results show that a signal enhancement factor of ˜25,000 can be achieved for the gold surface and an even higher enhancement factor can be achieved for the gold shell particles. Thus, we can obtain an enhanced CARS signal in a broad spectral range, which will substantially improve the detection sensitivity of hyperspectral CARS spectroscopy and imaging.

Parametric Raman anti-Stokes laser at 503 nm with phase-matched collinear beam interaction of orthogonally polarized Raman components in calcite under 532 nm 20 ps laser pumping

NASA Astrophysics Data System (ADS)

Smetanin, Sergei; Jelínek, Michal; Kubeček, Václav

2017-05-01

Lasers based on stimulated-Raman-scattering process can be used for the frequency-conversion to the wavelengths that are not readily available from solid-state lasers. Parametric Raman lasers allow generation of not only Stokes, but also anti-Stokes components. However, practically all the known crystalline parametric Raman anti-Stokes lasers have very low conversion efficiencies of about 1 % at theoretically predicted values of up to 40 % because of relatively narrow angular tolerance of phase matching in comparison with angular divergence of the interacting beams. In our investigation, to widen the angular tolerance of four-wave mixing and to obtain high conversion efficiency into the antiStokes wave we propose and study a new scheme of the parametric Raman anti-Stokes laser at 503 nm with phasematched collinear beam interaction of orthogonally polarized Raman components in calcite under 532 nm 20 ps laser pumping. We use only one 532-nm laser source to pump the Raman-active calcite crystal oriented at the phase matched angle for orthogonally polarized Raman components four-wave mixing. Additionally, we split the 532-nm laser radiation into the orthogonally polarized components entering to the Raman-active calcite crystal at the certain incidence angles to fulfill the tangential phase matching compensating walk-off of extraordinary waves for collinear beam interaction in the crystal with the widest angular tolerance of four-wave mixing. For the first time the highest 503-nm anti-Stokes conversion efficiency of 30 % close to the theoretical limit of about 40 % at overall optical efficiency of the parametric Raman anti-Stokes generation of up to 3.5 % in calcite is obtained due to realization of tangential phase matching insensitive to the angular mismatch.

Coherent anti-Stokes Raman scattering and spontaneous Raman scattering diagnostics of nonequilibrium plasmas and flows

NASA Astrophysics Data System (ADS)

Lempert, Walter R.; Adamovich, Igor V.

2014-10-01

The paper provides an overview of the use of coherent anti-Stokes Raman scattering (CARS) and spontaneous Raman scattering for diagnostics of low-temperature nonequilibrium plasmas and nonequilibrium high-enthalpy flows. A brief review of the theoretical background of CARS, four-wave mixing and Raman scattering, as well as a discussion of experimental techniques and data reduction, are included. The experimental results reviewed include measurements of vibrational level populations, rotational/translational temperature, electric fields in a quasi-steady-state and transient molecular plasmas and afterglow, in nonequilibrium expansion flows, and behind strong shock waves. Insight into the kinetics of vibrational energy transfer, energy thermalization mechanisms and dynamics of the pulse discharge development, provided by these experiments, is discussed. Availability of short pulse duration, high peak power lasers, as well as broadband dye lasers, makes possible the use of these diagnostics at relatively low pressures, potentially with a sub-nanosecond time resolution, as well as obtaining single laser shot, high signal-to-noise spectra at higher pressures. Possibilities for the development of single-shot 2D CARS imaging and spectroscopy, using picosecond and femtosecond lasers, as well as novel phase matching and detection techniques, are discussed.

Coherent Anti-Stokes Raman Spectroscopic Thermometry in a Supersonic Combustor

NASA Technical Reports Server (NTRS)

Cutler, A. D.; Danehy, P. M.; Springer, R. R.; OByrne, S.; Capriotti, D. P.; DeLoach, R.

2003-01-01

An experiment has been conducted to acquire data for the validation of computational fluid dynamics codes used in the design of supersonic combustors. The flow in a supersonic combustor, consisting of a diverging duct with a single downstream-angled wail injector, is studied. Combustor entrance Mach number is 2 and enthalpy nominally corresponds to Mach 7 flight. The primary measurement technique is coherent anti-Stokes Raman spectroscopy, but surface pressures and temperatures have also been acquired. Modern design of experiment techniques have been used to maximize the quality of the data set (for the given level of effort) and to minimize systematic errors. Temperature maps are obtained at several planes in the flow for a case in which the combustor is piloted by injecting fuel upstream of the main injector and one case in which it is not piloted. Boundary conditions and uncertainties are characterized.

Estimated phase transition and melting temperature of APTES self-assembled monolayer using surface-enhanced anti-stokes and stokes Raman scattering

NASA Astrophysics Data System (ADS)

Sun, Yingying; Yanagisawa, Masahiro; Kunimoto, Masahiro; Nakamura, Masatoshi; Homma, Takayuki

2016-02-01

A structure's temperature can be determined from the Raman spectrum using the frequency and the ratio of the intensities of the anti-Stokes and Stokes signals (the Ias/Is ratio). In this study, we apply this approach and an equation relating the temperature, Raman frequency, and Ias/Is ratio to in-situ estimation of the phase change point of a (3-aminopropyl)triethoxysilane self-assembled monolayer (APTES SAM). Ag nanoparticles were deposited on APTES to enhance the Raman signals. A time-resolved measurement mode was used to monitor the variation in the Raman spectra in situ. Moreover, the structural change in APTES SAM (from ordered to disordered structure) under heating was discussed in detail, and the phase change point (around 118 °C) was calculated.

Emerging technology: applications of Raman spectroscopy for prostate cancer.

PubMed

Kast, Rachel E; Tucker, Stephanie C; Killian, Kevin; Trexler, Micaela; Honn, Kenneth V; Auner, Gregory W

2014-09-01

There is a need in prostate cancer diagnostics and research for a label-free imaging methodology that is nondestructive, rapid, objective, and uninfluenced by water. Raman spectroscopy provides a molecular signature, which can be scaled from micron-level regions of interest in cells to macroscopic areas of tissue. It can be used for applications ranging from in vivo or in vitro diagnostics to basic science laboratory testing. This work describes the fundamentals of Raman spectroscopy and complementary techniques including surface enhanced Raman scattering, resonance Raman spectroscopy, coherent anti-Stokes Raman spectroscopy, confocal Raman spectroscopy, stimulated Raman scattering, and spatially offset Raman spectroscopy. Clinical applications of Raman spectroscopy to prostate cancer will be discussed, including screening, biopsy, margin assessment, and monitoring of treatment efficacy. Laboratory applications including cell identification, culture monitoring, therapeutics development, and live imaging of cellular processes are discussed. Potential future avenues of research are described, with emphasis on multiplexing Raman spectroscopy with other modalities.

Hyperspectral microscopic imaging by multiplex coherent anti-Stokes Raman scattering (CARS)

NASA Astrophysics Data System (ADS)

Khmaladze, Alexander; Jasensky, Joshua; Zhang, Chi; Han, Xiaofeng; Ding, Jun; Seeley, Emily; Liu, Xinran; Smith, Gary D.; Chen, Zhan

2011-10-01

Coherent anti-Stokes Raman scattering (CARS) microscopy is a powerful technique to image the chemical composition of complex samples in biophysics, biology and materials science. CARS is a four-wave mixing process. The application of a spectrally narrow pump beam and a spectrally wide Stokes beam excites multiple Raman transitions, which are probed by a probe beam. This generates a coherent directional CARS signal with several orders of magnitude higher intensity relative to spontaneous Raman scattering. Recent advances in the development of ultrafast lasers, as well as photonic crystal fibers (PCF), enable multiplex CARS. In this study, we employed two scanning imaging methods. In one, the detection is performed by a photo-multiplier tube (PMT) attached to the spectrometer. The acquisition of a series of images, while tuning the wavelengths between images, allows for subsequent reconstruction of spectra at each image point. The second method detects CARS spectrum in each point by a cooled coupled charged detector (CCD) camera. Coupled with point-by-point scanning, it allows for a hyperspectral microscopic imaging. We applied this CARS imaging system to study biological samples such as oocytes.

Ex-CARS: exotic configuration for coherent anti-Stokes Raman scattering microspectroscopy utilizing two laser sources

PubMed Central

Yakovlev, Vladislav V.; Petrov, Georgi I.; Noojin, Gary D.; Harbert, Corey; Denton, Michael; Thomas, Robert

2011-01-01

We propose and experimentally demonstrate a new coherent anti-Stokes Raman scattering setting, which relies on a coherent excitation of Raman vibration using a broadband ultrashort laser pulse and signal read-out using a conventional continuous wave laser radiation. Such an exotic arrangement does not require any synchronization of two laser sources and can be used for direct comparison of amplitudes of nonlinear and spontaneous Raman signals. Ex-CARS in time- (top panel) and frequency- (bottom panel) domain. PMID:20635427

Nonlinear optical susceptibility described with a spherical formalism applied to coherent anti-Stokes Raman scattering

NASA Astrophysics Data System (ADS)

Cleff, Carsten; Rigneault, Hervé; Brasselet, Sophie; Duboisset, Julien

2017-07-01

We describe coherent Raman scattering in a complete spherical formalism allowing a better understanding of the coherent Raman process with respect to its symmetry properties, which is especially helpful in polarized coherent Raman microscopy. We describe how to build the coherent Raman tensor from spontaneous Raman tensor for crystalline and disordered media. We introduce a distribution function for molecular bonds and show how this distribution function results in a new macroscopic symmetry which can be very different from the symmetry of vibrational modes. Finally, we explicitly show polarization configurations for coherent anti-Stokes Raman scattering to probe specific vibration symmetries in crystalline samples and lipid layers.

Quantitative, Comparable Coherent Anti-Stokes Raman Scattering (CARS) Spectroscopy: Correcting Errors in Phase Retrieval

PubMed Central

Camp, Charles H.; Lee, Young Jong; Cicerone, Marcus T.

2017-01-01

Coherent anti-Stokes Raman scattering (CARS) microspectroscopy has demonstrated significant potential for biological and materials imaging. To date, however, the primary mechanism of disseminating CARS spectroscopic information is through pseudocolor imagery, which explicitly neglects a vast majority of the hyperspectral data. Furthermore, current paradigms in CARS spectral processing do not lend themselves to quantitative sample-to-sample comparability. The primary limitation stems from the need to accurately measure the so-called nonresonant background (NRB) that is used to extract the chemically-sensitive Raman information from the raw spectra. Measurement of the NRB on a pixel-by-pixel basis is a nontrivial task; thus, reference NRB from glass or water are typically utilized, resulting in error between the actual and estimated amplitude and phase. In this manuscript, we present a new methodology for extracting the Raman spectral features that significantly suppresses these errors through phase detrending and scaling. Classic methods of error-correction, such as baseline detrending, are demonstrated to be inaccurate and to simply mask the underlying errors. The theoretical justification is presented by re-developing the theory of phase retrieval via the Kramers-Kronig relation, and we demonstrate that these results are also applicable to maximum entropy method-based phase retrieval. This new error-correction approach is experimentally applied to glycerol spectra and tissue images, demonstrating marked consistency between spectra obtained using different NRB estimates, and between spectra obtained on different instruments. Additionally, in order to facilitate implementation of these approaches, we have made many of the tools described herein available free for download. PMID:28819335

Spectrally-broad coherent anti-Stokes Raman scattering hyper-microscopy utilizing a Stokes supercontinuum pumped at 800 nm

PubMed Central

Porquez, Jeremy G.; Cole, Ryan A.; Tabarangao, Joel T.; Slepkov, Aaron D.

2016-01-01

We demonstrate spectral-focusing based coherent anti-Stokes Raman scattering (SF-CARS) hyper-microscopy capable of probing vibrational frequencies from 630 cm−1 to 3250 cm−1 using a single Ti:Sapphire femtosecond laser operating at 800 nm, and a commercially-available supercontinuum-generating fibre module. A broad Stokes supercontinuum with significant spectral power at wavelengths between 800 nm and 940 nm is generated by power tuning the fibre module using atypically long and/or chirped ~200 fs pump pulses, allowing convenient access to lower vibrational frequencies in the fingerprint spectral region. This work significantly reduces the instrumental and technical requirements for multimodal CARS microscopy, while expanding the spectral capabilities of an established approach to SF-CARS. PMID:27867735

Coherent anti-Stokes Raman Scattering (CARS) Microscopy Visualizes Pharmaceutical Tablets During Dissolution

PubMed Central

Fussell, Andrew L.; Kleinebudde, Peter; Herek, Jennifer; Strachan, Clare J.; Offerhaus, Herman L.

2014-01-01

Traditional pharmaceutical dissolution tests determine the amount of drug dissolved over time by measuring drug content in the dissolution medium. This method provides little direct information about what is happening on the surface of the dissolving tablet. As the tablet surface composition and structure can change during dissolution, it is essential to monitor it during dissolution testing. In this work coherent anti-Stokes Raman scattering microscopy is used to image the surface of tablets during dissolution while UV absorption spectroscopy is simultaneously providing inline analysis of dissolved drug concentration for tablets containing a 50% mixture of theophylline anhydrate and ethyl cellulose. The measurements showed that in situ CARS microscopy is capable of imaging selectively theophylline in the presence of ethyl cellulose. Additionally, the theophylline anhydrate converted to theophylline monohydrate during dissolution, with needle-shaped crystals growing on the tablet surface during dissolution. The conversion of theophylline anhydrate to monohydrate, combined with reduced exposure of the drug to the flowing dissolution medium resulted in decreased dissolution rates. Our results show that in situ CARS microscopy combined with inline UV absorption spectroscopy is capable of monitoring pharmaceutical tablet dissolution and correlating surface changes with changes in dissolution rate. PMID:25045833

Clinical coherent anti-Stokes Raman scattering and multiphoton tomography of human skin with a femtosecond laser and photonic crystal fiber

NASA Astrophysics Data System (ADS)

Breunig, Hans Georg; Weinigel, Martin; Bückle, Rainer; Kellner-Höfer, Marcel; Lademann, Jürgen; Darvin, Maxim E.; Sterry, Wolfram; König, Karsten

2013-02-01

We report on in vivo coherent anti-Stokes Raman scattering spectroscopy (CARS), two-photon fluorescence and second-harmonic-generation imaging on human skin with a novel multimodal clinical CARS/multiphoton tomograph. CARS imaging is realized by a combination of femtosecond pulses with broadband continuum pulses generated by a photonic crystal fiber. The images reveal the microscopic distribution of (i) non-fluorescent lipids, (ii) endogenous fluorophores and (iii) the collagen network inside the human skin in vivo with subcellular resolution. Examples of healthy as well as cancer-affected skin are presented.

Glucose concentration measured by the hybrid coherent anti-Stokes Raman-scattering technique

NASA Astrophysics Data System (ADS)

Wang, Xi; Zhang, Aihua; Zhi, Miaochan; Sokolov, Alexei V.; Welch, George R.

2010-01-01

We investigate the possibility of using a hybrid coherent anti-Stokes Raman scattering technique for noninvasive monitoring of blood glucose levels. Our technique combines instantaneous coherent excitation of several characteristic molecular vibrations with subsequent probing of these vibrations by an optimally shaped, time-delayed, narrowband laser pulse. This pulse configuration mitigates the nonresonant four-wave mixing background while maximizing the Raman-resonant signal and allows rapid and highly specific detection even in the presence of multiple scattering. Under certain conditions we find that the measured signal is linearly proportional to the glucose concentration due to optical interference with the residual background light, which allows reliable detection of spectral signatures down to medically relevant glucose levels.

Investigation of the Brill transition in nylon 6,6 by Raman, THz-Raman, and two-dimensional correlation spectroscopy.

PubMed

Bertoldo Menezes, D; Reyer, A; Musso, M

2018-02-05

The Brill transition is a phase transition process in polyamides related with structural changes between the hydrogen bonds of the lateral functional groups (CO) and (NH). In this study, we have used the potential of Raman spectroscopy for exploring this phase transition in polyamide 6,6 (nylon 6,6), due to the sensitivity of this spectroscopic technique to small intermolecular changes affecting vibrational properties of relevant functional groups. During a step by step heating and cooling process of the sample we collected Raman spectra allowing us from two-dimensional Raman correlation spectroscopy to identify which spectral regions suffered the largest influence during the Brill transition, and from Terahertz Stokes and anti-Stokes Raman spectroscopy to obtain complementary information, e.g. on the temperature of the sample. This allowed us to grasp signatures of the Brill transition from peak parameters of vibrational modes associated with (CC) skeletal stretches and (CNH) bending, and to verify the Brill transition temperature at around 160°C, as well as the reversibility of this phase transition. Copyright © 2017 Elsevier B.V. All rights reserved.

Rapid spectro-polarimetry to probe molecular symmetry in multiplex coherent anti-Stokes Raman scattering.

PubMed

Würthwein, Thomas; Brinkmann, Maximilian; Hellwig, Tim; Fallnich, Carsten

2017-11-21

We present the simultaneous detection of the spectrum and the complete polarization state of a multiplex coherent anti-Stokes Raman scattering signal with a fast division-of-amplitude spectro-polarimeter. The spectro-polarimeter is based on a commercial imaging spectrograph, a birefringent wedge prism, and a segmented polarizer. Compared to the standard rotating-retarder fixed-analyzer spectro-polarimeter, only a single measurement is required and an up to 21-fold reduced acquisition time is shown. The measured Stokes parameters allow us to differentiate between vibrational symmetries and to determine the depolarization ratio ρ by data post-processing.

Coherent anti-Stokes Raman scattering rigid endoscope toward robot-assisted surgery.

PubMed

Hirose, K; Aoki, T; Furukawa, T; Fukushima, S; Niioka, H; Deguchi, S; Hashimoto, M

2018-02-01

Label-free visualization of nerves and nervous plexuses will improve the preservation of neurological functions in nerve-sparing robot-assisted surgery. We have developed a coherent anti-Stokes Raman scattering (CARS) rigid endoscope to distinguish nerves from other tissues during surgery. The developed endoscope, which has a tube with a diameter of 12 mm and a length of 270 mm, achieved 0.91% image distortion and 8.6% non-uniformity of CARS intensity in the whole field of view (650 μm diameter). We demonstrated CARS imaging of a rat sciatic nerve and visualization of the fine structure of nerve fibers.

Pure electrical, highly-efficient and sidelobe free coherent Raman spectroscopy using acousto-optics tunable filter (AOTF)

NASA Astrophysics Data System (ADS)

Meng, Zhaokai; Petrov, Georgi I.; Yakovlev, Vladislav V.

2016-02-01

Fast and sensitive Raman spectroscopy measurements are imperative for a large number of applications in biomedical imaging, remote sensing and material characterization. Stimulated Raman spectroscopy offers a substantial improvement in the signal-to-noise ratio but is often limited to a discrete number of wavelengths. In this report, by introducing an electronically-tunable acousto-optical filter as a wavelength selector, a novel approach to a broadband stimulated Raman spectroscopy is demonstrated. The corresponding Raman shift covers the spectral range from 600 cm-1 to 4500 cm-1, sufficient for probing most vibrational Raman transitions. We validated the use of the new instrumentation to both coherent anti-Stokes scattering (CARS) and stimulated Raman scattering (SRS) spectroscopies.

Probe-pulse optimization for nonresonant suppression in hybrid fs/ps coherent anti-Stokes Raman scattering at high temperature.

PubMed

Miller, Joseph D; Slipchenko, Mikhail N; Meyer, Terrence R

2011-07-04

Hybrid femtosecond/picosecond coherent anti-Stokes Raman scattering (fs/ps CARS) offers accurate thermometry at kHz rates for combustion diagnostics. In high-temperature flames, selection of probe-pulse characteristics is key to simultaneously optimizing signal-to-nonresonant-background ratio, signal strength, and spectral resolution. We demonstrate a simple method for enhancing signal-to-nonresonant-background ratio by using a narrowband Lorentzian filter to generate a time-asymmetric probe pulse with full-width-half-maximum (FWHM) pulse width of only 240 fs. This allows detection within just 310 fs after the Raman excitation for eliminating nonresonant background while retaining 45% of the resonant signal at 2000 K. The narrow linewidth is comparable to that of a time-symmetric sinc2 probe pulse with a pulse width of ~2.4 ps generated with a conventional 4-f pulse shaper. This allows nonresonant-background-free, frequency-domain vibrational spectroscopy at high temperature, as verified using comparisons to a time-dependent theoretical fs/ps CARS model.

SPECIAL ISSUE DEVOTED TO THE 80TH BIRTHDAY OF S.A. AKHMANOV: Transient coherent anti-Stokes Raman scattering spectroscopy as a tool for measuring the diffusion coefficient and size of gas molecules

NASA Astrophysics Data System (ADS)

Nikitin, Sergei Yu

2009-07-01

Formulas are derived for evaluating the diffusion coefficient and size of gas molecules from transient coherent anti-Stokes Raman scattering measurements. Numerical estimates are presented for hydrogen.

Whispering gallery modes in photoluminescence and Raman spectra of a spherical microcavity with CdTe quantum dots: anti-Stokes emission and interference effects

PubMed Central

Gaponik, Nikolai; Gerlach, Matthias; Donegan, John F; Savateeva, Diana; Rogach, Andrey L

2006-01-01

We have studied the photoluminescence and Raman spectra of a system consisting of a polystyrene latex microsphere coated by CdTe colloidal quantum dots. The cavity-induced enhancement of the Raman scattering allows the observation of Raman spectra from only a monolayer of CdTe quantum dots. Periodic structure with very narrow peaks in the photoluminescence spectra of a single microsphere was detected both in the Stokes and anti-Stokes spectral regions, arising from the coupling between the emission of quantum dots and spherical cavity modes.

Novel auto-correction method in a fiber-optic distributed-temperature sensor using reflected anti-Stokes Raman scattering.

PubMed

Hwang, Dusun; Yoon, Dong-Jin; Kwon, Il-Bum; Seo, Dae-Cheol; Chung, Youngjoo

2010-05-10

A novel method for auto-correction of fiber optic distributed temperature sensor using anti-Stokes Raman back-scattering and its reflected signal is presented. This method processes two parts of measured signal. One part is the normal back scattered anti-Stokes signal and the other part is the reflected signal which eliminate not only the effect of local losses due to the micro-bending or damages on fiber but also the differential attenuation. Because the beams of the same wavelength are used to cancel out the local variance in transmission medium there is no differential attenuation inherently. The auto correction concept was verified by the bending experiment on different bending points. (c) 2010 Optical Society of America.

Coherent anti-Stokes Raman scattering spectroscope/microscope based on a widely tunable laser source

NASA Astrophysics Data System (ADS)

Dementjev, A.; Gulbinas, V.; Serbenta, A.; Kaucikas, M.; Niaura, G.

2010-03-01

We present a coherent anti-Stokes Raman scattering (CARS) microscope based on a robust and simple laser source. A picosecond laser operating in a cavity dumping regime at the 1 MHz repetition rate was used to pump a traveling wave optical parametric generator, which serves as a two-color excitation light source for the CARS microscope. We demonstrate the ability of the presented CARS microscope to measure CARS spectra and images by using several detection schemes.

Raman and coherent anti-Stokes Raman scattering microscopy studies of changes in lipid content and composition in hormone-treated breast and prostate cancer cells

NASA Astrophysics Data System (ADS)

Potcoava, Mariana C.; Futia, Gregory L.; Aughenbaugh, Jessica; Schlaepfer, Isabel R.; Gibson, Emily A.

2014-11-01

Increasing interest in the role of lipids in cancer cell proliferation and resistance to drug therapies has motivated the need to develop better tools for cellular lipid analysis. Quantification of lipids in cells is typically done by destructive chromatography protocols that do not provide spatial information on lipid distribution and prevent dynamic live cell studies. Methods that allow the analysis of lipid content in live cells are therefore of great importance. Using micro-Raman spectroscopy and coherent anti-Stokes Raman scattering (CARS) microscopy, we generated a lipid profile for breast (T47D, MDA-MB-231) and prostate (LNCaP, PC3) cancer cells upon exposure to medroxyprogesterone acetate (MPA) and synthetic androgen R1881. Combining Raman spectra with CARS imaging, we can study the process of hormone-mediated lipogenesis. Our results show that hormone-treated cancer cells T47D and LNCaP have an increased number and size of intracellular lipid droplets and higher degree of saturation than untreated cells. MDA-MB-231 and PC3 cancer cells showed no significant changes upon treatment. Principal component analysis with linear discriminant analysis of the Raman spectra was able to differentiate between cancer cells that were treated with MPA, R1881, and untreated.

Coherent anti-Stokes Raman scattering microscopy of single nanodiamonds

NASA Astrophysics Data System (ADS)

Pope, Iestyn; Payne, Lukas; Zoriniants, George; Thomas, Evan; Williams, Oliver; Watson, Peter; Langbein, Wolfgang; Borri, Paola

2014-11-01

Nanoparticles have attracted enormous attention for biomedical applications as optical labels, drug-delivery vehicles and contrast agents in vivo. In the quest for superior photostability and biocompatibility, nanodiamonds are considered one of the best choices due to their unique structural, chemical, mechanical and optical properties. So far, mainly fluorescent nanodiamonds have been utilized for cell imaging. However, their use is limited by the efficiency and costs in reliably producing fluorescent defect centres with stable optical properties. Here, we show that single non-fluorescing nanodiamonds exhibit strong coherent anti-Stokes Raman scattering (CARS) at the sp3 vibrational resonance of diamond. Using correlative light and electron microscopy, the relationship between CARS signal strength and nanodiamond size is quantified. The calibrated CARS signal in turn enables the analysis of the number and size of nanodiamonds internalized in living cells in situ, which opens the exciting prospect of following complex cellular trafficking pathways quantitatively.

Coherent anti-Stokes Raman scattering microscopy of single nanodiamonds.

PubMed

Pope, Iestyn; Payne, Lukas; Zoriniants, George; Thomas, Evan; Williams, Oliver; Watson, Peter; Langbein, Wolfgang; Borri, Paola

2014-11-01

Nanoparticles have attracted enormous attention for biomedical applications as optical labels, drug-delivery vehicles and contrast agents in vivo. In the quest for superior photostability and biocompatibility, nanodiamonds are considered one of the best choices due to their unique structural, chemical, mechanical and optical properties. So far, mainly fluorescent nanodiamonds have been utilized for cell imaging. However, their use is limited by the efficiency and costs in reliably producing fluorescent defect centres with stable optical properties. Here, we show that single non-fluorescing nanodiamonds exhibit strong coherent anti-Stokes Raman scattering (CARS) at the sp(3) vibrational resonance of diamond. Using correlative light and electron microscopy, the relationship between CARS signal strength and nanodiamond size is quantified. The calibrated CARS signal in turn enables the analysis of the number and size of nanodiamonds internalized in living cells in situ, which opens the exciting prospect of following complex cellular trafficking pathways quantitatively.

Optimizing the Laser-Pulse Configuration for Coherent Raman Spectroscopy

NASA Astrophysics Data System (ADS)

Pestov, Dmitry; Murawski, Robert K.; Ariunbold, Gombojav O.; Wang, Xi; Zhi, Miaochan; Sokolov, Alexei V.; Sautenkov, Vladimir A.; Rostovtsev, Yuri V.; Dogariu, Arthur; Huang, Yu; Scully, Marlan O.

2007-04-01

We introduce a hybrid technique that combines the robustness of frequency-resolved coherent anti-Stokes Raman scattering (CARS) with the advantages of time-resolved CARS spectroscopy. Instantaneous coherent broadband excitation of several characteristic molecular vibrations and the subsequent probing of these vibrations by an optimally shaped time-delayed narrowband laser pulse help to suppress the nonresonant background and to retrieve the species-specific signal. We used this technique for coherent Raman spectroscopy of sodium dipicolinate powder, which is similar to calcium dipicolinate (a marker molecule for bacterial endospores, such as Bacillus subtilis and Bacillus anthracis), and we demonstrated a rapid and highly specific detection scheme that works even in the presence of multiple scattering.

Optimizing the laser-pulse configuration for coherent Raman spectroscopy.

PubMed

Pestov, Dmitry; Murawski, Robert K; Ariunbold, Gombojav O; Wang, Xi; Zhi, Miaochan; Sokolov, Alexei V; Sautenkov, Vladimir A; Rostovtsev, Yuri V; Dogariu, Arthur; Huang, Yu; Scully, Marlan O

2007-04-13

We introduce a hybrid technique that combines the robustness of frequency-resolved coherent anti-Stokes Raman scattering (CARS) with the advantages of time-resolved CARS spectroscopy. Instantaneous coherent broadband excitation of several characteristic molecular vibrations and the subsequent probing of these vibrations by an optimally shaped time-delayed narrowband laser pulse help to suppress the nonresonant background and to retrieve the species-specific signal. We used this technique for coherent Raman spectroscopy of sodium dipicolinate powder, which is similar to calcium dipicolinate (a marker molecule for bacterial endospores, such as Bacillus subtilis and Bacillus anthracis), and we demonstrated a rapid and highly specific detection scheme that works even in the presence of multiple scattering.

Chemical imaging of tissue in vivo with video-rate coherent anti-Stokes Raman scattering microscopy.

PubMed

Evans, Conor L; Potma, Eric O; Puoris'haag, Mehron; Côté, Daniel; Lin, Charles P; Xie, X Sunney

2005-11-15

Imaging living organisms with molecular selectivity typically requires the introduction of specific labels. Many applications in biology and medicine, however, would significantly benefit from a noninvasive imaging technique that circumvents such exogenous probes. In vivo microscopy based on vibrational spectroscopic contrast offers a unique approach for visualizing tissue architecture with molecular specificity. We have developed a sensitive technique for vibrational imaging of tissues by combining coherent anti-Stokes Raman scattering (CARS) with video-rate microscopy. Backscattering of the intense forward-propagating CARS radiation in tissue gives rise to a strong epi-CARS signal that makes in vivo imaging possible. This substantially large signal allows for real-time monitoring of dynamic processes, such as the diffusion of chemical compounds, in tissues. By tuning into the CH(2) stretching vibrational band, we demonstrate CARS imaging and spectroscopy of lipid-rich tissue structures in the skin of a live mouse, including sebaceous glands, corneocytes, and adipocytes, with unprecedented contrast at subcellular resolution.

Optimizing coherent anti-Stokes Raman scattering by genetic algorithm controlled pulse shaping

NASA Astrophysics Data System (ADS)

Yang, Wenlong; Sokolov, Alexei

2010-10-01

The hybrid coherent anti-Stokes Raman scattering (CARS) has been successful applied to fast chemical sensitive detections. As the development of femto-second pulse shaping techniques, it is of great interest to find the optimum pulse shapes for CARS. The optimum pulse shapes should minimize the non-resonant four wave mixing (NRFWM) background and maximize the CARS signal. A genetic algorithm (GA) is developed to make a heuristic searching for optimized pulse shapes, which give the best signal the background ratio. The GA is shown to be able to rediscover the hybrid CARS scheme and find optimized pulse shapes for customized applications by itself.

Background-free coherent anti-stokes Raman scattering of gas- and liquid-phase samples in a mesoporous silica aerogel host.

PubMed

Konorov, Stanislav O; Turner, Robin F B; Blades, Michael W

2007-05-01

Efficient time-resolved coherent anti-Stokes Raman scattering (CARS) of atmospheric nitrogen and ethanol trapped in a nanoporous silica aerogel matrix is demonstrated. Silica aerogel hosts are attractive for analytical CARS spectroscopy due to their high porosity/low density, low refractive index, and low scattering cross-section. Differences between the resonant and nonresonant parts of the nonlinear optical susceptibilities lead to much longer relaxation times for analytes compared to the matrix. Time-resolved CARS can then be used to obtain a nearly background-free measurement at characteristic vibrations of the analyte. These results demonstrate the potential of this approach for rapid, sensitive, background-free analyses of analytes entrapped in the aerogel pores, which may be advantageous for some environmental, chemical, and biological sensing applications.

Hybrid single-source online Fourier transform coherent anti-Stokes Raman scattering/optical coherence tomography.

PubMed

Kamali, Tschackad; Považay, Boris; Kumar, Sunil; Silberberg, Yaron; Hermann, Boris; Werkmeister, René; Drexler, Wolfgang; Unterhuber, Angelika

2014-10-01

We demonstrate a multimodal optical coherence tomography (OCT) and online Fourier transform coherent anti-Stokes Raman scattering (FTCARS) platform using a single sub-12 femtosecond (fs) Ti:sapphire laser enabling simultaneous extraction of structural and chemical ("morphomolecular") information of biological samples. Spectral domain OCT prescreens the specimen providing a fast ultrahigh (4×12  μm axial and transverse) resolution wide field morphologic overview. Additional complementary intrinsic molecular information is obtained by zooming into regions of interest for fast label-free chemical mapping with online FTCARS spectroscopy. Background-free CARS is based on a Michelson interferometer in combination with a highly linear piezo stage, which allows for quick point-to-point extraction of CARS spectra in the fingerprint region in less than 125 ms with a resolution better than 4  cm(-1) without the need for averaging. OCT morphology and CARS spectral maps indicating phosphate and carbonate bond vibrations from human bone samples are extracted to demonstrate the performance of this hybrid imaging platform.

Coherent anti-Stokes Raman scattering microscopy of single nanodiamonds

PubMed Central

Pope, Iestyn; Payne, Lukas; Zoriniants, George; Thomas, Evan; Williams, Oliver; Watson, Peter; Langbein, Wolfgang; Borri, Paola

2016-01-01

Nanoparticles have attracted enormous attention for biomedical applications as optical labels, drug delivery vehicles, and contrast agents in vivo. In the quest for superior photostability and bio-compatibility, nanodiamonds (NDs) are considered one of the best choices due to their unique structural, chemical, mechanical, and optical properties. So far, mainly fluorescent NDs have been utilized for cell imaging. However, their use is limited by the efficiency and costs in reliably producing fluorescent defect centers with stable optical properties. Here, we show that single non-fluorescing NDs exhibit strong coherent anti-Stokes Raman scattering (CARS) at the sp3 vibrational resonance of diamond. Using correlative light and electron microscopy, the relationship between CARS signal strength and ND size is quantified. The calibrated CARS signal in turn enables the analysis of the number and size of NDs internalized in living cells in situ, which opens the exciting prospect of following complex cellular trafficking pathways quantitatively. PMID:25305746

A versatile setup using femtosecond adaptive spectroscopic techniques for coherent anti-Stokes Raman scattering

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shen, Yujie, E-mail: styojm@physics.tamu.edu; Voronine, Dmitri V.; Sokolov, Alexei V.

2015-08-15

We report a versatile setup based on the femtosecond adaptive spectroscopic techniques for coherent anti-Stokes Raman scattering. The setup uses a femtosecond Ti:Sapphire oscillator source and a folded 4f pulse shaper, in which the pulse shaping is carried out through conventional optical elements and does not require a spatial light modulator. Our setup is simple in alignment, and can be easily switched between the collinear single-beam and the noncollinear two-beam configurations. We demonstrate the capability for investigating both transparent and highly scattering samples by detecting transmitted and reflected signals, respectively.

New topics in coherent anti-stokes raman scattering gas-phase diagnostics : femtosecond rotational CARS and electric-field measurements.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lempert, Walter R.; Barnat, Edward V.; Kearney, Sean Patrick

2010-07-01

We discuss two recent diagnostic-development efforts in our laboratory: femtosecond pure-rotational Coherent anti-Stokes Raman scattering (CARS) for thermometry and species detection in nitrogen and air, and nanosecond vibrational CARS measurements of electric fields in air. Transient pure-rotational fs-CARS data show the evolution of the rotational Raman polarization in nitrogen and air over the first 20 ps after impulsive pump/Stokes excitation. The Raman-resonant signal strength at long time delays is large, and we additionally observe large time separation between the fs-CARS signatures of nitrogen and oxygen, so that the pure-rotational approach to fs-CARS has promise for simultaneous species and temperature measurementsmore » with suppressed nonresonant background. Nanosecond vibrational CARS of nitrogen for electric-field measurements is also demonstrated. In the presence of an electric field, a dipole is induced in the otherwise nonpolar nitrogen molecule, which can be probed with the introduction of strong collinear pump and Stokes fields, resulting in CARS signal radiation in the infrared. The electric-field diagnostic is demonstrated in air, where the strength of the coherent infrared emission and sensitivity our field measurements is quantified, and the scaling of the infrared signal with field strength is verified.« less

Comparison of coherent anti-Stokes Raman-scattering thermometry with thermocouple measurements and model predictions in both natural-gas and coal-dust flames.

PubMed

Lückerath, R; Woyde, M; Meier, W; Stricker, W; Schnell, U; Magel, H C; Görres, J; Spliethoff, H; Maier, H

1995-06-20

Mobile coherent anti-Stokes Raman-scattering equipment was applied for single-shot temperature measurements in a pilot-scale furnace with a thermal power of 300 kW, fueled with either natural gas or coal dust. Average temperatures deduced from N(2) coherent anti-Stokes Raman-scattering spectra were compared with thermocouple readings for identical flame conditions. There were evident differences between the results of both techniques, mainly in the case of the natural-gas flame. For the coal-dust flame, a strong influence of an incoherent and a coherent background, which led to remarkable changes in the spectral shape of the N(2)Q-branch spectra, was observed. Therefore an algorithm had to be developed to correct the coal-dust flame spectra before evaluation. The measured temperature profiles at two different planes in the furnace were compared with model calculations.

Coherent Anti-Stokes Raman Scattering Spectroscopy of Single Molecules in Solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sunney Xie, Wei Min, Chris Freudiger, Sijia Lu

2012-01-18

During this funding period, we have developed two breakthrough techniques. The first is stimulated Raman scattering microscopy, providing label-free chemical contrast for chemical and biomedical imaging based on vibrational spectroscopy. Spontaneous Raman microscopy provides specific vibrational signatures of chemical bonds, but is often hindered by low sensitivity. We developed a three-dimensional multiphoton vibrational imaging technique based on stimulated Raman scattering (SRS). The sensitivity of SRS imaging is significantly greater than that of spontaneous Raman microscopy, which is achieved by implementing high-frequency (megahertz) phase-sensitive detection. SRS microscopy has a major advantage over previous coherent Raman techniques in that it offers background-freemore » and readily interpretable chemical contrast. We demonstrated a variety of biomedical applications, such as differentiating distributions of omega-3 fatty acids and saturated lipids in living cells, imaging of brain and skin tissues based on intrinsic lipid contrast, and monitoring drug delivery through the epidermis. This technology offers exciting prospect for medical imaging. The second technology we developed is stimulated emission microscopy. Many chromophores, such as haemoglobin and cytochromes, absorb but have undetectable fluorescence because the spontaneous emission is dominated by their fast non-radiative decay. Yet the detection of their absorption is difficult under a microscope. We use stimulated emission, which competes effectively with the nonradiative decay, to make the chromophores detectable, as a new contrast mechanism for optical microscopy. We demonstrate a variety of applications of stimulated emission microscopy, such as visualizing chromoproteins, non-fluorescent variants of the green fluorescent protein, monitoring lacZ gene expression with a chromogenic reporter, mapping transdermal drug distribu- tions without histological sectioning, and label

Fast spectral coherent anti-Stokes Raman scattering microscopy with high-speed tunable picosecond laser.

PubMed

Cahyadi, Harsono; Iwatsuka, Junichi; Minamikawa, Takeo; Niioka, Hirohiko; Araki, Tsutomu; Hashimoto, Mamoru

2013-09-01

We develop a coherent anti-Stokes Raman scattering (CARS) microscopy system equipped with a tunable picosecond laser for high-speed wavelength scanning. An acousto-optic tunable filter (AOTF) is integrated in the laser cavity to enable wavelength scanning by varying the radio frequency waves applied to the AOTF crystal. An end mirror attached on a piezoelectric actuator and a pair of parallel plates driven by galvanometer motors are also introduced into the cavity to compensate for changes in the cavity length during wavelength scanning to allow synchronization with another picosecond laser. We demonstrate fast spectral imaging of 3T3-L1 adipocytes every 5  cm-1 in the Raman spectral region around 2850  cm-1 with an image acquisition time of 120 ms. We also demonstrate fast switching of Raman shifts between 2100 and 2850  cm-1, corresponding to CD2 symmetric stretching and CH2 symmetric stretching vibrations, respectively. The fast-switching CARS images reveal different locations of recrystallized deuterated and nondeuterated stearic acid.

Quantitative chemical imaging with background-free multiplex coherent anti-Stokes Raman scattering by dual-soliton Stokes pulses

PubMed Central

Chen, Kun; Wu, Tao; Wei, Haoyun; Zhou, Tian; Li, Yan

2016-01-01

Coherent anti-Stokes Raman microscopy (CARS) is a quantitative, chemically specific, and label-free optical imaging technique for studying inhomogeneous systems. However, the complicating influence of the nonresonant response on the CARS signal severely limits its sensitivity and specificity and especially limits the extent to which CARS microscopy has been used as a fully quantitative imaging technique. On the basis of spectral focusing mechanism, we establish a dual-soliton Stokes based CARS microspectroscopy and microscopy scheme capable of quantifying the spatial information of densities and chemical composition within inhomogeneous samples, using a single fiber laser. Dual-soliton Stokes scheme not only removes the nonresonant background but also allows robust acquisition of multiple characteristic vibrational frequencies. This all-fiber based laser source can cover the entire fingerprint (800-2200 cm−1) region with a spectral resolution of 15 cm−1. We demonstrate that quantitative degree determination of lipid-chain unsaturation in the fatty acids mixture can be achieved by the characterization of C = C stretching and CH2 deformation vibrations. For microscopy purposes, we show that the spatially inhomogeneous distribution of lipid droplets can be further quantitatively visualized using this quantified degree of lipid unsaturation in the acyl chain for contrast in the hyperspectral CARS images. The combination of compact excitation source and background-free capability to facilitate extraction of quantitative composition information with multiplex spectral peaks will enable wider applications of quantitative chemical imaging in studying biological and material systems. PMID:27867704

Radially polarized tip-enhanced near-field coherent anti-Stokes Raman scattering microscopy for vibrational nano-imaging

NASA Astrophysics Data System (ADS)

Lin, Jian; Zi Jian Er, Kenneth; Zheng, Wei; Huang, Zhiwei

2013-08-01

We report a radially polarized tip-enhanced near-field coherent anti-Stokes Raman scattering (RP-TE-CARS) microscopy technique for high-contrast vibrational imaging of subcellular organelles at nano-scale resolutions. The radially polarized pump and Stokes laser beams are tightly focused onto the sample while a gold-coated metallic probe is placed at the upper surface of the sample to enhance the electric field and CARS signals. The back-scattered CARS signal is measured with the gold-coated nano-tip being stationary at the focal region of laser beams. The RP-TE-CARS signal is ˜6-fold higher than that using linearly polarized laser excitation. We demonstrate the good performance of the RP-TE-CARS technique developed by imaging sub-micron polystyrene beads and mitochondria at nano-scale resolutions.

Single-shot detection of bacterial endospores via coherent Raman spectroscopy.

PubMed

Pestov, Dmitry; Wang, Xi; Ariunbold, Gombojav O; Murawski, Robert K; Sautenkov, Vladimir A; Dogariu, Arthur; Sokolov, Alexei V; Scully, Marlan O

2008-01-15

Recent advances in coherent Raman spectroscopy hold exciting promise for many potential applications. For example, a technique, mitigating the nonresonant four-wave-mixing noise while maximizing the Raman-resonant signal, has been developed and applied to the problem of real-time detection of bacterial endospores. After a brief review of the technique essentials, we show how extensions of our earlier experimental work [Pestov D, et al. (2007) Science 316:265-268] yield single-shot identification of a small sample of Bacillus subtilis endospores (approximately 10(4) spores). The results convey the utility of the technique and its potential for "on-the-fly" detection of biohazards, such as Bacillus anthracis. The application of optimized coherent anti-Stokes Raman scattering scheme to problems requiring chemical specificity and short signal acquisition times is demonstrated.

Multiplex coherent anti-Stokes Raman scattering microspectroscopy for monitoring molecular structural change in biological samples

NASA Astrophysics Data System (ADS)

Ohta, Takayuki; Hashizume, Hiroshi; Takeda, Keigo; Ishikawa, Kenji; Ito, Masafumi; Hori, Masaru

2014-10-01

Biological applications employing non-equilibrium plasma processing has been attracted much attention. It is essential to monitor the changes in an intracellular structure of the cell during the plasma exposure. In this study, we have analyzed the molecular structure of biological samples using multiplex coherent anti-Stokes Raman scattering (CARS) microspectroscopy. Two picosecond pulse lasers with fundamental (1064 nm) or the supercontinuum (460-2200 nm) were employed as a pump and Stokes beams of multiplex CARS microspectroscopy, respectively. The pump and the Stokes laser beams were collinearly overlapped and tightly focused into a sample using an objective lens of high numerical aperture. The CARS signal was collected by another microscope objective lens which is placed facing the first one. After passing through a short pass filter, the signal was dispersed by a polychromator, and was detected by a charge-coupled device camera. The sample was sandwiched by a coverslip and a glass bottom dish for the measurements and was placed on a piezo stage. The CARS signals of the quinhydrone crystal at 1655, 1584, 1237 and 1161 cm-1 were assigned to the C-C, C =O stretching, O-H and C-O stretching vibrational modes, respectively.

Stokes injected Raman capillary waveguide amplifier

DOEpatents

Kurnit, Norman A.

1980-01-01

A device for producing stimulated Raman scattering of CO.sub.2 laser radiation by rotational states in a diatomic molecular gas utilizing a Stokes injection signal. The system utilizes a cryogenically cooled waveguide for extending focal interaction length. The waveguide, in conjunction with the Stokes injection signal, reduces required power density of the CO.sub.2 radiation below the breakdown threshold for the diatomic molecular gas. A Fresnel rhomb is employed to circularly polarize the Stokes injection signal and CO.sub.2 laser radiation in opposite circular directions. The device can be employed either as a regenerative oscillator utilizing optical cavity mirrors or as a single pass amplifier. Additionally, a plurality of Raman gain cells can be staged to increase output power magnitude. Also, in the regenerative oscillator embodiment, the Raman gain cell cavity length and CO.sub.2 cavity length can be matched to provide synchronism between mode locked CO.sub.2 pulses and pulses produced within the Raman gain cell.

Multiplex coherent anti-Stokes Raman scattering microspectroscopy of brain tissue with higher ranking data classification for biomedical imaging

NASA Astrophysics Data System (ADS)

Pohling, Christoph; Bocklitz, Thomas; Duarte, Alex S.; Emmanuello, Cinzia; Ishikawa, Mariana S.; Dietzeck, Benjamin; Buckup, Tiago; Uckermann, Ortrud; Schackert, Gabriele; Kirsch, Matthias; Schmitt, Michael; Popp, Jürgen; Motzkus, Marcus

2017-06-01

Multiplex coherent anti-Stokes Raman scattering (MCARS) microscopy was carried out to map a solid tumor in mouse brain tissue. The border between normal and tumor tissue was visualized using support vector machines (SVM) as a higher ranking type of data classification. Training data were collected separately in both tissue types, and the image contrast is based on class affiliation of the single spectra. Color coding in the image generated by SVM is then related to pathological information instead of single spectral intensities or spectral differences within the data set. The results show good agreement with the H&E stained reference and spontaneous Raman microscopy, proving the validity of the MCARS approach in combination with SVM.

Towards Single-Shot Detection of Bacterial Endospores via Coherent Raman Spectroscopy

NASA Astrophysics Data System (ADS)

Pestov, Dmitry; Wang, Xi; Ariunbold, Gombojav; Murawski, Robert; Sautenkov, Vladimir; Sokolov, Alexei; Scully, Marlan

2007-10-01

Recent advances in coherent anti-Stokes Raman scattering (CARS) spectroscopy hold exciting promise to make the most out of now readily available ultrafast laser sources. Techniques have been devised to mitigate the nonresonant four-wave-mixing in favor of informative Raman-resonant signal. In particular, a hybrid technique for CARS (see Science 316, 265 (2007)) brings together the advantages of coherent broadband pump-Stokes excitation of molecular vibrations and their time-delayed but frequency-resolved probing via a spectrally narrowed and shaped laser pulse. We apply this technique to the problem of real-time detection of warfare bioagents and report single-shot acquisition of a distinct CARS spectrum from a small volume of B. subtilis endospores (˜10^4 spores), a harmless surrogate for B. anthracis. We study the dependence of the CARS signal on the energy of the ultrashort preparation pulses and find the limit on the pulse energy fluence (˜0.2 J/cm^2), imposed by the laser-induced damage of the spores.

Coherent anti-Stokes Raman scattering enhancement of thymine adsorbed on graphene oxide

PubMed Central

2014-01-01

Coherent anti-Stokes Raman scattering (CARS) of carbon nanostructures, namely, highly oriented pyrolytic graphite, graphene nanoplatelets, graphene oxide, and multiwall carbon nanotubes as well CARS spectra of thymine (Thy) molecules adsorbed on graphene oxide were studied. The spectra of the samples were compared with spontaneous Raman scattering (RS) spectra. The CARS spectra of Thy adsorbed on graphene oxide are characterized by shifts of the main bands in comparison with RS. The CARS spectra of the initial nanocarbons are definitely different: for all investigated materials, there is a redistribution of D- and G-mode intensities, significant shift of their frequencies (more than 20 cm-1), and appearance of new modes about 1,400 and 1,500 cm-1. The D band in CARS spectra is less changed than the G band; there is an absence of 2D-mode at 2,600 cm-1 for graphene and appearance of intensive modes of the second order between 2,400 and 3,000 cm-1. Multiphonon processes in graphene under many photon excitations seem to be responsible for the features of the CARS spectra. We found an enhancement of the CARS signal from thymine adsorbed on graphene oxide with maximum enhancement factor about 105. The probable mechanism of CARS enhancement is discussed. PMID:24948887

Hybrid femtosecond/picosecond rotational coherent anti-Stokes Raman scattering at flame temperatures using a second-harmonic bandwidth-compressed probe.

PubMed

Kearney, Sean P; Scoglietti, Daniel J

2013-03-15

We demonstrate an approach for picosecond probe-beam generation that enables hybrid femtosecond/picosecond pure-rotational coherent anti-Stokes Raman scattering (CARS) measurements in flames. Sum-frequency generation of bandwidth-compressed picosecond radiation from femtosecond pumps with phase-conjugate chirps provides probe pulses with energies in excess of 1 mJ that are temporally locked to the femtosecond pump/Stokes preparation. This method overcomes previous limitations on hybrid femtosecond/picosecond rotational CARS techniques, which have relied upon less efficient bandwidth-reduction processes that have generally resulted in prohibitively low probe energy for flame measurements. We provide the details of the second-harmonic approach and demonstrate the technique in near-adiabatic hydrogen/air flames.

Coherent anti-Stokes Raman scattering hyperspectral imaging of cartilage aiming for state discrimination of cell

NASA Astrophysics Data System (ADS)

Shiozawa, Manabu; Shirai, Masataka; Izumisawa, Junko; Tanabe, Maiko; Watanabe, Koich

2016-07-01

Noninvasive cell analyses are increasingly important in the medical field. A coherent anti-Stokes Raman scattering (CARS) microscope is the noninvasive imaging equipment and enables to obtain images indicating molecular distribution. However, due to low-signal intensity, it is still challenging to obtain images of the fingerprint region, in which many spectrum peaks correspond to compositions of a cell. Here, to identify cell differentiation by using multiplex CARS, we investigated hyperspectral imaging of the fingerprint region of living cells. To perform multiplex CARS, we used a prototype of a compact light source generating both pump light and broadband Stokes light. Assuming application to regenerative medicine, we chose a cartilage cell, whose differentiation is difficult to be identified by change of the cell morphology. Because one of the major components of cartilage is collagen, we focused on distribution of proline, which accounts for approximately 20% of collagen. The spectrum quality was improved by optical adjustments of the power branching ratio and divergence of Stokes light. Periphery of a cartilage cell was highlighted in a CARS image of proline, and this result suggests correspondence with collagen generated as an extracellular matrix. The possibility of noninvasive analyses by using CARS hyperspectral imaging was indicated.

Interference-free gas-phase thermometry at elevated pressure using hybrid femtosecond/picosecond rotational coherent anti-Stokes Raman scattering.

PubMed

Miller, Joseph D; Dedic, Chloe E; Roy, Sukesh; Gord, James R; Meyer, Terrence R

2012-02-27

Rotational-level-dependent dephasing rates and nonresonant background can lead to significant uncertainties in coherent anti-Stokes Raman scattering (CARS) thermometry under high-pressure, low-temperature conditions if the gas composition is unknown. Hybrid femtosecond/picosecond rotational CARS is employed to minimize or eliminate the influence of collisions and nonresonant background for accurate, frequency-domain thermometry at elevated pressure. The ability to ignore these interferences and achieve thermometric errors of <5% is demonstrated for N2 and O2 at pressures up to 15 atm. Beyond 15 atm, the effects of collisions cannot be ignored but can be minimized using a short probe delay (~6.5 ps) after Raman excitation, thereby improving thermometric accuracy with a time- and frequency-resolved theoretical model.

Multistaged stokes injected Raman capillary waveguide amplifier

DOEpatents

Kurnit, Norman A.

1980-01-01

A multistaged Stokes injected Raman capillary waveguide amplifier for providing a high gain Stokes output signal. The amplifier uses a plurality of optically coupled capillary waveguide amplifiers and one or more regenerative amplifiers to increase Stokes gain to a level sufficient for power amplification. Power amplification is provided by a multifocused Raman gain cell or a large diameter capillary waveguide. An external source of CO.sub.2 laser radiation can be injected into each of the capillary waveguide amplifier stages to increase Raman gain. Devices for injecting external sources of CO.sub.2 radiation include: dichroic mirrors, prisms, gratings and Ge Brewster plates. Alternatively, the CO.sub.2 input radiation to the first stage can be coupled and amplified between successive stages.

Single-shot gas-phase thermometry using pure-rotational hybrid femtosecond/picosecond coherent anti-Stokes Raman scattering.

PubMed

Miller, Joseph D; Roy, Sukesh; Slipchenko, Mikhail N; Gord, James R; Meyer, Terrence R

2011-08-01

High-repetition-rate, single-laser-shot measurements are important for the investigation of unsteady flows where temperature and species concentrations can vary significantly. Here, we demonstrate single-shot, pure-rotational, hybrid femtosecond/picosecond coherent anti-Stokes Raman scattering (fs/ps RCARS) thermometry based on a kHz-rate fs laser source. Interferences that can affect nanosecond (ns) and ps CARS, such as nonresonant background and collisional dephasing, are eliminated by selecting an appropriate time delay between the 100-fs pump/Stokes pulses and the pulse-shaped 8.4-ps probe. A time- and frequency-domain theoretical model is introduced to account for rotational-level dependent collisional dephasing and indicates that the optimal probe-pulse time delay is 13.5 ps to 30 ps. This time delay allows for uncorrected best-fit N2-RCARS temperature measurements with ~1% accuracy. Hence, the hybrid fs/ps RCARS approach can be performed with kHz-rate laser sources while avoiding corrections that can be difficult to predict in unsteady flows.

Single-shot gas-phase thermometry using pure-rotational hybrid femtosecond/picosecond coherent anti-Stokes Raman scattering

NASA Astrophysics Data System (ADS)

Miller, Joseph D.; Roy, Sukesh; Slipchenko, Mikhail N.; Gord, James R.; Meyer, Terrence R.

2011-08-01

High-repetition-rate, single-laser-shot measurements are important for the investigation of unsteady flows where temperature and species concentrations can vary significantly. Here, we demonstrate single-shot, pure-rotational, hybrid femtosecond/picosecond coherent anti-Stokes Raman scattering (fs/ps RCARS) thermometry based on a kHz-rate fs laser source. Interferences that can affect nanosecond (ns) and ps CARS, such as nonresonant background and collisional dephasing, are eliminated by selecting an appropriate time delay between the 100-fs pump/Stokes pulses and the pulse-shaped 8.4-ps probe. A time- and frequency-domain theoretical model is introduced to account for rotational-level dependent collisional dephasing and indicates that the optimal probe-pulse time delay is 13.5 ps to 30 ps. This time delay allows for uncorrected best-fit N2-RCARS temperature measurements with ~1% accuracy. Hence, the hybrid fs/ps RCARS approach can be performed with kHz-rate laser sources while avoiding corrections that can be difficult to predict in unsteady flows.

Temperature measurements in metalized propellant combustion using hybrid fs/ps coherent anti-Stokes Raman scattering.

PubMed

Kearney, Sean P; Guildenbecher, Daniel R

2016-06-20

We apply ultrafast pure-rotational coherent anti-Stokes Raman scattering (CARS) for temperature and relative oxygen concentration measurements in the plume emanating from a burning, aluminized ammonium-perchlorate propellant strand. Combustion of these metal-based propellants is a particularly hostile environment for laser-based diagnostics, with intense background luminosity and scattering from hot metal particles as large as several hundred micrometers in diameter. CARS spectra that were previously obtained using nanosecond pulsed lasers in an aluminum-particle-seeded flame are examined and are determined to be severely impacted by nonresonant background, presumably as a result of the plasma formed by particulate-enhanced laser-induced breakdown. Introduction of femtosecond/picosecond (fs/ps) laser pulses improves CARS detection by providing time-gated elimination of strong nonresonant background interference. Single-laser-shot fs/ps CARS spectra were acquired from the burning propellant plume, with picosecond probe-pulse delays of 0 and 16 ps from the femtosecond pump and Stokes pulses. At zero delay, nonresonant background overwhelms the Raman-resonant spectroscopic features. Time-delayed probing results in the acquisition of background-free spectra that were successfully fit for temperature and relative oxygen content. Temperature probability densities and temperature/oxygen correlations were constructed from ensembles of several thousand single-laser-shot measurements with the CARS measurement volume positioned within 3 mm or less of the burning propellant surface. The results show that ultrafast CARS is a potentially enabling technology for probing harsh, particle-laden flame environments.

Communication: hybrid femtosecond/picosecond rotational coherent anti-Stokes Raman scattering thermometry using a narrowband time-asymmetric probe pulse.

PubMed

Stauffer, Hans U; Miller, Joseph D; Roy, Sukesh; Gord, James R; Meyer, Terrence R

2012-03-21

A narrowband, time-asymmetric probe pulse is introduced into the hybrid femtosecond/picosecond rotational coherent anti-Stokes Raman scattering (fs/ps RCARS) technique to provide accurate and precise single-shot, high-repetition-rate gas-phase thermometric measurements. This narrowband pulse-generated by inserting a Fabry-Pérot étalon into the probe-pulse beam path-enables frequency-domain detection of pure-rotational transitions. The unique time-asymmetric nature of this pulse, in turn, allows for detection of resonant Raman-active rotational transitions free of signal contamination by nonresonant four-wave-mixing processes while still allowing detection at short probe-pulse delays, where collisional dephasing processes are negligible. We demonstrate that this approach provides excellent single-shot thermometric accuracy (<1% error) and precision (~2.5%) in gas-phase environments. © 2012 American Institute of Physics

Coherent Anti-Stokes Raman Scattering (CARS) as a Probe for Supersonic Hydrogen-Fuel/Air Mixing

NASA Technical Reports Server (NTRS)

Danehy, P. M.; O'Byrne, S.; Cutler, A. D.; Rodriguez, C. G.

2003-01-01

The dual-pump coherent anti-Stokes Raman spectroscopy (CARS) method was used to measure temperature and the absolute mole fractions of N2, O2 and H2 in a supersonic non-reacting fuel-air mixing experiment. Experiments were conducted in NASA Langley Research Center s Direct Connect Supersonic Combustion Test Facility. Under normal operation of this facility, hydrogen and air burn to increase the enthalpy of the test gas and O2 is added to simulate air. This gas is expanded through a Mach 2 nozzle and into a combustor model where fuel is then injected, mixes and burns. In the present experiment the O2 of the test gas is replaced by N2. The lack of oxidizer inhibited combustion of the injected H2 fuel jet allowing the fuel/air mixing process to be studied. CARS measurements were performed 427 mm downstream of the nozzle exit and 260 mm downstream of the fuel injector. Maps were obtained of the mean temperature, as well as the N2, O2 and H2 mean mole fraction fields. A map of mean H2O vapor mole fraction was also inferred from these measurements. Correlations between different measured parameters and their fluctuations are presented. The CARS measurements are compared with a preliminary computational prediction of the flow.

1-kHz two-dimensional coherent anti-Stokes Raman scattering (2D-CARS) for gas-phase thermometry.

PubMed

Miller, Joseph D; Slipchenko, Mikhail N; Mance, Jason G; Roy, Sukesh; Gord, James R

2016-10-31

Two-dimensional gas-phase coherent anti-Stokes Raman scattering (2D-CARS) thermometry is demonstrated at 1 kHz in a heated jet. A hybrid femtosecond/picosecond CARS configuration is used in a two-beam phase-matching arrangement with a 100-femtosecond pump/Stokes pulse and a 107-picosecond probe pulse. The femtosecond pulse is generated using a mode-locked oscillator and regenerative amplifier that is synchronized to a separate picosecond oscillator and burst-mode amplifier. The CARS signal is spectrally dispersed in a custom imaging spectrometer and detected using a high-speed camera with image intensifier. 1-kHz, single-shot planar measurements at room temperature exhibit error of 2.6% and shot-to-shot variations of 2.6%. The spatial variation in measured temperature is 9.4%. 2D-CARS temperature measurements are demonstrated in a heated O₂ jet to capture the spatiotemporal evolution of the temperature field.

Hybrid fs/ps Coherent Anti-Stokes Raman Scattering for Multiparameter Measurements of Combustion and Nonequilibrium

NASA Astrophysics Data System (ADS)

Dedic, Chloe Elizabeth

Hybrid femtosecond/picosecond coherent anti-Stokes Raman scattering (fs/ps CARS) is developed for measuring internal energy distributions, species concentration, and pressure for highly dynamic gas-phase environments. Systems of interest include next-generation combustors, plasma-based manufacturing and plasma-assisted combustion, and high-speed aerodynamic flow. These challenging environments include spatial variations and fast dynamics that require the spatial and temporal resolution offered by hybrid fs/ps CARS. A novel dual-pump fs/ps CARS approach is developed to simultaneously excite pure-rotational and rovibrational Raman coherences for dynamic thermometry (300-2400 K) and detection of major combustion species. This approach was also used to measure single-shot vibrational and rotational energy distributions of the nonequilibrium environment of a dielectric barrier discharge plasma. Detailed spatial distributions and shot-to-shot fluctuations of rotational and vibrational temperatures spanning 325-450 K and 1200-5000 K were recorded across the plasma and surrounding flow, and are compared to plasma emission spectroscopy measurements. Dual-pump hybrid fs/ps CARS allows for concise, kHz-rate measurements of vibrational and rotational energy distributions or temperatures at equilibrium and nonequilibrium without nonresonant wave-mixing or molecular collisional interference. Additionally, a highly transient ns laser spark is explored using CARS to measure temperature and pressure behind the shock wave and temperature of the expanding plasma kernel. Vibrational energy distributions at the exit of a microscale gaseous detonation tube are presented. Theory required to model fs/ps CARS response, including nonthermal energy distributions, is presented. The impact of nonequilibrium on measurement accuracy is explored, and a coherent line-mixing model is validated with high-pressure measurements. Temperature and pressure sensitivity are investigated for multiple

Temperature measurements in metalized propellant combustion using hybrid fs/ps coherent anti-Stokes Raman scattering

DOE PAGES

Kearney, Sean P.; Guildenbecher, Daniel R.

2016-06-20

We apply ultrafast pure-rotational coherent anti-Stokes Raman scattering (CARS) for temperature and relative oxygen concentration measurements in the plume emanating from a burning, aluminized ammonium-perchlorate propellant strand. Combustion of these metal-based propellants is a particularly hostile environment for laser-based diagnostics, with intense background luminosity and scattering from hot metal particles as large as several hundred micrometers in diameter. CARS spectra that were previously obtained using nanosecond pulsed lasers in an aluminum-particle-seeded flame are examined and are determined to be severely impacted by nonresonant background, presumably as a result of the plasma formed by particulate-enhanced laser-induced breakdown. Introduction of femtosecond/picosecond (fs/ps)more » laser pulses improves CARS detection by providing time-gated elimination of strong nonresonant background interference. Single-laser-shot fs/ps CARS spectra were acquired from the burning propellant plume, with picosecond probe-pulse delays of 0 and 16 ps from the femtosecond pump and Stokes pulses. At zero delay, nonresonant background overwhelms the Raman-resonant spectroscopic features. Time-delayed probing results in the acquisition of background-free spectra that were successfully fit for temperature and relative oxygen content. Temperature probability densities and temperature/oxygen correlations were constructed from ensembles of several thousand single-laser-shot measurements with the CARS measurement volume positioned within 3 mm or less of the burning propellant surface. Lastly, the results show that ultrafast CARS is a potentially enabling technology for probing harsh, particle-laden flame environments.« less

Temperature measurements in metalized propellant combustion using hybrid fs/ps coherent anti-Stokes Raman scattering

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kearney, Sean P.; Guildenbecher, Daniel R.

We apply ultrafast pure-rotational coherent anti-Stokes Raman scattering (CARS) for temperature and relative oxygen concentration measurements in the plume emanating from a burning, aluminized ammonium-perchlorate propellant strand. Combustion of these metal-based propellants is a particularly hostile environment for laser-based diagnostics, with intense background luminosity and scattering from hot metal particles as large as several hundred micrometers in diameter. CARS spectra that were previously obtained using nanosecond pulsed lasers in an aluminum-particle-seeded flame are examined and are determined to be severely impacted by nonresonant background, presumably as a result of the plasma formed by particulate-enhanced laser-induced breakdown. Introduction of femtosecond/picosecond (fs/ps)more » laser pulses improves CARS detection by providing time-gated elimination of strong nonresonant background interference. Single-laser-shot fs/ps CARS spectra were acquired from the burning propellant plume, with picosecond probe-pulse delays of 0 and 16 ps from the femtosecond pump and Stokes pulses. At zero delay, nonresonant background overwhelms the Raman-resonant spectroscopic features. Time-delayed probing results in the acquisition of background-free spectra that were successfully fit for temperature and relative oxygen content. Temperature probability densities and temperature/oxygen correlations were constructed from ensembles of several thousand single-laser-shot measurements with the CARS measurement volume positioned within 3 mm or less of the burning propellant surface. Lastly, the results show that ultrafast CARS is a potentially enabling technology for probing harsh, particle-laden flame environments.« less

Method And System For Examining Biological Materials Using Low Power Cw Excitation Raman Spectroscopy.

DOEpatents

Alfano, Robert R.; Wang, Wubao

2003-05-06

A method and system for examining biological materials using low-power cw excitation Raman spectroscopy. A low-power continuous wave (cw) pump laser beam and a low-power cw Stokes (or anti-Stokes) probe laser beam simultaneously illuminate a biological material and traverse the biological material in collinearity. The pump beam, whose frequency is varied, is used to induce Raman emission from the biological material. The intensity of the probe beam, whose frequency is kept constant, is monitored as it leaves the biological material. When the difference between the pump and probe excitation frequencies is equal to a Raman vibrational mode frequency of the biological material, the weak probe signal becomes amplified by one or more orders of magnitude (typically up to about 10.sup.4 -10.sup.6) due to the Raman emission from the pump beam. In this manner, by monitoring the intensity of the probe beam emitted from the biological material as the pump beam is varied in frequency, one can obtain an excitation Raman spectrum for the biological material tested. The present invention may be applied to in the in vivo and/or in vitro diagnosis of diabetes, heart disease, hepatitis, cancers and other diseases by measuring the characteristic excitation Raman lines of blood glucose, cholesterol, serum glutamic oxalacetic transaminase (SGOT)/serum glutamic pyruvic transaminase (SGPT), tissues and other corresponding Raman-active body constituents, respectively.

Label-Free Delineation of Brain Tumors by Coherent Anti-Stokes Raman Scattering Microscopy in an Orthotopic Mouse Model and Human Glioblastoma

PubMed Central

Tamosaityte, Sandra; Leipnitz, Elke; Geiger, Kathrin D.; Schackert, Gabriele; Koch, Edmund; Steiner, Gerald; Kirsch, Matthias

2014-01-01

Background Coherent anti-Stokes Raman scattering (CARS) microscopy provides fine resolution imaging and displays morphochemical properties of unstained tissue. Here, we evaluated this technique to delineate and identify brain tumors. Methods Different human tumors (glioblastoma, brain metastases of melanoma and breast cancer) were induced in an orthotopic mouse model. Cryosections were investigated by CARS imaging tuned to probe C-H molecular vibrations, thereby addressing the lipid content of the sample. Raman microspectroscopy was used as reference. Histopathology provided information about the tumor's localization, cell proliferation and vascularization. Results The morphochemical contrast of CARS images enabled identifying brain tumors irrespective of the tumor type and properties: All tumors were characterized by a lower CARS signal intensity than the normal parenchyma. On this basis, tumor borders and infiltrations could be identified with cellular resolution. Quantitative analysis revealed that the tumor-related reduction of CARS signal intensity was more pronounced in glioblastoma than in metastases. Raman spectroscopy enabled relating the CARS intensity variation to the decline of total lipid content in the tumors. The analysis of the immunohistochemical stainings revealed no correlation between tumor-induced cytological changes and the extent of CARS signal intensity reductions. The results were confirmed on samples of human glioblastoma. Conclusions CARS imaging enables label-free, rapid and objective identification of primary and secondary brain tumors. Therefore, it is a potential tool for diagnostic neuropathology as well as for intraoperative tumor delineation. PMID:25198698

Standoff detection of trace amounts of solids by nonlinear Raman spectroscopy using shaped femtosecond pulses

NASA Astrophysics Data System (ADS)

Katz, O.; Natan, A.; Silberberg, Y.; Rosenwaks, S.

2008-04-01

We demonstrate a single-beam, standoff (>10m) detection and identification of various materials including minute amounts of explosives under ambient light conditions. This is obtained by multiplex coherent anti-Stokes Raman scattering spectroscopy (CARS) using a single femtosecond phase-shaped laser pulse. We exploit the strong nonresonant background for amplification of the backscattered resonant CARS signals by employing a homodyne detection scheme. The simple and highly sensitive spectroscopic technique has a potential for hazardous materials standoff detection applications.

Temperature dependence of sapphire fiber Raman scattering

DOE PAGES

Liu, Bo; Yu, Zhihao; Tian, Zhipeng; ...

2015-04-27

Anti-Stokes Raman scattering in sapphire fiber has been observed for the first time. Temperature dependence of Raman peaks’ intensity, frequency shift, and linewidth were also measured. Three anti-Stokes Raman peaks were observed at temperatures higher than 300°C in a 0.72-m-long sapphire fiber excited by a second-harmonic Nd YAG laser. The intensity of anti-Stokes peaks are comparable to that of Stokes peaks when the temperature increases to 1033°C. We foresee the combination of sapphire fiber Stokes and anti-Stokes measurement in use as a mechanism for ultrahigh temperature sensing.

Nitric oxide concentration measurements in atmospheric pressure flames using electronic-resonance-enhanced coherent anti-Stokes Raman scattering

NASA Astrophysics Data System (ADS)

Chai, N.; Kulatilaka, W. D.; Naik, S. V.; Laurendeau, N. M.; Lucht, R. P.; Kuehner, J. P.; Roy, S.; Katta, V. R.; Gord, J. R.

2007-06-01

We report the application of electronic-resonance-enhanced coherent anti-Stokes Raman scattering (ERE-CARS) for measurements of nitric oxide concentration ([NO]) in three different atmospheric pressure flames. Visible pump (532 nm) and Stokes (591 nm) beams are used to probe the Q-branch of the Raman transition. A significant resonance enhancement is obtained by tuning an ultraviolet probe beam (236 nm) into resonance with specific rotational transitions in the (v’=0, v”=1) vibrational band of the A2Σ+-X2Π electronic system of NO. ERE-CARS spectra are recorded at various heights within a hydrogen-air flame producing relatively low concentrations of NO over a Hencken burner. Good agreement is obtained between NO ERE-CARS measurements and the results of flame computations using UNICORN, a two-dimensional flame code. Excellent agreement between measured and calculated NO spectra is also obtained when using a modified version of the Sandia CARSFT code for heavily sooting acetylene-air flames (φ=0.8 to φ=1.6) on the same Hencken burner. Finally, NO concentration profiles are measured using ERE-CARS in a laminar, counter-flow, non-premixed hydrogen-air flame. Spectral scans are recorded by probing the Q1 (9.5), Q1 (13.5) and Q1 (17.5) Raman transitions. The measured shape of the [NO] profile is in good agreement with that predicted using the OPPDIF code, even without correcting for collisional effects. These comparisons between [NO] measurements and predictions establish the utility of ERE-CARS for detection of NO in flames with large temperature and concentration gradients as well as in sooting environments.

Broadband hyperspectral coherent anti-Stokes Raman scattering microscopy for stain-free histological imaging with principal component analysis

NASA Astrophysics Data System (ADS)

Xu, Jingjiang; Guo, Baoshan; Wong, Kenneth K. Y.; Tsia, Kevin K.

2014-02-01

Routine procedures in standard histopathology involve laborious steps of tissue processing and staining for final examination. New techniques which can bypass these procedures and thus minimize the tissue handling error would be of great clinical value. Coherent anti-Stokes Raman scattering (CARS) microscopy is an attractive tool for label-free biochemical-specific characterization of biological specimen. However, a vast majority of prior works on CARS (or stimulated Raman scattering (SRS)) bioimaging restricted analyses on a narrowband or well-distinctive Raman spectral signatures. Although hyperspectral SRS/CARS imaging has recently emerged as a better solution to access wider-band spectral information in the image, studies mostly focused on a limited spectral range, e.g. CH-stretching vibration of lipids, or non-biological samples. Hyperspectral image information in the congested fingerprint spectrum generally remains untapped for biological samples. In this regard, we further explore ultrabroadband hyperspectral multiplex (HM-CARS) to perform chemoselective histological imaging with the goal of exploring its utility in stain-free clinical histopathology. Using the supercontinuum Stokes, our system can access the CARS spectral window as wide as >2000cm-1. In order to unravel the congested CARS spectra particularly in the fingerprint region, we first employ a spectral phase-retrieval algorithm based on Kramers-Kronig (KK) transform to minimize the non-resonant background in the CARS spectrum. We then apply principal component analysis (PCA) to identify and map the spatial distribution of different biochemical components in the tissues. We demonstrate chemoselective HM-CARS imaging of a colon tissue section which displays the key cellular structures that correspond well with standard stained-tissue observation.

Molecular Orientation in Dry and Hydrated Cellulose Fibers: A Coherent Anti-Stokes Raman Scattering Microscopy Study

PubMed Central

Zimmerley, Maxwell; Younger, Rebecca; Valenton, Tiffany; Oertel, David C.; Ward, Jimmie L.; Potma, Eric O.

2012-01-01

Coherent anti-Stokes Raman scattering (CARS) microscopy is combined with spontaneous Raman scattering microspectroscopy and second harmonic generation (SHG) microscopy to interrogate the molecular alignment in dry and hydrated cellulose fibers. Two types of cellulose were investigated: natural cellulose I in cotton fibers and regenerated cellulose II in rayon fibers. On the basis of the orientation of the methylene symmetric stretching vibration, the molecular alignment of cellulose microfibrils is found to be conserved on the micrometer scale. Whereas the molecular orientation in cotton shows modest variability along the fiber, the alignment of the cellulose units in rayon is highly consistent throughout the fiber. The ordered alignment is retained upon fiber hydration. Upon hydration of the cellulose fibers, an anisotropic electronic contribution is observed, which indicates an ordered incorporation of water molecules into the fiber structure. The third-order and second-order electronic polarizability of cellulose I are directed along the axis of the polyglucan chain. No second-order optical response is observed in cellulose II, supporting the antiparallel arrangement of the polyglucan chains in regenerated cellulose. PMID:20684644

Single fiber temperature probe configuration using anti-Stokes luminescence from Cr:GdAlO3

NASA Astrophysics Data System (ADS)

Eldridge, Jeffrey I.

2018-06-01

Single-photon excitation of anti-Stokes-shifted emission from a thermographic phosphor allows operation of a luminescence decay-based single fiber temperature probe with negligible interference from background fiber-generated Raman scattering. While single fiber probe configurations for luminescence-based fiber optic thermometers offer advantages of simple design, compactness, and superior emission light collection efficiency, their effective use has been limited by interference from Raman scattering in the fiber probe and excitation delivery fiber that produces distortion of the luminescence decay that follows the excitation pulse. The near elimination of interference by background fiber-generated Raman scattering was demonstrated by incorporating a Cr-doped GdAlO3 (Cr:GdAlO3) thermographic phosphor as the sensing element at the end of a single fiber luminescence decay-based thermometer and detecting anti-Stokes-shifted luminescence centered at 542 or 593 nm produced by 695 nm excitation. Measurements were performed using both silica (up to 1150 °C) and single-crystal YAG (up to 1200 °C) fiber-based thermometers. Selection of emission detection centered at 542 nm greatly benefited the YAG fiber probe measurements by practically eliminating detection of otherwise significant luminescence from Cr3+ impurities in the YAG fiber. For both the silica and YAG fiber probes, the relative benefit of adopting single-photon excitation of anti-Stokes-shifted luminescence was evaluated by comparison with results obtained by conventional 532 nm excitation of Stokes-shifted luminescence.

In vivo histology: optical biopsies with chemical contrast using clinical multiphoton/coherent anti-Stokes Raman scattering tomography

NASA Astrophysics Data System (ADS)

Weinigel, M.; Breunig, H. G.; Kellner-Höfer, M.; Bückle, R.; Darvin, M. E.; Klemp, M.; Lademann, J.; König, K.

2014-05-01

The majority of existing coherent anti-Stokes Raman scattering (CARS) imaging systems are still huge and complicated laboratory systems and neither compact nor user-friendly nor mobile medically certified CARS systems. We have developed a new flexible multiphoton/CARS tomograph for imaging in a clinical environment. The system offers exceptional 360° flexibility with a very stable setup and enables label free ‘in vivo histology’ with chemical contrast within seconds. It can be completely operated by briefly trained non-laser experts. The imaging capability and flexibility of the novel in vivo tomograph are shown on optical biopsies with subcellular resolution and chemical contrast of patients suffering from psoriasis and squamous cell carcinoma.

Coherent anti-Stokes Raman scattering (CARS) spectroscopy in Caenorhabditis elegans and Globodera pallida: evidence for an ivermectin-activated decrease in lipid stores.

PubMed

Smus, Justyna P; Ludlow, Elizabeth; Dallière, Nicolas; Luedtke, Sarah; Monfort, Tual; Lilley, Catherine; Urwin, Peter; Walker, Robert J; O'Connor, Vincent; Holden-Dye, Lindy; Mahajan, Sumeet

2017-12-01

Macrocyclic lactones are arguably the most successful chemical class with efficacy against parasitic nematodes. Here we investigated the effect of the macrocyclic lactone ivermectin on lipid homeostasis in the plant parasitic nematode Globodera pallida and provide new insight into its mode of action. A non-invasive, non-destructive, label-free and chemically selective technique called Coherent anti-Stokes Raman scattering (CARS) spectroscopy was used to study lipid stores in G. pallida. We optimised the protocol using the free-living nematode Caenorhabditis elegans and then used CARS to quantify lipid stores in the pre-parasitic, non-feeding J2 stage of G. pallida. This revealed a concentration of lipid stores in the posterior region of J2 s within 24 h of hatching which decreased to undetectable levels over the course of 28 days. We tested the effect of ivermectin on J2 viability and lipid stores. Within 24 h, ivermectin paralysed J2 s. Counterintuitively, over the same time-course ivermectin increased the rate of depletion of J2 lipid, suggesting that in ivermectin-treated J2 s there is a disconnection between the energy requirements for motility and metabolic rate. This decrease in lipid stores would be predicted to negatively impact on J2 infective potential. These data suggest that the benefit of macrocyclic lactones as seed treatments may be underpinned by a multilevel effect involving both neuromuscular inhibition and acceleration of lipid metabolism. © 2017 The Authors. Pest Management Science published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry. © 2017 The Authors. Pest Management Science published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

Inflammation-related alterations of lipids after spinal cord injury revealed by Raman spectroscopy

NASA Astrophysics Data System (ADS)

Tamosaityte, Sandra; Galli, Roberta; Uckermann, Ortrud; Sitoci-Ficici, Kerim H.; Koch, Maria; Later, Robert; Schackert, Gabriele; Koch, Edmund; Steiner, Gerald; Kirsch, Matthias

2016-06-01

Spinal cord injury (SCI) triggers several lipid alterations in nervous tissue. It is characterized by extensive demyelination and the inflammatory response leads to accumulation of activated microglia/macrophages, which often transform into foam cells by accumulation of lipid droplets after engulfment of the damaged myelin sheaths. Using an experimental rat model, Raman microspectroscopy was applied to retrieve the modifications of the lipid distribution following SCI. Coherent anti-Stokes Raman scattering (CARS) and endogenous two-photon fluorescence (TPEF) microscopies were used for the detection of lipid-laden inflammatory cells. The Raman mapping of CH2 deformation mode intensity at 1440 cm-1 retrieved the lipid-depleted injury core. Preserved white matter and inflammatory regions with myelin fragmentation and foam cells were localized by specifically addressing the distribution of esterified lipids, i.e., by mapping the intensity of the carbonyl Raman band at 1743 cm-1, and were in agreement with CARS/TPEF microscopy. Principal component analysis revealed that the inflammatory regions are notably rich in saturated fatty acids. Therefore, Raman spectroscopy enabled to specifically detect inflammation after SCI and myelin degradation products.

Pressure measurements using hybrid femtosecond/picosecond rotational coherent anti-Stokes Raman scattering.

PubMed

Kearney, Sean P; Danehy, Paul M

2015-09-01

We investigate the feasibility of gas-phase pressure measurements using fs/ps rotational CARS. Femtosecond pump and Stokes pulses impulsively prepare a rotational Raman coherence, which is probed by a high-energy 5-ps pulse introduced at a time delay from the Raman preparation. These ultrafast laser pulses are shorter than collisional-dephasing time scales, enabling a new hybrid time- and frequency-domain detection scheme for pressure. Single-laser-shot rotational CARS spectra were recorded from N2 contained in a room-temperature gas cell for pressures from 0.4 to 3 atm and probe delays ranging from 16 to 298 ps. Sensitivity of the accuracy and precision of the pressure data to probe delay was investigated. The technique exhibits superior precision and comparable accuracy to previous laser-diagnostic pressure measurements.

Effect of scattering on coherent anti-Stokes Raman scattering (CARS) signals.

PubMed

Ranasinghesagara, Janaka C; De Vito, Giuseppe; Piazza, Vincenzo; Potma, Eric O; Venugopalan, Vasan

2017-04-17

We develop a computational framework to examine the factors responsible for scattering-induced distortions of coherent anti-Stokes Raman scattering (CARS) signals in turbid samples. We apply the Huygens-Fresnel wave-based electric field superposition (HF-WEFS) method combined with the radiating dipole approximation to compute the effects of scattering-induced distortions of focal excitation fields on the far-field CARS signal. We analyze the effect of spherical scatterers, placed in the vicinity of the focal volume, on the CARS signal emitted by different objects (2μm diameter solid sphere, 2μm diameter myelin cylinder and 2μm diameter myelin tube). We find that distortions in the CARS signals arise not only from attenuation of the focal field but also from scattering-induced changes in the spatial phase that modifies the angular distribution of the CARS emission. Our simulations further show that CARS signal attenuation can be minimized by using a high numerical aperture condenser. Moreover, unlike the CARS intensity image, CARS images formed by taking the ratio of CARS signals obtained using x- and y-polarized input fields is relatively insensitive to the effects of spherical scatterers. Our computational framework provide a mechanistic approach to characterizing scattering-induced distortions in coherent imaging of turbid media and may inspire bottom-up approaches for adaptive optical methods for image correction.

Effect of scattering on coherent anti-Stokes Raman scattering (CARS) signals

PubMed Central

Ranasinghesagara, Janaka C.; De Vito, Giuseppe; Piazza, Vincenzo; Potma, Eric O.; Venugopalan, Vasan

2017-01-01

We develop a computational framework to examine the factors responsible for scattering-induced distortions of coherent anti-Stokes Raman scattering (CARS) signals in turbid samples. We apply the Huygens-Fresnel wave-based electric field superposition (HF-WEFS) method combined with the radiating dipole approximation to compute the effects of scattering-induced distortions of focal excitation fields on the far-field CARS signal. We analyze the effect of spherical scatterers, placed in the vicinity of the focal volume, on the CARS signal emitted by different objects (2μm diameter solid sphere, 2μm diameter myelin cylinder and 2μm diameter myelin tube). We find that distortions in the CARS signals arise not only from attenuation of the focal field but also from scattering-induced changes in the spatial phase that modifies the angular distribution of the CARS emission. Our simulations further show that CARS signal attenuation can be minimized by using a high numerical aperture condenser. Moreover, unlike the CARS intensity image, CARS images formed by taking the ratio of CARS signals obtained using x- and y-polarized input fields is relatively insensitive to the effects of spherical scatterers. Our computational framework provide a mechanistic approach to characterizing scattering-induced distortions in coherent imaging of turbid media and may inspire bottom-up approaches for adaptive optical methods for image correction. PMID:28437941

Diagnosing lung cancer using coherent anti-Stokes Raman scattering microscopy

NASA Astrophysics Data System (ADS)

Gao, Liang; Yang, Yaliang; Xing, Jiong; Thrall, Michael J.; Wang, Zhiyong; Li, Fuhai; Luo, Pengfei; Wong, Kelvin K.; Zhao, Hong; Wong, Stephen T. C.

2011-03-01

Lung carcinoma is the most prevalent type of cancer in the world, and it is responsible for more deaths than other types of cancer. During diagnosis, a pathologist primarily aims to differentiate small cell carcinoma from non-small cell carcinoma on biopsy and cytology specimens, which is time consuming due to the time required for tissue processing and staining. To speed up the diagnostic process, we investigated the feasibility of using coherent anti-Stokes Raman scattering (CARS) microscopy as a label-free strategy to image lung lesions and differentiate subtypes of lung cancers. Different mouse lung cancer models were developed by injecting human lung cancer cell lines, including adenocarcinoma, squamous cell carcinoma, and small cell carcinoma, into lungs of the nude mice. CARS images were acquired from normal lung tissues and different subtypes of cancer lesions ex vivo using intrinsic contrasts from symmetric CH2 bonds. These images showed good correlation with the hematoxylin and eosin (H&E) stained sections from the same tissue samples with regard to cell size, density, and cell-cell distance. These features are routinely used in diagnosing lung lesions. Our results showed that the CARS technique is capable of providing a visualizable platform to differentiate different kinds of lung cancers using the same pathological features without histological staining and thus has the potential to serve as a more efficient examination tool for diagnostic pathology. In addition, incorporating with suitable fiber-optic probes would render the CARS technique as a promising approach for in vivo diagnosis of lung cancer.

Intracellular imaging of docosanol in living cells by coherent anti-Stokes Raman scattering microscopy

NASA Astrophysics Data System (ADS)

You, Sixian; Liu, Yuan; Arp, Zane; Zhao, Youbo; Chaney, Eric J.; Marjanovic, Marina; Boppart, Stephen A.

2017-07-01

Docosanol is an over-the-counter topical agent that has proved to be one of the most effective therapies for treating herpes simplex labialis. However, the mechanism by which docosanol suppresses lesion formation remains poorly understood. To elucidate its mechanism of action, we investigated the uptake of docosanol in living cells using coherent anti-Stokes Raman scattering microscopy. Based on direct visualization of the deuterated docosanol, we observed highly concentrated docosanol inside living cells 24 h after drug treatment. In addition, different spatial patterns of drug accumulation were observed in different cell lines. In keratinocytes, which are the targeted cells of docosanol, the drug molecules appeared to be docking at the periphery of the cell membrane. In contrast, the drug molecules in fibroblasts appeared to accumulate in densely packed punctate regions throughout the cytoplasm. These results suggest that this molecular imaging approach is suitable for the longitudinal tracking of drug molecules in living cells to identify cell-specific trafficking and may also have implications for elucidating the mechanism by which docosanol suppresses lesion formation.

Quantitative Chemical Imaging and Unsupervised Analysis Using Hyperspectral Coherent Anti-Stokes Raman Scattering Microscopy

PubMed Central

2013-01-01

In this work, we report a method to acquire and analyze hyperspectral coherent anti-Stokes Raman scattering (CARS) microscopy images of organic materials and biological samples resulting in an unbiased quantitative chemical analysis. The method employs singular value decomposition on the square root of the CARS intensity, providing an automatic determination of the components above noise, which are retained. Complex CARS susceptibility spectra, which are linear in the chemical composition, are retrieved from the CARS intensity spectra using the causality of the susceptibility by two methods, and their performance is evaluated by comparison with Raman spectra. We use non-negative matrix factorization applied to the imaginary part and the nonresonant real part of the susceptibility with an additional concentration constraint to obtain absolute susceptibility spectra of independently varying chemical components and their absolute concentration. We demonstrate the ability of the method to provide quantitative chemical analysis on known lipid mixtures. We then show the relevance of the method by imaging lipid-rich stem-cell-derived mouse adipocytes as well as differentiated embryonic stem cells with a low density of lipids. We retrieve and visualize the most significant chemical components with spectra given by water, lipid, and proteins segmenting the image into the cell surrounding, lipid droplets, cytosol, and the nucleus, and we reveal the chemical structure of the cells, with details visualized by the projection of the chemical contrast into a few relevant channels. PMID:24099603

Picosecond coherent anti-Stokes Raman scattering (CARS) study of vibrational dephasing of carbon disulfide and benzene in solution

NASA Technical Reports Server (NTRS)

Perry, Joseph W.; Woodward, Anne M.; Stephenson, John C.

1986-01-01

The vibrational dephasing of the 656/cm mode (nu1, a1g) of CS2 and the 991/cm mode (nu2, a1g) of benzene have been studied as a function of concentration in mixtures with a number of solvents using a ps time-resolved CARS technique. This technique employs two tunable synchronously-pumped mode-locked dye lasers in a stimulated Raman pump, coherent anti-Stokes Raman probe time-resolved experiment. Results are obtained for CS2 in carbon tetrachloride, benzene, nitrobenzene, and ethanol and for benzene nu2 in CS2. The dephasing rates of CS2 nu1 increase on dilution with the polar solvents and decrease or remain constant on dilution with the nonpolar solvents. The CS2/benzene solutions show a contrasting behavior, with the CS2 nu1 dephasing rate being nearly independent of concentration whereas the benzene nu2 dephasing rate decreases on dilution. These results are compared to theoretical models for vibrational dephasing of polyatomic molecules in solution.

Near-infrared Raman spectroscopy to detect anti-Toxoplasma gondii antibodies in blood sera of domestic cats

NASA Astrophysics Data System (ADS)

Duarte, Janaina; Pacheco, Marcos T. T.; Silveira, Landulfo, Jr.; Machado, Rosangela Z.; Martins, Rodrigo A. L.; Zangaro, Renato A.; Villaverde, Antonio G. J. B.

2001-05-01

Near-infrared (NIR) Raman spectroscopy has been studied for the last years for many biomedical applications. It is a powerful tool for biological materials analysis. Toxoplasmosis is an important zoonosis in public health, cats being the principal responsible for the transmission of the disease in Brazil. The objective of this work is to investigate a new method of diagnosis of this disease. NIR Raman spectroscopy was used to detect anti Toxoplasma gondii antibodies in blood sera from domestic cats, without sample preparation. In all, six blood serum samples were used for this study. A previous serological test was done by the Indirect Immunoenzymatic Assay (ELISA) to permit a comparative study between both techniques and it showed that three serum samples were positive and the other three were negative to toxoplasmosis. Raman spectra were taken for all the samples and analyzed by using the principal components analysis (PCA). A diagnosis parameter was defined from the analysis of the second and third principal components of the Raman spectra. It was found that this parameter can detect the infection level of the animal. The results have indicated that NIR Raman spectroscopy, associated to the PCA can be a promising technique for serological analysis, such as toxoplasmosis, allowing a fast and sensitive method of diagnosis.

Method And System For Examining Biological Materials Using Low Power Cw Excitation Raman Spectroscopy.

DOEpatents

Alfano, Robert R.; Wang, Wubao

2000-11-21

A method and system for examining biological materials using low-power cw excitation Raman spectroscopy. In accordance with the teachings of the invention, a low-power continuous wave (cw) pump laser beam and a low-power cw Stokes (or anti-Stokes) probe laser beam simultaneously illuminate a biological material and traverse the biological material in collinearity. The pump beam, whose frequency is varied, is used to induce Raman emission from the biological material. The intensity of the probe beam, whose frequency is kept constant, is monitored as it leaves the biological material. When the difference between the pump and probe excitation frequencies is equal to a Raman vibrational mode frequency of the biological material, the weak probe signal becomes amplified by one or more orders of magnitude (typically up to about 10.sup.4 -10.sup.6) due to the Raman emission from the pump beam. In this manner, by monitoring the intensity of the probe beam emitted from the biological material as the pump beam is varied in frequency, one can obtain an excitation Raman spectrum for the biological material tested. The present invention may be applied to in the in vivo and/or in vitro diagnosis of diabetes, heart disease, hepatitis, cancers and other diseases by measuring the characteristic excitation Raman lines of blood glucose, cholesterol, serum glutamic oxalacetic transaminase (SGOT)/serum glutamic pyruvic tansaminase (SGPT), tissues and other corresponding Raman-active body constituents, respectively. For example, it may also be used to diagnose diseases associated with the concentration of Raman-active constituents in urine, lymph and saliva It may be used to identify cancer in the breast, cervix, uterus, ovaries and the like by measuring the fingerprint excitation Raman spectra of these tissues. It may also be used to reveal the growing of tumors or cancers by measuring the levels of nitric oxide in tissue.

Longitudinal in vivo coherent anti-Stokes Raman scattering imaging of demyelination and remyelination in injured spinal cord

NASA Astrophysics Data System (ADS)

Shi, Yunzhou; Zhang, Delong; Huff, Terry B.; Wang, Xiaofei; Shi, Riyi; Xu, Xiao-Ming; Cheng, Ji-Xin

2011-10-01

In vivo imaging of white matter is important for the mechanistic understanding of demyelination and evaluation of remyelination therapies. Although white matter can be visualized by a strong coherent anti-Stokes Raman scattering (CARS) signal from axonal myelin, in vivo repetitive CARS imaging of the spinal cord remains a challenge due to complexities induced by the laminectomy surgery. We present a careful experimental design that enabled longitudinal CARS imaging of de- and remyelination at single axon level in live rats. In vivo CARS imaging of secretory phospholipase A2 induced myelin vesiculation, macrophage uptake of myelin debris, and spontaneous remyelination by Schwann cells are sequentially monitored over a 3 week period. Longitudinal visualization of de- and remyelination at a single axon level provides a novel platform for rational design of therapies aimed at promoting myelin plasticity and repair.

Dual-Pump Coherent Anti-Stokes Raman Scattering Temperature and CO2 Concentration Measurements

NASA Technical Reports Server (NTRS)

Lucht, Robert P.; Velur-Natarajan, Viswanathan; Carter, Campbell D.; Grinstead, Keith D., Jr.; Gord, James R.; Danehy, Paul M.; Fiechtner, G. J.; Farrow, Roger L.

2003-01-01

Measurements of temperature and CO2 concentration using dual-pump coherent anti-Stokes Raman scattering, (CARS) are described. The measurements were performed in laboratory flames,in a room-temperature gas cell, and on an engine test stand at the U.S. Air Force Research Laboratory, Wright-Patterson Air Force Base. A modeless dye laser, a single-mode Nd:YAG laser, and an unintensified back-illuminated charge-coupled device digital camera were used for these measurements. The CARS measurements were performed on a single-laser-shot basis. The standard deviations of the temperatures and CO2 mole fractions determined from single-shot dual-pump CARS spectra in steady laminar propane/air flames were approximately 2 and 10% of the mean values of approximately 2000 K and 0.10, respectively. The precision and accuracy of single-shot temperature measurements obtained from the nitrogen part of the dual-pump CARS system were investigated in detail in near-adiabatic hydrogen/air/CO2 flames. The precision of the CARS temperature measurements was found to be comparable to the best results reported in the literature for conventional two-laser, single-pump CARS. The application of dual-pump CARS for single-shot measurements in a swirl-stabilized combustor fueled with JP-8 was also demonstrated.

Enhanced Control of Transient Raman Scattering Using Buffered Hydrogen in Hollow-Core Photonic Crystal Fibers

NASA Astrophysics Data System (ADS)

Hosseini, P.; Novoa, D.; Abdolvand, A.; Russell, P. St. J.

2017-12-01

Many reports on stimulated Raman scattering in mixtures of Raman-active and noble gases indicate that the addition of a dispersive buffer gas increases the phase mismatch to higher-order Stokes and anti-Stokes sidebands, resulting in a preferential conversion to the first few Stokes lines, accompanied by a significant reduction in the Raman gain due to collisions with gas molecules. Here we report that, provided the dispersion can be precisely controlled, the effective Raman gain in a gas-filled hollow-core photonic crystal fiber can actually be significantly enhanced when a buffer gas is added. This counterintuitive behavior occurs when the nonlinear coupling between the interacting fields is strong and can result in a performance similar to that of a pure Raman-active gas, but at a much lower total gas pressure, allowing competing effects such as Raman backscattering to be suppressed. We report high modal purity in all the emitted sidebands, along with anti-Stokes conversion efficiencies as high as 5% in the visible and 2% in the ultraviolet. This new class of gas-based waveguide device, which allows the nonlinear optical response to be beneficially pressure-tuned by the addition of buffer gases, may find important applications in laser science and spectroscopy.

Anti-Stokes resonant x-ray Raman scattering for atom specific and excited state selective dynamics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kunnus, Kristjan; Josefsson, Ida; Rajkovic, Ivan

Here, ultrafast electronic and structural dynamics of matter govern rate and selectivity of chemical reactions, as well as phase transitions and efficient switching in functional materials. Since x-rays determine electronic and structural properties with elemental, chemical, orbital and magnetic selectivity, short pulse x-ray sources have become central enablers of ultrafast science. Despite of these strengths, ultrafast x-rays have been poor at picking up excited state moieties from the unexcited ones. With time-resolved anti-Stokes resonant x-ray Raman scattering (AS-RXRS) performed at the LCLS, and ab initio theory we establish background free excited state selectivity in addition to the elemental, chemical, orbitalmore » and magnetic selectivity of x-rays. This unparalleled selectivity extracts low concentration excited state species along the pathway of photo induced ligand exchange of Fe(CO)5 in ethanol. Conceptually a full theoretical treatment of all accessible insights to excited state dynamics with AS-RXRS with transform-limited x-ray pulses is given—which will be covered experimentally by upcoming transform-limited x-ray sources.« less

Anti-Stokes resonant x-ray Raman scattering for atom specific and excited state selective dynamics

DOE PAGES

Kunnus, Kristjan; Josefsson, Ida; Rajkovic, Ivan; ...

2016-10-07

Here, ultrafast electronic and structural dynamics of matter govern rate and selectivity of chemical reactions, as well as phase transitions and efficient switching in functional materials. Since x-rays determine electronic and structural properties with elemental, chemical, orbital and magnetic selectivity, short pulse x-ray sources have become central enablers of ultrafast science. Despite of these strengths, ultrafast x-rays have been poor at picking up excited state moieties from the unexcited ones. With time-resolved anti-Stokes resonant x-ray Raman scattering (AS-RXRS) performed at the LCLS, and ab initio theory we establish background free excited state selectivity in addition to the elemental, chemical, orbitalmore » and magnetic selectivity of x-rays. This unparalleled selectivity extracts low concentration excited state species along the pathway of photo induced ligand exchange of Fe(CO)5 in ethanol. Conceptually a full theoretical treatment of all accessible insights to excited state dynamics with AS-RXRS with transform-limited x-ray pulses is given—which will be covered experimentally by upcoming transform-limited x-ray sources.« less

Impact of input field characteristics on vibrational femtosecond coherent anti-Stokes Raman scattering thermometry.

PubMed

Yang, Chao-Bo; He, Ping; Escofet-Martin, David; Peng, Jiang-Bo; Fan, Rong-Wei; Yu, Xin; Dunn-Rankin, Derek

2018-01-10

In this paper, three ultrashort-pulse coherent anti-Stokes Raman scattering (CARS) thermometry approaches are summarized with a theoretical time-domain model. The difference between the approaches can be attributed to variations in the input field characteristics of the time-domain model. That is, all three approaches of ultrashort-pulse (CARS) thermometry can be simulated with the unified model by only changing the input fields features. As a specific example, the hybrid femtosecond/picosecond CARS is assessed for its use in combustion flow diagnostics; thus, the examination of the input field has an impact on thermometry focuses on vibrational hybrid femtosecond/picosecond CARS. Beginning with the general model of ultrashort-pulse CARS, the spectra with different input field parameters are simulated. To analyze the temperature measurement error brought by the input field impacts, the spectra are fitted and compared to fits, with the model neglecting the influence introduced by the input fields. The results demonstrate that, however the input pulses are depicted, temperature errors still would be introduced during an experiment. With proper field characterization, however, the significance of the error can be reduced.

Combining deep learning and coherent anti-Stokes Raman scattering imaging for automated differential diagnosis of lung cancer

NASA Astrophysics Data System (ADS)

Weng, Sheng; Xu, Xiaoyun; Li, Jiasong; Wong, Stephen T. C.

2017-10-01

Lung cancer is the most prevalent type of cancer and the leading cause of cancer-related deaths worldwide. Coherent anti-Stokes Raman scattering (CARS) is capable of providing cellular-level images and resolving pathologically related features on human lung tissues. However, conventional means of analyzing CARS images requires extensive image processing, feature engineering, and human intervention. This study demonstrates the feasibility of applying a deep learning algorithm to automatically differentiate normal and cancerous lung tissue images acquired by CARS. We leverage the features learned by pretrained deep neural networks and retrain the model using CARS images as the input. We achieve 89.2% accuracy in classifying normal, small-cell carcinoma, adenocarcinoma, and squamous cell carcinoma lung images. This computational method is a step toward on-the-spot diagnosis of lung cancer and can be further strengthened by the efforts aimed at miniaturizing the CARS technique for fiber-based microendoscopic imaging.

Hybrid femtosecond/picosecond coherent anti-Stokes Raman scattering for gas-phase temperature measurements

NASA Astrophysics Data System (ADS)

Miller, Joseph Daniel

Hybrid femtosecond/picosecond coherent anti-Stokes Raman scattering (fs/ps CARS) is employed for quantitative gas-phase temperature measurements in combustion processes and heated flows. In this approach, ultrafast 100-fs laser pulses are used to induce vibrational and rotational transitions in N2 and O2, while a third spectrally narrowed picosecond pulse is used to probe the molecular response. Temporal suppression of the nonresonant contribution and elimination of collisional effects are achieved by delay of the probe pulse, while sufficient spectral resolution is maintained for frequency-domain detection and thermometry. A theoretical framework is developed to model experimental spectra by phenomenologically describing the temporal evolution of the vibrational and rotational wavepackets as a function of temperature and pressure. Interference-free, single-shot vibrational fs/ps CARS thermometry is demonstrated at 1-kHz from 1400-2400 K in a H2-air flame, with accuracy better than 3%. A time-asymmetric exponential pulse shape is introduced to optimize nonresonant suppression with a 103 reduction at a probe delay of 0.31 ps. Low-temperature single-shot thermometry (300-700 K) with better than 1.5% accuracy is demonstrated using a fully degenerate rotational fs/ps CARS scheme, and the influence of collision energy transfer on thermometry error is quantified at atmospheric pressure. Interference-free thermometry, without nonresonant contributions and collision-induced error, is demonstrated for the first time using rotational fs/ps CARS at room temperature and pressures from 1-15 atm. Finally, the temporal and spectral resolution of fs/ps CARS is exploited for transition-resolved time-domain measurements of N2 and O2 self-broadened S-branch Raman linewidths at pressures of 1-20 atm.

Microfluidic chip for non-invasive analysis of tumor cells interaction with anti-cancer drug doxorubicin by AFM and Raman spectroscopy.

PubMed

Zhang, Han; Xiao, Lifu; Li, Qifei; Qi, Xiaojun; Zhou, Anhong

2018-03-01

Raman spectroscopy has been playing an increasingly significant role for cell classification. Here, we introduce a novel microfluidic chip for non-invasive Raman cell natural fingerprint collection. Traditional Raman spectroscopy measurement of the cells grown in a Polydimethylsiloxane (PDMS) based microfluidic device suffers from the background noise from the substrate materials of PDMS when intended to apply as an in vitro cell assay. To overcome this disadvantage, the current device is designed with a middle layer of PDMS layer sandwiched by two MgF 2 slides which minimize the PDMS background signal in Raman measurement. Three cancer cell lines, including a human lung cancer cell A549, and human breast cancer cell lines MDA-MB-231 and MDA-MB-231/BRMS1, were cultured in this microdevice separately for a period of three days to evaluate the biocompatibility of the microfluidic system. In addition, atomic force microscopy (AFM) was used to measure the Young's modulus and adhesion force of cancer cells at single cell level. The AFM results indicated that our microchannel environment did not seem to alter the cell biomechanical properties. The biochemical responses of cancer cells exposed to anti-cancer drug doxorubicin (DOX) up to 24 h were assessed by Raman spectroscopy. Principal component analysis over the Raman spectra indicated that cancer cells untreated and treated with DOX can be distinguished. This PDMS microfluidic device offers a non-invasive and reusable tool for in vitro Raman measurement of living cells, and can be potentially applied for anti-cancer drug screening.

Novel Raman Techniques for Imaging and Sensing

NASA Astrophysics Data System (ADS)

Edwards, Perry S.

Raman scattering spectroscopy is extensively demonstrated as a label-free, chemically selective sensing and imaging technique for a multitude of chemical and biological applications. The ability to detect "fingerprint" spectral signatures of individual molecules, without the need to introduce chemical labelers, makes Raman scattering a powerful sensing technique. However, spectroscopy based on spontaneous Raman scattering traditionally suffers from inherently weak signals due to small Raman scattering cross-sections. Thus, considerable efforts have been put forth to find pathways towards enhancing Raman signals to bolster sensitivity for detecting small concentrations of molecules or particles. The development of coherent Raman techniques that can offer orders of magnitude increase in signal have garnered significant interest in recent years for their application in imaging; such techniques include coherent anti-Stokes Raman scattering and stimulated Raman scattering. Additionally, methods to enhance the local field of either the pump or generated Raman signal, such as through surface enhanced Raman scattering, have been investigated for their orders of magnitude improvement in sensitivity and single molecule sensing capability. The work presented in this dissertation describes novel techniques for performing high speed and highly sensitive Raman imaging as well as sensing applications towards bioimaging and biosensing. Coherent anti-Stokes Raman scattering (CARS) is combined with holography to enable recording of high-speed (single laser shot), wide field CARS holograms which can be used to reconstruct the both the amplitude and the phase of the anti-Stokes field therefore allowing 3D imaging. This dissertation explores CARS holography as a viable label-free bio-imaging technique. A Raman scattering particle sensing system is also developed that utilizes wave guide properties of optical fibers and ring-resonators to perform enhanced particle sensing. Resonator

Combining deep learning and coherent anti-Stokes Raman scattering imaging for automated differential diagnosis of lung cancer.

PubMed

Weng, Sheng; Xu, Xiaoyun; Li, Jiasong; Wong, Stephen T C

2017-10-01

Lung cancer is the most prevalent type of cancer and the leading cause of cancer-related deaths worldwide. Coherent anti-Stokes Raman scattering (CARS) is capable of providing cellular-level images and resolving pathologically related features on human lung tissues. However, conventional means of analyzing CARS images requires extensive image processing, feature engineering, and human intervention. This study demonstrates the feasibility of applying a deep learning algorithm to automatically differentiate normal and cancerous lung tissue images acquired by CARS. We leverage the features learned by pretrained deep neural networks and retrain the model using CARS images as the input. We achieve 89.2% accuracy in classifying normal, small-cell carcinoma, adenocarcinoma, and squamous cell carcinoma lung images. This computational method is a step toward on-the-spot diagnosis of lung cancer and can be further strengthened by the efforts aimed at miniaturizing the CARS technique for fiber-based microendoscopic imaging. (2017) COPYRIGHT Society of Photo-Optical Instrumentation Engineers (SPIE).

Mobile, Multi-modal, Label-Free Imaging Probe Analysis of Choroidal Oximetry and Retinal Hypoxia

DTIC Science & Technology

2016-10-01

Unlimited 13. SUPPLEMENTARY NOTES 14. ABSTRACT Coherent anti-stokes Raman spectroscopy ( CARS ) can be used to detect differences in the oxygen content...oxygen, eye, retina, photoreceptor, neuron, TRPM7, neurodegeneration, neurotoxicity, coherent anti-Stokes Raman spectroscopy, CARS , mouse 16...ANSI Std. Z39.18 Section 1: Introduction The study is based on the premise that Coherent Anti-Stokes Raman scattering ( CARS ) imaging provides a

Paranodal myelin retraction in relapsing experimental autoimmune encephalomyelitis visualized by coherent anti-Stokes Raman scattering microscopy

NASA Astrophysics Data System (ADS)

Fu, Yan; Frederick, Terra J.; Huff, Terry B.; Goings, Gwendolyn E.; Miller, Stephen D.; Cheng, Ji-Xin

2011-10-01

How demyelination is initiated is a standing question for pathology of multiple sclerosis. By label-free coherent anti-Stokes Raman scattering (CARS) imaging of myelin lipids, we investigate myelin integrity in the lumbar spinal cord tissue isolated from naïve SJL mice, and from mice at the onset, peak acute, and remission stages of relapsing experimental autoimmune encephalomyelitis (EAE). Progressive demyelinating disease is initially characterized by the retraction of paranodal myelin both at the onset of disease and at the borders of acute demyelinating lesions. Myelin retraction is confirmed by elongated distribution of neurofascin proteins visualized by immunofluorescence. The disruption of paranodal myelin subsequently exposes Kv1.2 channels at the juxtaparanodes and lead to the displacement of Kv1.2 channels to the paranodal and nodal domains. Paranodal myelin is partially restored during disease remission, indicating spontaneous myelin regeneration. These findings suggest that paranodal domain injury precedes formation of internodal demyelinating lesions in relapsing EAE. Our results also demonstrate that CARS microscopy is an effective readout of myelin disease burden.

Evans blue dye-enhanced imaging of the brain microvessels using spectral focusing coherent anti-Stokes Raman scattering microscopy

PubMed Central

Lee, Bo-Ram; Joo, Kyung-Il; Choi, Eun Sook; Jahng, Junghoon; Kim, Hyunmin

2017-01-01

We performed dye-enhanced imaging of mouse brain microvessels using spectral focusing coherent anti-Stokes Raman scattering (SF-CARS) microscopy. The resonant signals from C-H stretching in forward CARS usually show high background intensity in tissues, which makes CARS imaging of microvessels difficult. In this study, epi-detection of back-scattered SF-CARS signals showed a negligible background, but the overall intensity of resonant CARS signals was too low to observe the network of brain microvessels. Therefore, Evans blue (EB) dye was used as contrasting agent to enhance the back-scattered SF-CARS signals. Breakdown of brain microvessels by inducing hemorrhage in a mouse was clearly visualized using backward SF-CARS signals, following intravenous injection of EB. The improved visualization of brain microvessels with EB enhanced the sensitivity of SF-CARS, detecting not only the blood vessels themselves but their integrity as well in the brain vasculature. PMID:29049299

Measurement of the surface-enhanced coherent anti-Stokes Raman scattering (SECARS) due to the 1574 cm(-1) surface-enhanced Raman scattering (SERS) mode of benzenethiol using low-power (<20 mW) CW diode lasers.

PubMed

Aggarwal, Roshan L; Farrar, Lewis W; Greeneltch, Nathan G; Van Duyne, Richard P; Polla, Dennis L

2013-02-01

The surface-enhanced coherent anti-Stokes Raman scattering (SECARS) from a self-assembled monolayer (SAM) of benzenethiol on a silver-coated surface-enhanced Raman scattering (SERS) substrate has been measured for the 1574 cm(-1) SERS mode. A value of 9.6 ± 1.7×10(-14) W was determined for the resonant component of the SECARS signal using 17.8 mW of 784.9 nm pump laser power and 7.1 mW of 895.5 nm Stokes laser power; the pump and Stokes lasers were polarized parallel to each other but perpendicular to the grooves of the diffraction grating in the spectrometer. The measured value of resonant component of the SECARS signal is in agreement with the calculated value of 9.3×10(-14) W using the measured value of 8.7 ± 0.5 cm(-1) for the SERS linewidth Γ (full width at half-maximum) and the value of 5.7 ± 1.4×10(-7) for the product of the Raman cross section σSERS and the surface concentration Ns of the benzenethiol SAM. The xxxx component of the resonant part of the third-order nonlinear optical susceptibility |3 χxxxx((3)R)| for the 1574 cm(-1) SERS mode has been determined to be 4.3 ± 1.1×10(-5) cm·g(-1)·s(2). The SERS enhancement factor for the 1574 cm(-1) mode was determined to be 3.6 ± 0.9×10(7) using the value of 1.8×10(15) molecules/cm(2) for Ns.

Coherent Raman Studies of Shocked Liquids

NASA Astrophysics Data System (ADS)

McGrane, Shawn; Brown, Kathryn; Dang, Nhan; Bolme, Cynthia; Moore, David

2013-06-01

Transient vibrational spectroscopies offer the potential to directly observe time dependent shock induced chemical reaction kinetics. We report recent experiments that couple a hybrid picosecond/femtosecond coherent anti-Stokes Raman spectroscopy (CARS) diagnostic with our tabletop ultrafast laser driven shock platform. Initial results on liquids shocked to 20 GPa suggest that sub-picosecond dephasing at high pressure and temperature may limit the application of this nonresonant background free version of CARS. Initial results using interferometric CARS to increase sensitivity and overcome these limitations will be presented.

Ultra high resolution molecular beam cars spectroscopy with application to planetary atmospheric molecules

NASA Technical Reports Server (NTRS)

Byer, R. L.

1982-01-01

The measurement of high resolution pulsed and continuous wave (CW) coherent anti-Stokes Raman spectroscopy (CARS) measurements in pulsed and steady state supersonic expansions were demonstrated. Pulsed molecular beam sources were characterized, and saturation of a Raman transition and, for the first time, the Raman spectrum of a complex molecular cluster were observed. The observation of CW CARS spectra in a molecular expansion and the effects of transit time broadening is described. Supersonic expansion is established as a viable technique for high resolution Raman spectroscopy of cold molecules with resolutions of 100 MH2.

Raman Spectroscopy.

ERIC Educational Resources Information Center

Gerrard, Donald L.

1984-01-01

Reviews literature on Raman spectroscopy from late 1981 to late 1983. Topic areas include: instrumentation and sampling; liquids and solutions; gases and matrix isolation; biological molecules; polymers; high-temperature and high-pressure studies; Raman microscopy; thin films and surfaces; resonance-enhanced and surface-enhanced spectroscopy; and…

Polarization Sensitive Coherent Raman Measurements of DCVJ

NASA Astrophysics Data System (ADS)

Anderson, Josiah; Cooper, Nathan; Lawhead, Carlos; Shiver, Tegan; Ujj, Laszlo

2014-03-01

Coherent Raman spectroscopy which recently developed into coherent Raman microscopy has been used to produce label free imaging of thin layers of material and find the spatial distributions of certain chemicals within samples, e.g. cancer cells.(1) Not all aspects of coherent scattering have been used for imaging. Among those for example are special polarization sensitive measurements. Therefore we have investigated the properties of polarization sensitive CARS spectra of a highly fluorescent molecule, DCVJ.(2) Spectra has been recorded by using parallel polarized and perpendicular polarized excitations. A special polarization arrangement was developed to suppress the non-resonant background scattering from the sample. These results can be used to improve the imaging properties of a coherent Raman microscope in the future. This is the first time coherent Raman polarization sensitive measurements have been used to characterize the vibrational modes of DCVJ. 1: K. I. Gutkowski, et al., ``Fluorescence of dicyanovinyl julolidine in a room temperature ionic liquid '' Chemical Physics Letters 426 (2006) 329 - 333 2: Fouad El-Diasty, ``Coherent anti-Stokes Raman scattering: Spectroscopy and microscopy'' Vibrational Spectroscopy 55 (2011) 1-37

Developing single-laser sources for multimodal coherent anti-Stokes Raman scattering microscopy

NASA Astrophysics Data System (ADS)

Pegoraro, Adrian Frank

Coherent anti-Stokes Raman scattering (CARS) microscopy has developed rapidly and is opening the door to new types of experiments. This work describes the development of new laser sources for CARS microscopy and their use for different applications. It is specifically focused on multimodal nonlinear optical microscopy—the simultaneous combination of different imaging techniques. This allows us to address a diverse range of applications, such as the study of biomaterials, fluid inclusions, atherosclerosis, hepatitis C infection in cells, and ice formation in cells. For these applications new laser sources are developed that allow for practical multimodal imaging. For example, it is shown that using a single Ti:sapphire oscillator with a photonic crystal fiber, it is possible to develop a versatile multimodal imaging system using optimally chirped laser pulses. This system can perform simultaneous two photon excited fluorescence, second harmonic generation, and CARS microscopy. The versatility of the system is further demonstrated by showing that it is possible to probe different Raman modes using CARS microscopy simply by changing a time delay between the excitation beams. Using optimally chirped pulses also enables further simplification of the laser system required by using a single fiber laser combined with nonlinear optical fibers to perform effective multimodal imaging. While these sources are useful for practical multimodal imaging, it is believed that for further improvements in CARS microscopy sensitivity, new excitation schemes are necessary. This has led to the design of a new, high power, extended cavity oscillator that should be capable of implementing new excitation schemes for CARS microscopy as well as other techniques. Our interest in multimodal imaging has led us to other areas of research as well. For example, a fiber-coupling scheme for signal collection in the forward direction is demonstrated that allows for fluorescence lifetime imaging

Method and system to measure temperature of gases using coherent anti-stokes doppler spectroscopy

DOEpatents

Rhodes, Mark

2013-12-17

A method of measuring a temperature of a noble gas in a chamber includes providing the noble gas in the chamber. The noble gas is characterized by a pressure and a temperature. The method also includes directing a first laser beam into the chamber and directing a second laser beam into the chamber. The first laser beam is characterized by a first frequency and the second laser beam is characterized by a second frequency. The method further includes converting at least a portion of the first laser beam and the second laser beam into a coherent anti-Stokes beam, measuring a Doppler broadening of the coherent anti-Stokes beam, and computing the temperature using the Doppler broadening.

Coherent anti-stokes Raman scattering (CARS) microscopy: a novel technique for imaging the retina.

PubMed

Masihzadeh, Omid; Ammar, David A; Kahook, Malik Y; Lei, Tim C

2013-05-01

To image the cellular and noncellular structures of the retina in an intact mouse eye without the application of exogenous fluorescent labels using noninvasive, nondestructive techniques. Freshly enucleated mouse eyes were imaged using two nonlinear optical techniques: coherent anti-Stokes Raman scattering (CARS) and two-photon autofluorescence (TPAF). Cross sectional transverse sections and sequential flat (en face) sagittal sections were collected from a region of sclera approximately midway between the limbus and optic nerve. Imaging proceeded from the surface of the sclera to a depth of ∼60 μm. The fluorescent signal from collagen fibers within the sclera was evident in the TPAF channel; the scleral collagen fibers showed no organization and appeared randomly packed. The sclera contained regions lacking TPAF and CARS fluorescence of ∼3 to 15 μm in diameter that could represent small vessels or scleral fibroblasts. Intense punctate CARS signals from the retinal pigment epithelial layer were of a size and shape of retinyl storage esters. Rod outer segments could be identified by the CARS signal from their lipid-rich plasma membranes. CARS microscopy can be used to image the outer regions of the mammalian retina without the use of a fluorescent dye or exogenously expressed recombinant protein. With technical advancements, CARS/TPAF may represent a new avenue for noninvasively imaging the retina and might complement modalities currently used in clinical practice.

Remote detection of chem/bio hazards via coherent anti-Stokes Raman spectroscopy

DTIC Science & Technology

2017-09-12

hour per response, including the time for reviewing lnstnJctions, searching existing data sources, gathering and maintaining the data needed, and... time remote detection of hazardous microparticles in atmosphere and to evaluate the range of distances for typical species and the parameters of laser...detectable photons from a prototype molecule at a distance. 1S. SUBJECT TERMS Stimulated Raman scattering, Remote detection, biochemical agents, explosives

Diagnostic Imaging in Flames with Instantaneous Planar Coherent Raman Spectroscopy.

PubMed

Bohlin, A; Kliewer, C J

2014-04-03

Spatial mapping of temperature and molecular species concentrations is vitally important in studies of gaseous chemically reacting flows. Temperature marks the evolution of heat release and energy transfer, while species concentration gradients provide critical information on mixing and chemical reaction. Coherent anti-Stokes Raman spectroscopy (CARS) was pioneered in measurements of such processes almost 40 years ago and is authoritative in terms of the accuracy and precision it may provide. While a reacting flow is fully characterized in three-dimensional space, a limitation of CARS has been its applicability as a point-wise measurement technique, motivating advancement toward CARS imaging, and attempts have been made considering one-dimensional probing. Here, we report development of two-dimensional CARS, with the first diagnostics of a planar field in a combusting flow within a single laser pulse, resulting in measured isotherms ranging from 450 K up to typical hydrocarbon flame temperatures of about 2000 K with chemical mapping of O2 and N2.

Low-threshold collinear parametric Raman comb generation in calcite under 532 and 1064 nm picosecond laser pumping

NASA Astrophysics Data System (ADS)

Smetanin, S. N.; Jelínek, M., Jr.; Kubeček, V.; Jelínková, H.

2015-09-01

Optimal conditions of low-threshold collinear parametric Raman comb generation in calcite (CaCO3) are experimentally investigated under 20 ps laser pulse excitation, in agreement with the theoretical study. The collinear parametric Raman generation of the highest number of Raman components in the short calcite crystals corresponding to the optimal condition of Stokes-anti-Stokes coupling was achieved. At the excitation wavelength of 1064 nm, using the optimum-length crystal resulted in the effective multi-octave frequency Raman comb generation containing up to five anti-Stokes and more than four Stokes components (from 674 nm to 1978 nm). The 532 nm pumping resulted in the frequency Raman comb generation from the 477 nm 2nd anti-Stokes up to the 692 nm 4th Stokes component. Using the crystal with a non-optimal length leads to the Stokes components generation only with higher thresholds because of the cascade-like stimulated Raman scattering with suppressed parametric coupling.

Improving sensitivity and source attribution of homemade explosives with low-frequency/THz-Raman spectroscopy

NASA Astrophysics Data System (ADS)

Carriere, James T. A.; Havermeyer, Frank; Heyler, Randy A.

2014-05-01

Rapid identification and source attribution of homemade explosives (HMEs) is vital to national defense and homeland security efforts. Since HMEs can be prepared in a variety of methods with different component ingredients, telltale traces can be left behind in the final structural form of the material. These differences manifest as polymorphs, isomers, conformers or even contaminants that can all impact the low energy vibrational modes of the molecule. Conventional Raman spectroscopy systems confine their measurements to the "chemical fingerprint" region and are unable to detect low frequency Raman signals (<200cm-1) where these low energy modes are found. This gap in sensitivity limits the conclusions that can be drawn from a single Raman measurement and creates the need for multiple measurement techniques to confirm any results. We present results from a new rugged, portable approach that is capable of extending the range of Raman to include these low frequency signals down to ~5cm-1, plus complementary anti-Stokes spectra, with measurement times on the order of seconds. We demonstrate the diversity of signals that lie in this region that directly correlate to the molecular structure of the material, resulting in a new Raman "structural fingerprint" region. By correlating the measured results with known samples from a spectral library, rapid identification of the specific method of manufacture can be made.

Raman spectroscopy

USDA-ARS?s Scientific Manuscript database

Raman spectroscopy has gained increased use and importance in recent years for accurate and precise detection of physical and chemical properties of food materials, due to the greater specificity and sensitivity of Raman techniques over other analytical techniques. This book chapter presents Raman s...

Coronagraphic Notch Filter for Raman Spectroscopy

NASA Technical Reports Server (NTRS)

Cohen, David; Stirbl, Robert

2004-01-01

A modified coronagraph has been proposed as a prototype of improved notch filters in Raman spectrometers. Coronagraphic notch filters could offer alternatives to both (1) the large and expensive double or triple monochromators in older Raman spectrometers and (2) holographic notch filters, which are less expensive but are subject to environmental degradation as well as to limitations of geometry and spectral range. Measurement of a Raman spectrum is an exercise in measuring and resolving faint spectral lines close to a bright peak: In Raman spectroscopy, a monochromatic beam of light (the pump beam) excites a sample of material that one seeks to analyze. The pump beam generates a small flux of scattered light at wavelengths slightly greater than that of the pump beam. The shift in wavelength of the scattered light from the pump wavelength is known in the art as the Stokes shift. Typically, the flux of scattered light is of the order of 10 7 that of the pump beam and the Stokes shift lies in the wave-number range of 100 to 3,000 cm 1. A notch filter can be used to suppress the pump-beam spectral peak while passing the nearby faint Raman spectral lines. The basic principles of design and operation of a coronagraph offer an opportunity for engineering the spectral transmittance of the optics in a Raman spectrometer. A classical coronagraph may be understood as two imaging systems placed end to end, such that the first system forms an intermediate real image of a nominally infinitely distant object and the second system forms a final real image of the intermediate real image. If the light incident on the first telescope is collimated, then the intermediate image is a point-spread function (PSF). If an appropriately tailored occulting spot (e.g., a Gaussian-apodized spot with maximum absorption on axis) is placed on the intermediate image plane, then the instrument inhibits transmission of light from an on-axis source. However, the PSFs of off-axis light sources are

Raman spectroscopy for cancer detection and characterization in metastasis models

NASA Astrophysics Data System (ADS)

Koga, Shigehiro; Oshima, Yusuke; Sato, Mitsunori; Ishimaru, Kei; Yoshida, Motohira; Yamamoto, Yuji; Matsuno, Yusuke; Watanabe, Yuji

2017-02-01

Raman spectroscopy provides a wealth of diagnostic information to the surgeon with in situ cancer detection and label-free histopathology in clinical practice. Raman spectroscopy is a developing optical technique which can analyze biological tissues with light scattering. The difference in frequencies between the incident light and the scattering light are called Raman shifts, which correspond to the vibrational energy of the molecular bonds. Raman spectrum gives information about the molecular structure and composition in biological specimens. We had been previously reported that Raman spectroscopy could distinguish various histological types of human lung cancer cells from normal cells in vitro. However, to identify and detect cancer diagnostic biomarkers in vivo on Raman spectroscopy is still challenging, because malignancy can be characterized not only by the cancer cells but also by the environmental factors including immune cells, stroma cells, secretion vesicles and extracellular matrix. Here we investigate morphological and molecular dynamics in both cancer cells and their environment in xenograft models and spontaneous metastasis models using Raman spectroscopy combined with fluorescence microscopy and photoluminescence imaging. We are also constructing a custom-designed Raman spectral imaging system for both in vitro and in vivo assay of tumor tissues to reveal the metastasis process and to evaluate therapeutic effects of anti-cancer drugs and their drug delivery toward the clinical application of the technique.

Development of high-resolution n(2) coherent anti-stokes Raman scattering for measuring pressure, temperature, and density in high-speed gas flows.

PubMed

Woodmansee, M A; Lucht, R P; Dutton, J C

2000-11-20

Mean and instantaneous measurements of pressure, temperature, and density have been acquired in an optically accessible gas cell and in the flow field of an underexpanded sonic jet by use of the high-resolution N(2) coherent anti-Stokes Raman scattering (CARS) technique. This nonintrusive method resolves the pressure- and temperature-sensitive rotational transitions of the nu = 0 ? 1 N(2) Q-branch to within Domega = 0.10 cm(-1). To extract thermodynamic information from the experimental spectra, theoretical spectra, generated by a N(2) spectral modeling program, are fit to the experimental spectra in a least-squares manner. In the gas cell, the CARS-measured pressures compare favorably with transducer-measured pressures. The precision and accuracy of the single-shot CARS pressure measurements increase at subatmospheric conditions. Along the centerline of the underexpanded jet, the agreement between the mean CARS P/T/rho measurements and similar quantities extracted from a Reynolds-averaged Navier-Stokes computational fluid dynamic simulation is generally excellent. This CARS technique is able to capture the low-pressure and low-temperature conditions of the M = 3.4 flow entering the Mach disk, as well as the subsonic conditions immediately downstream of this normal shock.

Coherent Anti-Stokes Raman Scattering (CARS) Microscopy: A Novel Technique for Imaging the Retina

PubMed Central

Masihzadeh, Omid; Ammar, David A.; Kahook, Malik Y.; Lei, Tim C.

2013-01-01

Purpose. To image the cellular and noncellular structures of the retina in an intact mouse eye without the application of exogenous fluorescent labels using noninvasive, nondestructive techniques. Methods. Freshly enucleated mouse eyes were imaged using two nonlinear optical techniques: coherent anti-Stokes Raman scattering (CARS) and two-photon autofluorescence (TPAF). Cross sectional transverse sections and sequential flat (en face) sagittal sections were collected from a region of sclera approximately midway between the limbus and optic nerve. Imaging proceeded from the surface of the sclera to a depth of ∼60 μm. Results. The fluorescent signal from collagen fibers within the sclera was evident in the TPAF channel; the scleral collagen fibers showed no organization and appeared randomly packed. The sclera contained regions lacking TPAF and CARS fluorescence of ∼3 to 15 μm in diameter that could represent small vessels or scleral fibroblasts. Intense punctate CARS signals from the retinal pigment epithelial layer were of a size and shape of retinyl storage esters. Rod outer segments could be identified by the CARS signal from their lipid-rich plasma membranes. Conclusions. CARS microscopy can be used to image the outer regions of the mammalian retina without the use of a fluorescent dye or exogenously expressed recombinant protein. With technical advancements, CARS/TPAF may represent a new avenue for noninvasively imaging the retina and might complement modalities currently used in clinical practice. PMID:23580484

Coherent anti-Stokes Raman scattering microscopy driving the future of loaded mesoporous silica imaging.

PubMed

Fussell, Andrew L; Mah, Pei Ting; Offerhaus, Herman; Niemi, Sanna-Mari; Salonen, Jarno; Santos, Hélder A; Strachan, Clare

2014-11-01

This study reports the use of variants of coherent anti-Stokes Raman scattering (CARS) microscopy as a novel method for improved physicochemical characterization of drug-loaded silica particles. Ordered mesoporous silica is a biomaterial that can be loaded to carry a number of biochemicals, including poorly water-soluble drugs, by allowing the incorporation of drug into nanometer-sized pores. In this work, the loading of two poorly water-soluble model drugs, itraconazole and griseofulvin, in MCM-41 silica microparticles is characterized qualitatively, using the novel approach of CARS microscopy, which has advantages over other analytical approaches used to date and is non-destructive, rapid, label free, confocal and has chemical and physical specificity. The study investigated the effect of two solvent-based loading methods, namely immersion and rotary evaporation, and microparticle size on the three-dimensional (3-D) distribution of the two loaded drugs. Additionally, hyperspectral CARS microscopy was used to confirm the amorphous nature of the loaded drugs. Z-stacked CARS microscopy suggested that the drug, but not the loading method or particle size range, affected 3-D drug distribution. Hyperspectral CARS confirmed that the drug loaded in the MCM-41 silica microparticles was in an amorphous form. The results show that CARS microscopy and hyperspectral CARS microscopy can be used to provide further insights into the structural nature of loaded mesoporous silica microparticles as biomaterials. Copyright © 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Measuring Rocket Engine Temperatures with Hydrogen Raman Spectroscopy

NASA Technical Reports Server (NTRS)

Wehrmeyer, Joseph A.; Osborne, Robin J.; Trinh, Huu P.; Turner, James (Technical Monitor)

2001-01-01

Optically accessible, high pressure, hot fire test articles are available at NASA Marshall for use in development of advanced rocket engine propellant injectors. Single laser-pulse ultraviolet (UV) Raman spectroscopy has been used in the past in these devices for analysis of high pressure H2- and CH4-fueled combustion, but relies on an independent pressure measurement in order to provide temperature information. A variation of UV Raman (High Resolution Hydrogen Raman Spectroscopy) is under development and will allow temperature measurement without the need for an independent pressure measurement, useful for flows where local pressure may not be accurately known. The technique involves the use of a spectrometer with good spectral resolution, requiring a small entrance slit for the spectrometer. The H2 Raman spectrum, when created by a narrow linewidth laser source and obtained from a good spectral resolution spectrograph, has a spectral shape related to temperature. By best-fit matching an experimental spectrum to theoretical spectra at various temperatures, a temperature measurement is obtained. The spectral model accounts for collisional narrowing, collisional broadening, Doppler broadening, and collisional line shifting of each Raman line making up the H2 Stokes vibrational Q-branch spectrum. At pressures from atmospheric up to those associated with advanced preburner components (5500 psia), collisional broadening though present does not cause significant overlap of the Raman lines, allowing high resolution H2 Raman to be used for temperature measurements in plumes and in high pressure test articles. Experimental demonstrations of the technique are performed for rich H2-air flames at atmospheric pressure and for high pressure, 300 K H2-He mixtures. Spectrometer imaging quality is identified as being critical for successful implementation of technique.

In planta imaging of Δ9-tetrahydrocannabinolic acid in Cannabis sativa L. with hyperspectral coherent anti-Stokes Raman scattering microscopy

NASA Astrophysics Data System (ADS)

Garbacik, Erik T.; Korai, Roza P.; Frater, Eric H.; Korterik, Jeroen P.; Otto, Cees; Offerhaus, Herman L.

2013-04-01

Nature has developed many pathways to produce medicinal products of extraordinary potency and specificity with significantly higher efficiencies than current synthetic methods can achieve. Identification of these mechanisms and their precise locations within plants could substantially increase the yield of a number of natural pharmaceutics. We report label-free imaging of Δ9-tetrahydrocannabinolic acid (THCa) in Cannabis sativa L. using coherent anti-Stokes Raman scattering microscopy. In line with previous observations we find high concentrations of THCa in pistillate flowering bodies and relatively low amounts within flowering bracts. Surprisingly, we find differences in the local morphologies of the THCa-containing bodies: organelles within bracts are large, diffuse, and spheroidal, whereas in pistillate flowers they are generally compact, dense, and have heterogeneous structures. We have also identified two distinct vibrational signatures associated with THCa, both in pure crystalline form and within Cannabis plants; at present the exact natures of these spectra remain an open question.

In planta imaging of Δ⁹-tetrahydrocannabinolic acid in Cannabis sativa L. with hyperspectral coherent anti-Stokes Raman scattering microscopy.

PubMed

Garbacik, Erik T; Korai, Roza P; Frater, Eric H; Korterik, Jeroen P; Otto, Cees; Offerhaus, Herman L

2013-04-01

Nature has developed many pathways to produce medicinal products of extraordinary potency and specificity with significantly higher efficiencies than current synthetic methods can achieve. Identification of these mechanisms and their precise locations within plants could substantially increase the yield of a number of natural pharmaceutics. We report label-free imaging of Δ⁹-tetrahydrocannabinolic acid (THCa) in Cannabis sativa L. using coherent anti-Stokes Raman scattering microscopy. In line with previous observations we find high concentrations of THCa in pistillate flowering bodies and relatively low amounts within flowering bracts. Surprisingly, we find differences in the local morphologies of the THCa-containing bodies: organelles within bracts are large, diffuse, and spheroidal, whereas in pistillate flowers they are generally compact, dense, and have heterogeneous structures. We have also identified two distinct vibrational signatures associated with THCa, both in pure crystalline form and within Cannabis plants; at present the exact natures of these spectra remain an open question.

Optical Spectroscopy for Noninvasive Monitoring of Stem Cell Differentiation

PubMed Central

Downes, Andrew; Mouras, Rabah; Elfick, Alistair

2010-01-01

There is a requirement for a noninvasive technique to monitor stem cell differentiation. Several candidates based on optical spectroscopy are discussed in this review: Fourier transform infrared (FTIR) spectroscopy, Raman spectroscopy, and coherent anti-Stokes Raman scattering (CARS) microscopy. These techniques are briefly described, and the ability of each to distinguish undifferentiated from differentiated cells is discussed. FTIR spectroscopy has demonstrated its ability to distinguish between stem cells and their derivatives. Raman spectroscopy shows a clear reduction in DNA and RNA concentrations during embryonic stem cell differentiation (agreeing with the well-known reduction in the nucleus to cytoplasm ratio) and also shows clear increases in mineral content during differentiation of mesenchymal stem cells. CARS microscopy can map these DNA, RNA, and mineral concentrations at high speed, and Mutliplex CARS spectroscopy/microscopy is highlighted as the technique with most promise for future applications. PMID:20182537

In vivo lipid saturation study of C. elegans using quantitative broadband coherent anti-Stokes Raman imaging (Conference Presentation)

NASA Astrophysics Data System (ADS)

Littleton, Bradley; Kavanagh, Thomas; Nie, Yu; Abbate, Vincenzo; Hylands, Peter; Sturzenbaum, Stephen; Richards, David

2016-03-01

In vivo lipid saturation maps of microscopic nematodes (Caenorhabditis elegans) have been produced using our novel Spectral Interferometric Polarisation Coherent anti-Stokes Raman Scattering (SIP-CARS) imaging technique. This technique employs simple passive polarisation optics and a balanced homodyne detection scheme to exploit symmetries in the CARS polarisation response resulting in the complete cancellation of the non-resonant background (NRB) and real component of the CARS signal (with no prior or post assumptions as regards to their form). The remaining imaginary component of the CARS response is linear with analyte concentration and directly relatable to the spontaneous Raman spectrum [1]. Furthermore, the resonant CARS signal is interferometrically amplified by the non-resonant response, a necessity for rapid imaging at biologically relevant powers [2]. This technique permits acquisition of a broad NRB-free spectrum, in excess of 1800cm-1, in a single exposure at each pixel. This allows simultaneous determination of lipid droplet saturation, from the fingerprint region, and lipid order, from the C-H stretch region from which maps can be readily constructed. Additionally exploiting the dispersive nature of our signal collection two-photon autofluorescence can be isolated and images subsequently produced. We have successfully applied this technique to identify differences in lipid saturation distributions in selective C. elegans mutants and demonstrated that the technique is sufficiently sensitive to detect the effects of lipid metabolism altering drugs on wild type C. elegans. [1] Littleton et al, Phys Rev Lett, 111, 103902 (2013) [2] Parekh et al, Biophys J, 99, 2695-2704 (2010)

Application of Raman spectroscopy in type 2 diabetes screening in blood using leucine and isoleucine amino-acids as biomarkers and in comparative anti-diabetic drugs efficacy studies.

PubMed

Birech, Zephania; Mwangi, Peter Waweru; Bukachi, Fredrick; Mandela, Keith Makori

2017-01-01

Diabetes is an irreversible condition characterized by elevated blood glucose levels. Currently, there are no predictive biomarkers for this disease and the existing ones such as hemoglobin A1c and fasting blood glucose are used only when diabetes symptoms are noticed. The objective of this work was first to explore the potential of leucine and isoleucine amino acids as diabetes type 2 biomarkers using their Raman spectroscopic signatures. Secondly, we wanted to explore whether Raman spectroscopy can be applied in comparative efficacy studies between commercially available anti-diabetic drug pioglitazone and the locally used anti-diabetic herbal extract Momordica spinosa (Gilg.)Chiov. Sprague Dawley (SD) rat's blood was used and were pipetted onto Raman substrates prepared from conductive silver paste smeared glass slides. Prominent Raman bands associated with glucose (926, 1302, 1125 cm-1), leucine (1106, 1248, 1302, 1395 cm-1) and isolecucine (1108, 1248, 1437 and 1585 cm-1) were observed. The Raman bands centered at 1125 cm-1, 1395 cm-1 and 1437 cm-1 associated respectively to glucose, leucine and isoleucine were chosen as biomarker Raman peaks for diabetes type 2. These Raman bands displayed decreased intensities in blood from diabetic SD rats administered antidiabetic drugs pioglitazone and herbal extract Momordica spinosa (Gilg.)Chiov. The intensity decrease indicated reduced concentration levels of the respective biomarker molecules: glucose (1125 cm-1), leucine (1395 cm-1) and isoleucine (1437 cm-1) in blood. The results displayed the power and potential of Raman spectroscopy in rapid (10 seconds) diabetes and pre-diabetes screening in blood (human or rat's) with not only glucose acting as a biomarker but also leucine and isoleucine amino-acids where intensities of respectively assigned bands act as references. It also showed that using Raman spectroscopic signatures of the chosen biomarkers, the method can be an alternative for performing comparative

Application of Raman spectroscopy in type 2 diabetes screening in blood using leucine and isoleucine amino-acids as biomarkers and in comparative anti-diabetic drugs efficacy studies

PubMed Central

Mwangi, Peter Waweru; Bukachi, Fredrick; Mandela, Keith Makori

2017-01-01

Diabetes is an irreversible condition characterized by elevated blood glucose levels. Currently, there are no predictive biomarkers for this disease and the existing ones such as hemoglobin A1c and fasting blood glucose are used only when diabetes symptoms are noticed. The objective of this work was first to explore the potential of leucine and isoleucine amino acids as diabetes type 2 biomarkers using their Raman spectroscopic signatures. Secondly, we wanted to explore whether Raman spectroscopy can be applied in comparative efficacy studies between commercially available anti-diabetic drug pioglitazone and the locally used anti-diabetic herbal extract Momordica spinosa (Gilg.)Chiov. Sprague Dawley (SD) rat’s blood was used and were pipetted onto Raman substrates prepared from conductive silver paste smeared glass slides. Prominent Raman bands associated with glucose (926, 1302, 1125 cm−1), leucine (1106, 1248, 1302, 1395 cm−1) and isolecucine (1108, 1248, 1437 and 1585 cm−1) were observed. The Raman bands centered at 1125 cm−1, 1395 cm−1 and 1437 cm−1 associated respectively to glucose, leucine and isoleucine were chosen as biomarker Raman peaks for diabetes type 2. These Raman bands displayed decreased intensities in blood from diabetic SD rats administered antidiabetic drugs pioglitazone and herbal extract Momordica spinosa (Gilg.)Chiov. The intensity decrease indicated reduced concentration levels of the respective biomarker molecules: glucose (1125 cm−1), leucine (1395 cm−1) and isoleucine (1437 cm−1) in blood. The results displayed the power and potential of Raman spectroscopy in rapid (10 seconds) diabetes and pre-diabetes screening in blood (human or rat’s) with not only glucose acting as a biomarker but also leucine and isoleucine amino-acids where intensities of respectively assigned bands act as references. It also showed that using Raman spectroscopic signatures of the chosen biomarkers, the method can be an alternative for

Anti-Stokes Luminescence in High Quality Quantum Wells

NASA Astrophysics Data System (ADS)

Vinattieri, A.; Bogani, F.; Miotto, A.; Ceccherini, S.

1997-11-01

We present a detailed investigation of the anti-Stokes (AS) luminescence which originates from exciton recombination when below gap excitation is used, in a set of high quality quantum well structures. We observe strong excitonic resonances in the AS signal as measured from photoluminescence and photoluminescence excitation spectra. We demonstrate that neither the electromagnetic coupling between the wells nor the morphological disorder can explain this up-conversion effect. Time-resolved luminescence data after ps excitation and fs correlation spectroscopy results provide clear evidence of the occurrence of a two-step absorption which is assisted by the exciton population resonantly excited by the first photon.

Enlightening the ultrahigh electrical conductivities of doped double-wall carbon nanotube fibers by Raman spectroscopy and first-principles calculations.

PubMed

Tristant, Damien; Zubair, Ahmed; Puech, Pascal; Neumayer, Frédéric; Moyano, Sébastien; Headrick, Robert J; Tsentalovich, Dmitri E; Young, Colin C; Gerber, Iann C; Pasquali, Matteo; Kono, Junichiro; Leotin, Jean

2016-12-01

Highly aligned, packed, and doped carbon nanotube (CNT) fibers with electrical conductivities approaching that of copper have recently become available. These fibers are promising for high-power electrical applications that require light-weight, high current-carrying capacity cables. However, a microscopic understanding of how doping affects the electrical conductance of such CNT fibers in a quantitative manner has been lacking. Here, we performed Raman spectroscopy measurements combined with first-principles calculations to determine the position of the average Fermi energy and to obtain the temperature of chlorosulfonic-acid-doped double-wall CNT fibers under high current. Due to the unique way in which double-wall CNT Raman spectra depend on doping, it is possible to use Raman data to determine the doping level quantitatively. The correspondence between the Fermi level shift and the carbon charge transfer is derived from a tight-binding model and validated by several calculations. For the doped fiber, we were able to associate an average Fermi energy shift of ∼-0.7 eV with a conductance increase by a factor of ∼5. Furthermore, since current induces heating, local temperature determination is possible. Through the Stokes-to-anti-Stokes intensity ratio of the G-band peaks, we estimated a temperature rise at the fiber surface of ∼135 K at a current density of 2.27 × 10 8 A m -2 identical to that from the G-band shift, suggesting that thermalization between CNTs is well achieved.

Comparison of chirped-probe-pulse and hybrid femtosecond/picosecond coherent anti-Stokes Raman scattering for combustion thermometry.

PubMed

Richardson, Daniel R; Stauffer, Hans U; Roy, Sukesh; Gord, James R

2017-04-10

A comparison is made between two ultrashort-pulse coherent anti-Stokes Raman scattering (CARS) thermometry techniques-hybrid femtosecond/picosecond (fs/ps) CARS and chirped-probe-pulse (CPP) fs-CARS-that have become standards for high-repetition-rate thermometry in the combustion diagnostics community. These two variants of fs-CARS differ only in the characteristics of the ps-duration probe pulse; in hybrid fs/ps CARS a spectrally narrow, time-asymmetric probe pulse is used, whereas a highly chirped, spectrally broad probe pulse is used in CPP fs-CARS. Temperature measurements were performed using both techniques in near-adiabatic flames in the temperature range 1600-2400 K and for probe time delays of 0-30 ps. Under these conditions, both techniques are shown to exhibit similar temperature measurement accuracies and precisions to previously reported values and to each other. However, it is observed that initial calibration fits to the spectrally broad CPP results require more fitting parameters and a more robust optimization algorithm and therefore significantly increased computational cost and complexity compared to the fitting of hybrid fs/ps CARS data. The optimized model parameters varied more for the CPP measurements than for the hybrid fs/ps measurements for different experimental conditions.

Using Raman spectroscopy and SERS for in situ studies of rhizosphere bacteria

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mohseni, Hooman; Agahi, Massoud H.; Razeghi, Manijeh

Bacteria colonize plant roots to form a symbiotic relationship with the plant and can play in important role in promoting plant growth. Raman spectroscopy is a useful technique to study these bacterial systems and the chemical signals they utilize to interact with the plant. We present a Raman study of Pantoea YR343 that was isolated from the rhizosphere of Populus deltoides (Eastern Cottonwood). Pantoea sp. YR343 produce yellowish carotenoid pigment that play a role in protection against UV radiation, in the anti-oxidative pathways and in membrane fluidity. Raman spectroscopy is used to non-invasively characterize the membrane bound carotenoids. The spectramore » collected from a mutant strain created by knocking out the crtB gene that encodes a phytoene synthase responsible for early stage of carotenoid biosynthesis, lack the carotenoid peaks. Surface Enhanced Raman Spectroscopy is being employed to detect the plant phytoharmone indoleacetic acid that is synthesized by the bacteria. This work describes our recent progress towards utilizing Raman spectroscopy as a label free, non-destructive method of studying plant-bacteria interactions in the rhizosphere.« less

Imaging of Lipids in Microalgae with Coherent Anti-Stokes Raman Scattering Microscopy1[OPEN

PubMed Central

Cavonius, Lillie; Fink, Helen; Kiskis, Juris; Albers, Eva; Undeland, Ingrid; Enejder, Annika

2015-01-01

Microalgae have great prospects as a sustainable resource of lipids for refinement into nutraceuticals and biodiesel, which increases the need for detailed insights into their intracellular lipid synthesis/storage mechanisms. As an alternative strategy to solvent- and label-based lipid quantification techniques, we introduce time-gated coherent anti-Stokes Raman scattering (CARS) microscopy for monitoring lipid contents in living algae, despite strong autofluorescence from the chloroplasts, at approximately picogram and subcellular levels by probing inherent molecular vibrations. Intracellular lipid droplet synthesis was followed in Phaeodactylum tricornutum algae grown under (1) light/nutrient-replete (control [Ctrl]), (2) light-limited (LL), and (3) nitrogen-starved (NS) conditions. Good correlation (r2 = 0.924) was found between lipid volume data yielded by CARS microscopy and total fatty acid content obtained from gas chromatography-mass spectrometry analysis. In Ctrl and LL cells, micron-sized lipid droplets were found to increase in number throughout the growth phases, particularly in the stationary phase. During more excessive lipid accumulation, as observed in NS cells, promising commercial harvest as biofuels and nutritional lipids, several micron-sized droplets were present already initially during cultivation, which then fused into a single giant droplet toward stationary phase alongside with new droplets emerging. CARS microspectroscopy further indicated lower lipid fluidity in NS cells than in Ctrl and LL cells, potentially due to higher fatty acid saturation. This agreed with the fatty acid profiles gathered by gas chromatography-mass spectrometry. CARS microscopy could thus provide quantitative and semiqualitative data at the single-cell level along with important insights into lipid-accumulating mechanisms, here revealing two different modes for normal and excessive lipid accumulation. PMID:25583924

In vivo chemical and structural analysis of plant cuticular waxes using stimulated Raman scattering microscopy.

PubMed

Littlejohn, George R; Mansfield, Jessica C; Parker, David; Lind, Rob; Perfect, Sarah; Seymour, Mark; Smirnoff, Nicholas; Love, John; Moger, Julian

2015-05-01

The cuticle is a ubiquitous, predominantly waxy layer on the aerial parts of higher plants that fulfils a number of essential physiological roles, including regulating evapotranspiration, light reflection, and heat tolerance, control of development, and providing an essential barrier between the organism and environmental agents such as chemicals or some pathogens. The structure and composition of the cuticle are closely associated but are typically investigated separately using a combination of structural imaging and biochemical analysis of extracted waxes. Recently, techniques that combine stain-free imaging and biochemical analysis, including Fourier transform infrared spectroscopy microscopy and coherent anti-Stokes Raman spectroscopy microscopy, have been used to investigate the cuticle, but the detection sensitivity is severely limited by the background signals from plant pigments. We present a new method for label-free, in vivo structural and biochemical analysis of plant cuticles based on stimulated Raman scattering (SRS) microscopy. As a proof of principle, we used SRS microscopy to analyze the cuticles from a variety of plants at different times in development. We demonstrate that the SRS virtually eliminates the background interference compared with coherent anti-Stokes Raman spectroscopy imaging and results in label-free, chemically specific confocal images of cuticle architecture with simultaneous characterization of cuticle composition. This innovative use of the SRS spectroscopy may find applications in agrochemical research and development or in studies of wax deposition during leaf development and, as such, represents an important step in the study of higher plant cuticles. © 2015 American Society of Plant Biologists. All Rights Reserved.

Label-free imaging of trabecular meshwork cells using Coherent Anti-Stokes Raman Scattering (CARS) microscopy

PubMed Central

Lei, Tim C.; Ammar, David A.; Masihzadeh, Omid; Gibson, Emily A.

2011-01-01

Purpose To image the human trabecular meshwork (TM) using a non-invasive, non-destructive technique without the application of exogenous label. Methods Flat-mounted TM samples from a human cadaver eye were imaged using two nonlinear optical techniques: coherent anti-Stokes Raman scattering (CARS) and two-photon autofluorescence (TPAF). In TPAF, two optical photons are simultaneously absorbed and excite molecules in the sample that then emit a higher energy photon. The signal is predominately from collagen and elastin. The CARS technique uses two laser frequencies to specifically excite carbon-hydrogen bonds, allowing the visualization of lipid-rich cell membranes. Multiple images were taken along an axis perpendicular to the surface of the TM for subsequent analysis. Results Analysis of multiple TPAF images of the TM reveals the characteristic overlapping bundles of collagen of various sizes. Simultaneous CARS imaging revealed elliptical structures of ~7×10 µm in diameter populating the meshwork which were consistent with TM cells. Irregularly shaped objects of ~4 µm diameter appeared in both the TPAF and CARS channels, and are consistent with melanin granules. Conclusions CARS techniques were successful in imaging live TM cells in freshly isolated human TM samples. Similar images have been obtained with standard histological techniques, however the method described here has the advantage of being performed on unprocessed, unfixed tissue free from the potential distortions of the fine tissue morphology that can occur due to infusion of fixatives and treatment with alcohols. CARS imaging of the TM represents a new avenue for exploring details of aqueous outflow and TM cell physiology. PMID:22025898

Label-free imaging of Drosophila in vivo by coherent anti-Stokes Raman scattering and two-photon excitation autofluorescence microscopy

NASA Astrophysics Data System (ADS)

Chien, Cheng-Hao; Chen, Wei-Wen; Wu, June-Tai; Chang, Ta-Chau

2011-01-01

Drosophila is one of the most valuable model organisms for studying genetics and developmental biology. The fat body in Drosophila, which is analogous to the liver and adipose tissue in human, stores lipids that act as an energy source during its development. At the early stages of metamorphosis, the fat body remodeling occurs involving the dissociation of the fat body into individual fat cells. Here we introduce a combination of coherent anti-Stokes Raman scattering (CARS) and two-photon excitation autofluorescence (TPE-F) microscopy to achieve label-free imaging of Drosophila in vivo at larval and pupal stages. The strong CARS signal from lipids allows direct imaging of the larval fat body and pupal fat cells. In addition, the use of TPE-F microscopy allows the observation of other internal organs in the larva and autofluorescent globules in fat cells. During the dissociation of the fat body, the findings of the degradation of lipid droplets and an increase in autofluorescent globules indicate the consumption of lipids and the recruitment of proteins in fat cells. Through in vivo imaging and direct monitoring, CARS microscopy may help elucidate how metamorphosis is regulated and study the lipid metabolism in Drosophila.

Temperature dependent of IVR investigated by steady-state and time-frequency resolved CARS for liquid nitrobenzene and nitromethane

NASA Astrophysics Data System (ADS)

Yang, Yanqiang; Zhu, Gangbei; Yan, Lin; Liu, Xiaosong; Yang's Ultrafast Spectroscopy Group Team

2017-06-01

Intramolecular vibrational energy redistribution (IVR) is important process in thermal decomposition, shock chemistry and photochemistry. Anti-Stokes Raman scattering is sensitive to the vibrational population in excited states because only vibrational excited states are responsible to the anti-Stokes Raman scattering, does not vibrational ground states. In this report, steady-state anti-Stokes Raman spectroscopy and broad band ultrafast coherent anti-Stokes Raman scattering (CARS) are performed. The steady-state anti-Stokes Raman spectroscopy shows temperature dependent of vibrational energy redistribution in vibrational excited-state molecule, and reveal that, in liquid nitrobenzene, with temperature increasing, vibrational energy is mainly redistributed in NO2 symmetric stretching mode, and phenyl ring stretching mode of νCC. For liquid nitromethane, it is found that, with temperature increasing, vibrational energy concentrate in CN stretching mode and methyl umbrella vibrational mode. In the broad band ultrafast CARS experiment, multiple vibrational modes are coherently excited to vibrational excited states, and the time-frequency resolved CARS spectra show the coincident IVR processes. This work is supported by the National Natural Science Foundation of China (Grant Numbers 21673211 and 11372053), and the Science Challenging Program (Grant Number JCKY2016212A501).

Fast low frequency (down to 10 cm(-1)) multichannel Raman spectroscopy using an iodine vapor filter.

PubMed

Okajima, Hajime; Hamaguchi, Hiro-o

2009-08-01

We have constructed a multi-channel Raman spectrometer that is capable of recording the low frequency region down to 5 cm(-1) with a measurement time of a few tenths of a second. An iodine vapor filter, which uses a narrow (approximately 0.03 cm(-1)) absorption line of iodine for Rayleigh scattering elimination, is combined with a multi-channel Raman spectrometer composed of a single polychromator and a charge-coupled device (CCD) camera. Thanks to the high Rayleigh scattering elimination efficiency of the filter, which is over 10(6), Raman spectra of microcrystalline L-cystine from -300 cm(-1) to 1000 cm(-1) are simultaneously measurable with a small gap of 10 cm(-1) (-5 cm(-1) to 5 cm(-1)). Although raw spectra contain many sharp spikes due to the fine structures of iodine absorption, they can be correctly compensated with the use of a transmittance spectrum measured under the same experimental conditions. Many Raman bands including the 9.8 cm(-1) band are measured with a high signal-to-noise ratio in both the Stokes and anti-Stokes sides with a measurement time as short as 0.2 s.

Single-shot time stretch stimulated Raman spectroscopy (Conference Presentation)

NASA Astrophysics Data System (ADS)

Saltarelli, Francesco; Kumar, Vikas; Viola, Daniele; Crisafi, Francesco; Preda, Fabrizio; Cerullo, Giulio; Polli, Dario

2017-02-01

Stimulated Raman scattering spectroscopy is a powerful technique for label-free molecular identification, but its broadband implementation is technically challenging. We introduce and experimentally demonstrate a novel approach based on photonic time stretch. The broadband femtosecond Stokes pulse, after interacting with the sample, is stretched by a telecom fiber to 15ns, mapping its spectrum in time. The signal is sampled through a fast analog-to-digital converter, providing single-shot spectra at 80-kHz rate. We demonstrate 10^-5 sensitivity over 500 cm-1 in the C-H region. Our results pave the way to high-speed broadband vibrational imaging for materials science and biophotonics.

Scanning angle Raman spectroscopy: Investigation of Raman scatter enhancement techniques for chemical analysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Meyer, Matthew W.

2013-01-01

This thesis outlines advancements in Raman scatter enhancement techniques by applying evanescent fields, standing-waves (waveguides) and surface enhancements to increase the generated mean square electric field, which is directly related to the intensity of Raman scattering. These techniques are accomplished by employing scanning angle Raman spectroscopy and surface enhanced Raman spectroscopy. A 1064 nm multichannel Raman spectrometer is discussed for chemical analysis of lignin. Extending dispersive multichannel Raman spectroscopy to 1064 nm reduces the fluorescence interference that can mask the weaker Raman scattering. Overall, these techniques help address the major obstacles in Raman spectroscopy for chemical analysis, which include themore » inherently weak Raman cross section and susceptibility to fluorescence interference.« less

Quantitative fiber-optic Raman spectroscopy for tissue Raman measurements

NASA Astrophysics Data System (ADS)

Duraipandian, Shiyamala; Bergholt, Mads; Zheng, Wei; Huang, Zhiwei

2014-03-01

Molecular profiling of tissue using near-infrared (NIR) Raman spectroscopy has shown great promise for in vivo detection and prognostication of cancer. The Raman spectra measured from the tissue generally contain fundamental information about the absolute biomolecular concentrations in tissue and its changes associated with disease transformation. However, producing analogues tissue Raman spectra present a great technical challenge. In this preliminary study, we propose a method to ensure the reproducible tissue Raman measurements and validated with the in vivo Raman spectra (n=150) of inner lip acquired using different laser powers (i.e., 30 and 60 mW). A rapid Raman spectroscopy system coupled with a ball-lens fiber-optic Raman probe was utilized for tissue Raman measurements. The investigational results showed that the variations between the spectra measured with different laser powers are almost negligible, facilitating the quantitative analysis of tissue Raman measurements in vivo.

Selective suppression of CARS signal with three-beam competing stimulated Raman scattering processes.

PubMed

Choi, Dae Sik; Rao, B Jayachander; Kim, Doyeon; Shim, Sang-Hee; Rhee, Hanju; Cho, Minhaeng

2018-06-14

Coherent Raman scattering spectroscopy and microscopy are useful methods for studying the chemical and biological structures of molecules with Raman-active modes. In particular, coherent anti-Stokes Raman scattering (CARS) microscopy, which is a label-free method capable of imaging structures by displaying the vibrational contrast of the molecules, has been widely used. However, the lack of a technique for switching-off the CARS signal has prevented the development of the super-resolution Raman imaging method. Here, we demonstrate that a selective suppression of the CARS signal is possible by using a three-beam double stimulated Raman scattering (SRS) scheme; the three beams are the pump, Stokes, and depletion lights in order of frequency. Both pump-Stokes and pump-depletion beam pairs can generate SRS processes by tuning their beat frequencies to match two different vibrational modes, then two CARS signals induced by pump-Stokes-pump and pump-depletion-pump interactions can be generated, where the two CARS signals are coupled with each other because they both involve interactions with the common pump beam. Herein, we show that as the intensity of the depletion beam is increased, one can selectively suppress the pump-Stokes-pump CARS signal because the pump-depletion SRS depletes the pump photons. A detailed theoretical description of the coupled differential equations for the three incident fields and the generated CARS signal fields is presented. Taking benzene as a molecular system, we obtained a maximum CARS suppression efficiency of about 97% with our experimental scheme, where the ring breathing mode of the benzene is associated with pump-Stokes-pump CARS, while the C-H stretching mode is associated with the competing pump-depletion SRS process. We anticipate that this selective switching-off scheme will be of use in developing super-resolution label-free CARS microscopy.

Detection of bacterial endospores by means of ultrafast coherent Raman spectroscopy

NASA Astrophysics Data System (ADS)

Pestov, Dmitry Sergeyevich

This work is devoted to formulation and development of a laser spectroscopic technique for rapid detection of biohazards, such as Bacillus anthracis spores. Coherent anti-Stokes Raman scattering (CARS) is used as an underlying process for active retrieval of species-specific characteristics of an analyte. Vibrational modes of constituent molecules are Raman-excited by a pair of ultrashort, femtosecond laser pulses, and then probed through inelastic scattering of a third, time-delayed laser field. We first employ the already known time-resolved CARS technique. We apply it to the spectroscopy of easy-to-handle methanol-water mixtures, and then continue building our expertise on solutions of dipicolinic acid (DPA) and its salts, which happen to be marker molecules for bacterial spores. Various acquisition schemes are evaluated, and the preference is given to multi-channel frequency-resolved detection, when the whole CARS spectrum is recorded as a function of the probe pulse delay. We demonstrate a simple detection algorithm that manages to differentiate DPA solution from common interferents. We investigate experimentally the advantages and disadvantages of near-resonant probing of the excited molecular coherence, and finally observe the indicative backscattered CARS signal from DPA and NaDPA powders. The possibility of selective Raman excitation via pulse shaping of the preparation pulses is also demonstrated. The analysis of time-resolved CARS experiments on powders and B. subtilis spores, a harmless surrogate for B. anthracis, facilitates the formulation of a new approach, where we take full advantage of the multi-channel frequency-resolved acquisition and spectrally discriminate the Raman-resonant CARS signal from the background due to other instantaneous four-wave mixing (FWM) processes. Using narrowband probing, we decrease the magnitude of the nonresonant FWM, which is further suppressed by the timing of the laser pulses. The devised technique, referred to as

Near-infrared Raman spectroscopy to detect anti-Toxoplasma gondii antibody in blood sera of domestic cats: quantitative analysis based on partial least-squares multivariate statistics

NASA Astrophysics Data System (ADS)

Duarte, Janaína; Pacheco, Marcos T. T.; Villaverde, Antonio Balbin; Machado, Rosangela Z.; Zângaro, Renato A.; Silveira, Landulfo

2010-07-01

Toxoplasmosis is an important zoonosis in public health because domestic cats are the main agents responsible for the transmission of this disease in Brazil. We investigate a method for diagnosing toxoplasmosis based on Raman spectroscopy. Dispersive near-infrared Raman spectra are used to quantify anti-Toxoplasma gondii (IgG) antibodies in blood sera from domestic cats. An 830-nm laser is used for sample excitation, and a dispersive spectrometer is used to detect the Raman scattering. A serological test is performed in all serum samples by the enzyme-linked immunosorbent assay (ELISA) for validation. Raman spectra are taken from 59 blood serum samples and a quantification model is implemented based on partial least squares (PLS) to quantify the sample's serology by Raman spectra compared to the results provided by the ELISA test. Based on the serological values provided by the Raman/PLS model, diagnostic parameters such as sensitivity, specificity, accuracy, positive prediction values, and negative prediction values are calculated to discriminate negative from positive samples, obtaining 100, 80, 90, 83.3, and 100%, respectively. Raman spectroscopy, associated with the PLS, is promising as a serological assay for toxoplasmosis, enabling fast and sensitive diagnosis.

Exploring the interactions between peptides and lipid bilayers using coherent anti-Stokes Raman scattering and two-photon fluorescence

NASA Astrophysics Data System (ADS)

Mari, M.; Mouras, R.; Downes, A.; Elfick, A.

2011-06-01

We have used a versatile and powerful microscope[1] for multi-modal biomedical imaging on which we combine Coherent Anti-Stokes Raman Scattering (CARS) with Two Photon Excitation Fluorescence (TPEF) using a Nd: YVO4 pump laser. We acquired 2PEF, CARS, and phase contrast images of Multilamellar Vesicles (MLVs) and Giant Unilamellar Vesicles (GUVs), as well as Raman spectra of the constituent lipids. A wide range of peptides are harmful to cells by altering the structure of the biological membranes. This effect depends on the composition of the membrane and the chemical structure of the peptide. The peptide we studied is the beta amyloid Aβ which is a major component of the amyloid plaques deposited on neuronal membranes of Alzheimer's disease (AD) patients. AD is neurodegenerative disorder in which the hallmark symptoms include cognitive decline and dementia[2] and is characterized by the formation of extracellular amyloid fibrils on the neuronal membranes of the brain. Many questions still remain unanswered concerning the destabilization of cellular ionic homeostasis due to pores formed during the interactions of lipid membranes with peptides. In this project, biomimics of cell membranes are used. The structures that best mimic the plasma membranes are MLVs or GUVs. These vesicles are formed using the gentle hydration technique[3] or the electroformation technique[4] respectively and are composed of phospholipids such as DOPC, DPPC, D62PPC and their binary mixtures. The MLVs and GUVs imaging by CARS and TPEF microscopy not only permits the direct imaging of the leakage phenomenon caused by the toxic peptide (Aβ) on the lipid bilayer, but also records simultaneously the lateral structure of the bilayer and peptide distribution in the plane across the membrane.

Role of Raman spectroscopy and surface enhanced Raman spectroscopy in colorectal cancer

PubMed Central

Jenkins, Cerys A; Lewis, Paul D; Dunstan, Peter R; Harris, Dean A

2016-01-01

Colorectal cancer (CRC) is the fourth most common cancer in the United Kingdom and is the second largest cause of cancer related death in the United Kingdom after lung cancer. Currently in the United Kingdom there is not a diagnostic test that has sufficient differentiation between patients with cancer and those without cancer so the current referral system relies on symptomatic presentation in a primary care setting. Raman spectroscopy and surface enhanced Raman spectroscopy (SERS) are forms of vibrational spectroscopy that offer a non-destructive method to gain molecular information about biological samples. The techniques offer a wide range of applications from in vivo or in vitro diagnostics using endoscopic probes, to the use of micro-spectrometers for analysis of biofluids. The techniques have the potential to detect molecular changes prior to any morphological changes occurring in the tissue and therefore could offer many possibilities to aid the detection of CRC. The purpose of this review is to look at the current state of diagnostic technology in the United Kingdom. The development of Raman spectroscopy and SERS in clinical applications relation for CRC will then be discussed. Finally, future areas of research of Raman/SERS as a clinical tool for the diagnosis of CRC are also discussed. PMID:27190582

Structural studies of polytene chromosomes and bone implant coatings: Raman microspectroscopy and atomic force microscopy

NASA Astrophysics Data System (ADS)

de Grauw, Kees

Raman microscopy and atomic force microscopy (AFM) are used for the investigation of the composition and structure of the banding patterns of polytene chromosomes and of hydroxyapatite bone-implant coatings. For Raman microspectroscopy two new measuring methods are introduced: line-scan Raman and Low-wavenumber Raman microspectroscopy. A transparent and easy to use model to predict the depth resolution of a confocal microscope is described. A Chevron-type of filter set was developed for simultaneous measurements of Stokes and anti-Stokes Raman scattering close to the exciting laser frequency. Bands of polytene chromosomes appeared to contain a higher concentration of DNA and proteins compared to interbands. AFM measurements revealed that bands consist of a densely packed chromatin structure and are hardly affected by stretching of the chromosome. Interbands have a more open chromatin structure and are more accessible to solvent molecules. For the study of bone implant coatings Raman micro spectroscopy appeared to provide an easy, non- destructive, way to obtain information about the apatite structure and the degree of crystallinity. It was shown that the degree of crystallinity was constant over coatings produced by plasma spraying while the material density did vary.

Impulsive Raman spectroscopy via precision measurement of frequency shift with low energy excitation.

PubMed

Raanan, Dekel; Ren, Liqing; Oron, Dan; Silberberg, Yaron

2018-02-01

Stimulated Raman scattering (SRS) has recently become useful for chemically selective bioimaging. It is usually measured via modulation transfer from the pump beam to the Stokes beam. Impulsive stimulated Raman spectroscopy, on the other hand, relies on the spectral shift of ultrashort pulses as they propagate in a Raman active sample. This method was considered impractical with low energy pulses since the observed shifts are very small compared to the excitation pulse bandwidth, spanning many terahertz. Here we present a new apparatus, using tools borrowed from the field of precision measurement, for the detection of low-frequency Raman lines via stimulated-Raman-scattering-induced spectral shifts. This method does not require any spectral filtration and is therefore an excellent candidate to resolve low-lying Raman lines (<200  cm -1 ), which are commonly masked by the strong Rayleigh scattering peak. Having the advantage of the high repetition rate of the ultrafast oscillator, we reduce the noise level by implementing a lock-in detection scheme with a wavelength shift sensitivity well below 100 fm. This is demonstrated by the measurement of low-frequency Raman lines of various liquid samples.

Optimization of anisotropic photonic density of states for Raman cooling of solids

NASA Astrophysics Data System (ADS)

Chen, Yin-Chung; Ghosh, Indronil; Schleife, André; Carney, P. Scott; Bahl, Gaurav

2018-04-01

Optical refrigeration of solids holds tremendous promise for applications in thermal management. It can be achieved through multiple mechanisms including inelastic anti-Stokes Brillouin and Raman scattering. However, engineering of these mechanisms remains relatively unexplored. The major challenge lies in the natural unfavorable imbalance in transition rates for Stokes and anti-Stokes scattering. We consider the influence of anisotropic photonic density of states on Raman scattering and derive expressions for cooling in such photonically anisotropic systems. We demonstrate optimization of the Raman cooling figure of merit considering all possible orientations for the material crystal and two example photonic crystals. We find that the anisotropic description of the photonic density of states and the optimization process is necessary to obtain the best Raman cooling efficiency for systems having lower symmetry. This general result applies to a wide array of other laser cooling methods in the presence of anisotropy.

Communication: atomic force detection of single-molecule nonlinear optical vibrational spectroscopy.

PubMed

Saurabh, Prasoon; Mukamel, Shaul

2014-04-28

Atomic Force Microscopy (AFM) allows for a highly sensitive detection of spectroscopic signals. This has been first demonstrated for NMR of a single molecule and recently extended to stimulated Raman in the optical regime. We theoretically investigate the use of optical forces to detect time and frequency domain nonlinear optical signals. We show that, with proper phase matching, the AFM-detected signals closely resemble coherent heterodyne-detected signals. Applications are made to AFM-detected and heterodyne-detected vibrational resonances in Coherent Anti-Stokes Raman Spectroscopy (χ((3))) and sum or difference frequency generation (χ((2))).

Raman linewidth measurements using time-resolved hybrid picosecond/nanosecond rotational CARS.

PubMed

Nordström, Emil; Hosseinnia, Ali; Brackmann, Christian; Bood, Joakim; Bengtsson, Per-Erik

2015-12-15

We report an innovative approach for time-domain measurements of S-branch Raman linewidths using hybrid picosecond/nanosecond pure-rotational coherent anti-Stokes Raman spectroscopy (RCARS). The Raman coherences are created by two picosecond excitation pulses and are probed using a narrow-band nanosecond pulse at 532 nm. The generated RCARS signal contains the entire coherence decay in a single pulse. By extracting the decay times of the individual transitions, the J-dependent Raman linewidths can be calculated. Self-broadened S-branch linewidths for nitrogen and oxygen at 293 K and ambient pressure are in good agreement with previous time-domain measurements. Experimental considerations of the approach are discussed along with its merits and limitations. The approach can be extended to a wide range of pressures and temperatures and has potential for simultaneous single-shot thermometry and linewidth determination.

Applications of Raman spectroscopy in life science

NASA Astrophysics Data System (ADS)

Martin, Airton A.; T. Soto, Cláudio A.; Ali, Syed M.; Neto, Lázaro P. M.; Canevari, Renata A.; Pereira, Liliane; Fávero, Priscila P.

2015-06-01

Raman spectroscopy has been applied to the analysis of biological samples for the last 12 years providing detection of changes occurring at the molecular level during the pathological transformation of the tissue. The potential use of this technology in cancer diagnosis has shown encouraging results for the in vivo, real-time and minimally invasive diagnosis. Confocal Raman technics has also been successfully applied in the analysis of skin aging process providing new insights in this field. In this paper it is presented the latest biomedical applications of Raman spectroscopy in our laboratory. It is shown that Raman spectroscopy (RS) has been used for biochemical and molecular characterization of thyroid tissue by micro-Raman spectroscopy and gene expression analysis. This study aimed to improve the discrimination between different thyroid pathologies by Raman analysis. A total of 35 thyroid tissues samples including normal tissue (n=10), goiter (n=10), papillary (n=10) and follicular carcinomas (n=5) were analyzed. The confocal Raman spectroscopy allowed a maximum discrimination of 91.1% between normal and tumor tissues, 84.8% between benign and malignant pathologies and 84.6% among carcinomas analyzed. It will be also report the application of in vivo confocal Raman spectroscopy as an important sensor for detecting advanced glycation products (AGEs) on human skin.

Imaging the Effects of Prostaglandin Analogues on Cultured Trabecular Meshwork Cells by Coherent Anti-Stokes Raman Scattering

PubMed Central

Lei, Tim C.; Masihzadeh, Omid; Kahook, Malik Y.; Ammar, David A.

2013-01-01

Purpose. The aim of this study was to nondestructively monitor morphological changes to the lipid membranes of primary cultures of living human trabecular meshwork cells (hTMC) without the application of exogenous label. Methods. Live hTMC were imaged using two nonlinear optical techniques: coherent anti-Stokes Raman scattering (CARS) and two-photon autofluorescence (TPAF). The hTMC were treated with a commercial formulation of latanoprost (0.5 μg/mL) for 24 hours before imaging. Untreated cells and cells treated with vehicle containing the preservative benzalkonium chloride (BAK; 2 μg/mL) were imaged as controls. After CARS/TPAF imaging, hTMC were fixed, stained with the fluorescent lipid dye Nile Red, and imaged by conventional confocal microscopy to verify lipid membrane structures. Results. Analysis of CARS/TPAF images of hTMC treated with latanoprost revealed multiple intracellular lipid membranes absent from untreated or BAK-treated hTMC. Treatment of hTMC with sodium fluoride or ouabain, agents shown to cause morphological changes to hTMC, also did not induce formation of intracellular lipid membranes. Conclusions. CARS microscopy detected changes in living hTMC morphology that were validated by subsequent histological stain. Prostaglandin-induced changes to hTMC involved rearrangement of lipid membranes within these cells. These in vitro results identify a novel biological response to a class of antiglaucoma drugs, and further experiments are needed to establish how this effect is involved in the hypotensive action of prostaglandin analogues in vivo. PMID:23900606

Theoretical study of collinear optical frequency comb generation under multi-wave, transient stimulated Raman scattering in crystals

NASA Astrophysics Data System (ADS)

Smetanin, S. N.

2014-11-01

Using mathematical modelling we have studied the conditions of low-threshold collinear optical frequency comb generation under transient (picosecond) stimulated Raman scattering (SRS) and parametric four-wave coupling of SRS components in crystals. It is shown that Raman-parametric generation of an octave-spanning optical frequency comb occurs most effectively under intermediate, transient SRS at a pump pulse duration exceeding the dephasing time by five-to-twenty times. We have found the optimal values of not only the laser pump pulse duration, but also of the Raman crystal lengths corresponding to highly efficient generation of an optical frequency comb from the second anti-Stokes to the fourth Stokes Raman components. For the KGd(WO4)2 (high dispersion) and Ba(NO3)2 (low dispersion) crystals pumped at a wavelength of 1.064 μm and a pulse duration five or more times greater than the dephasing time, the optimum length of the crystal was 0.3 and 0.6 cm, respectively, which is consistent with the condition of the most effective Stokes - anti-Stokes coupling ΔkL ≈ 15, where Δk is the wave detuning from phase matching of Stokes - anti-Stokes coupling, determined by the refractive index dispersion of the SRS medium.

Ring-Down Spectroscopy for Characterizing a CW Raman Laser

NASA Technical Reports Server (NTRS)

Matsko, Andrey; Savchenkov, Anatoliy; Maleki, Lute

2007-01-01

.A relatively simple technique for characterizing an all-resonant intracavity continuous-wave (CW) solid-state Raman laser involves the use of ring-down spectroscopy. As used here, characterizing signifies determining such parameters as threshold pump power, Raman gain, conversion efficiency, and quality factors (Q values) of the pump and Stokes cavity modes. Heretofore, in order to characterize resonant-cavity-based Raman lasers, it has usually been necessary to manipulate the frequencies and power levels of pump lasers and, in each case, to take several sets of measurements. In cases involving ultra-high-Q resonators, it also has been desirable to lock pump lasers to resonator modes to ensure the quality of measurement data. Simpler techniques could be useful. In the present ring-down spectroscopic technique, one infers the parameters of interest from the decay of the laser out of its steady state. This technique does not require changing the power or frequency of the pump laser or locking the pump laser to the resonator mode. The technique is based on a theoretical analysis of what happens when the pump laser is abruptly switched off after the Raman generation reaches the steady state. The analysis starts with differential equations for the evolution of the amplitudes of the pump and Stokes electric fields, leading to solutions for the power levels of the pump and Stokes fields as functions of time and of the aforementioned parameters. Among other things, these solutions show how the ring-down time depends, to some extent, on the electromagnetic energy accumulated in the cavity. The solutions are readily converted to relatively simple equations for the parameters as functions of quantities that can be determined from measurements of the time-dependent power levels. For example, the steady-state intracavity conversion efficiency is given by G1/G2 1 and the threshold power is given by Pin(G2/G1)2, where Pin is the steady-state input pump power immediately prior to

Dynamic characteristics of a multi-wavelength Brillouin-Raman fiber laser assisted by multiple four-wave mixing processes in a ring cavity

NASA Astrophysics Data System (ADS)

Shirazi, M. R.; Mohamed Taib, J.; De La Rue, R. M.; Harun, S. W.; Ahmad, H.

2015-03-01

Dynamic characteristics of a multi-wavelength Brillouin-Raman fiber laser (MBRFL) assisted by four-wave mixing have been investigated through the development of Stokes and anti-Stokes lines under different combinations of Brillouin and Raman pump power levels and different Raman pumping schemes in a ring cavity. For a Stokes line of order higher than three, the threshold power was less than the saturation power of its last-order Stokes line. By increasing the Brillouin pump power, the nth order anti-Stokes and the (n+4)th order Stokes power levels were unexpectedly increased almost the same before the Stokes line threshold power. It was also found out that the SBS threshold reduction (SBSTR) depended linearly on the gain factor for the 1st and 2nd Stokes lines, as the first set. This relation for the 3rd and 4th Stokes lines as the second set, however, was almost linear with the same slope before SBSTR -6 dB, then, it approached to the linear relation in the first set when the gain factor was increased to 50 dB. Therefore, the threshold power levels of Stokes lines for a given Raman gain can be readily estimated only by knowing the threshold power levels in which there is no Raman amplification.

Cascaded a-cut Nd:YVO4 self-Raman with second-Stokes laser at 1313 nm

NASA Astrophysics Data System (ADS)

Xie, Zhi; Duan, Yanmin; Guo, Junhong; Huang, Xiaohong; Yan, Lifen; Zhu, Haiyong

2017-11-01

A diode-end-pumped, acousto-optic Q-switched second-Stokes self-Raman laser at 1313 nm was demonstrated in a common a-cut Nd:YVO4 crystal, with the primary Raman shift of 890 cm-1. At the incident pump power of 17.1 W, the maximum average output power up to 2.51 W and pulse width of 5 ns for second-Stokes were obtained with the pulse repetition frequency of 50 kHz. The slope efficiency and conversion efficiency with respect to the incident pump power are about 23.7% and 14.7%. The efficient output should be attributed to suitable transmittance of the output coupler used.

Raman Plus X: Biomedical Applications of Multimodal Raman Spectroscopy.

PubMed

Das, Nandan K; Dai, Yichuan; Liu, Peng; Hu, Chuanzhen; Tong, Lieshu; Chen, Xiaoya; Smith, Zachary J

2017-07-07

Raman spectroscopy is a label-free method of obtaining detailed chemical information about samples. Its compatibility with living tissue makes it an attractive choice for biomedical analysis, yet its translation from a research tool to a clinical tool has been slow, hampered by fundamental Raman scattering issues such as long integration times and limited penetration depth. In this review we detail the how combining Raman spectroscopy with other techniques yields multimodal instruments that can help to surmount the translational barriers faced by Raman alone. We review Raman combined with several optical and non-optical methods, including fluorescence, elastic scattering, OCT, phase imaging, and mass spectrometry. In each section we highlight the power of each combination along with a brief history and presentation of representative results. Finally, we conclude with a perspective detailing both benefits and challenges for multimodal Raman measurements, and give thoughts on future directions in the field.

Raman Plus X: Biomedical Applications of Multimodal Raman Spectroscopy

PubMed Central

Das, Nandan K.; Dai, Yichuan; Liu, Peng; Hu, Chuanzhen; Tong, Lieshu; Chen, Xiaoya

2017-01-01

Raman spectroscopy is a label-free method of obtaining detailed chemical information about samples. Its compatibility with living tissue makes it an attractive choice for biomedical analysis, yet its translation from a research tool to a clinical tool has been slow, hampered by fundamental Raman scattering issues such as long integration times and limited penetration depth. In this review we detail the how combining Raman spectroscopy with other techniques yields multimodal instruments that can help to surmount the translational barriers faced by Raman alone. We review Raman combined with several optical and non-optical methods, including fluorescence, elastic scattering, OCT, phase imaging, and mass spectrometry. In each section we highlight the power of each combination along with a brief history and presentation of representative results. Finally, we conclude with a perspective detailing both benefits and challenges for multimodal Raman measurements, and give thoughts on future directions in the field. PMID:28686212

Study and application of new Raman spectroscopy

NASA Astrophysics Data System (ADS)

Liu, Qiushi; Zhang, Xiaohua

2016-03-01

Spatially Offset Raman Spectroscopy (SORS) is a new type of Raman Spectroscopy technology, which can detect the medium concealed in the opaque or sub-transparent material fast and nondestructively. The article summarized Spatially Offset Raman Spectroscopy`s international and domestic study and application progress on contraband detecting, medical science (bone ingredient, cancer diagnose etc.), agricultural products, historical relic identification etc. and stated the technology would become an effective measurement which had wide application prospect.

Cutaneous porphyrins exhibit anti-stokes fluorescence that is detectable in sebum (Conference Presentation)

NASA Astrophysics Data System (ADS)

Tian, Giselle; Zeng, Haishan; Zhao, Jianhua; Wu, Zhenguo; Al Jasser, Mohammed; Lui, Harvey; Mclean, David I.

2016-02-01

Porphyrins produced by Propionibacterium acnes represent the principal fluorophore associated with acne, and appear as orange-red luminescence under the Wood's lamp. Assessment of acne based on Wood's lamp (UV) or visible light illumination is limited by photon penetration depth and has limited sensitivity for earlier stage lesions. Inducing fluorescence with near infrared (NIR) excitation may provide an alternative way to assess porphyrin-related skin disorders. We discovered that under 785 nm CW laser excitation PpIX powder exhibits fluorescence emission in the shorter wavelength range of 600-715 nm with an intensity that is linearly dependent on the excitation power. We attribute this shorter wavelength emission to anti-Stokes fluorescence. Similar anti-Stokes fluorescence was also detected focally in all skin-derived samples containing porphyrins. Regular (Stokes) fluorescence was present under UV and visible light excitation on ex vivo nasal skin and sebum from uninflamed acne, but not on nose surface smears or sebum from inflamed acne. Co-registered CW laser-excited anti-Stokes fluorescence and fs laser-excited multi-photon fluorescence images of PpIX powder showed similar features. In the skin samples because of the anti-Stokes effect, the NIR-induced fluorescence was presumably specific for porphyrins since there appeared to be no anti-Stokes emission signals from other typical skin fluorophores such as lipids, keratins and collagen. Anti-Stokes fluorescence under NIR CW excitation is more sensitive and specific for porphyrin detection than UV- or visible light-excited regular fluorescence and fs laser-excited multi-photon fluorescence. This approach also has higher image contrast compared to NIR fs laser-based multi-photon fluorescence imaging. The anti-Stokes fluorescence of porphyrins within sebum could potentially be applied to detecting and targeting acne lesions for treatment via fluorescence image guidance.

Characterization and discrimination of human breast cancer and normal breast tissues using resonance Raman spectroscopy

NASA Astrophysics Data System (ADS)

Wu, Binlin; Smith, Jason; Zhang, Lin; Gao, Xin; Alfano, Robert R.

2018-02-01

Worldwide breast cancer incidence has increased by more than twenty percent in the past decade. It is also known that in that time, mortality due to the affliction has increased by fourteen percent. Using optical-based diagnostic techniques, such as Raman spectroscopy, has been explored in order to increase diagnostic accuracy in a more objective way along with significantly decreasing diagnostic wait-times. In this study, Raman spectroscopy with 532-nm excitation was used in order to incite resonance effects to enhance Stokes Raman scattering from unique biomolecular vibrational modes. Seventy-two Raman spectra (41 cancerous, 31 normal) were collected from nine breast tissue samples by performing a ten-spectra average using a 500-ms acquisition time at each acquisition location. The raw spectral data was subsequently prepared for analysis with background correction and normalization. The spectral data in the Raman Shift range of 750- 2000 cm-1 was used for analysis since the detector has highest sensitivity around in this range. The matrix decomposition technique nonnegative matrix factorization (NMF) was then performed on this processed data. The resulting leave-oneout cross-validation using two selective feature components resulted in sensitivity, specificity and accuracy of 92.6%, 100% and 96.0% respectively. The performance of NMF was also compared to that using principal component analysis (PCA), and NMF was shown be to be superior to PCA in this study. This study shows that coupling the resonance Raman spectroscopy technique with subsequent NMF decomposition method shows potential for high characterization accuracy in breast cancer detection.

FT-Raman Spectroscopy: A Catalyst for the Raman Explosion?

ERIC Educational Resources Information Center

Chase, Bruce

2007-01-01

The limitations of Fourier transform (FT) Raman spectroscopy, which is used to detect and analyze the scattered radiation, are discussed. FT-Raman has served to revitalize a field that was lagging and the presence of Raman instrumentation as a routine analytical tool is established for the foreseeable future.

Garry Rumbles | NREL

Science.gov Websites

, colloidal quantum dots, and single-walled carbon nanotubes. Laser-based experiments (time-resolved fluorescence spectroscopy; time-resolved resonance Raman spectroscopy; laser-induced fluorescence spectroscopy ; time-resolved evanescent wave-induced fluorescence spectroscopy; picosecond coherent anti-Stokes Raman

Theoretical study of collinear optical frequency comb generation under multi-wave, transient stimulated Raman scattering in crystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smetanin, S N

2014-11-30

Using mathematical modelling we have studied the conditions of low-threshold collinear optical frequency comb generation under transient (picosecond) stimulated Raman scattering (SRS) and parametric four-wave coupling of SRS components in crystals. It is shown that Raman-parametric generation of an octave-spanning optical frequency comb occurs most effectively under intermediate, transient SRS at a pump pulse duration exceeding the dephasing time by five-to-twenty times. We have found the optimal values of not only the laser pump pulse duration, but also of the Raman crystal lengths corresponding to highly efficient generation of an optical frequency comb from the second anti-Stokes to the fourthmore » Stokes Raman components. For the KGd(WO{sub 4}){sub 2} (high dispersion) and Ba(NO{sub 3}){sub 2} (low dispersion) crystals pumped at a wavelength of 1.064 μm and a pulse duration five or more times greater than the dephasing time, the optimum length of the crystal was 0.3 and 0.6 cm, respectively, which is consistent with the condition of the most effective Stokes – anti-Stokes coupling ΔkL ≈ 15, where Δk is the wave detuning from phase matching of Stokes – anti-Stokes coupling, determined by the refractive index dispersion of the SRS medium. (nonlinear optical phenomena)« less

New structural transformations in congruent ferroelectric LiNbO3 fibres evidenced by Raman spectroscopy

NASA Astrophysics Data System (ADS)

Noiret, I.; Lefebvre, J.; Schamps, J.; Delattre, F.; Brenier, A.; Ferriol, M.

2000-03-01

Temperature dependent Stokes and anti-Stokes Raman-scattering experiments have been performed to study the ferroelectric phase of congruent LiNbO3 fibres in the external and internal mode regions. Mode splittings and changes in the slope of frequency-temperature plots at 590 and 790 K show the occurrence of two structural transformations at these temperatures. The anisotropy of the correlation time associated with the width of the central component and anomalies observed in previous neutron investigations are related to a migration process of the lithium atoms along the hexagonal axis and along the pseudo-cubic axis of the highly distorted related perovskite structure. The observed transformations are tentatively assigned to long-range correlated rearrangements in the intrinsic defect structure of the crystal.

Blood analysis by Raman spectroscopy.

PubMed

Enejder, Annika M K; Koo, Tae-Woong; Oh, Jeankun; Hunter, Martin; Sasic, Slobodan; Feld, Michael S; Horowitz, Gary L

2002-11-15

Concentrations of multiple analytes were simultaneously measured in whole blood with clinical accuracy, without sample processing, using near-infrared Raman spectroscopy. Spectra were acquired with an instrument employing nonimaging optics, designed using Monte Carlo simulations of the influence of light-scattering-absorbing blood cells on the excitation and emission of Raman light in turbid medium. Raman spectra were collected from whole blood drawn from 31 individuals. Quantitative predictions of glucose, urea, total protein, albumin, triglycerides, hematocrit, and hemoglobin were made by means of partial least-squares (PLS) analysis with clinically relevant precision (r(2) values >0.93). The similarity of the features of the PLS calibration spectra to those of the respective analyte spectra illustrates that the predictions are based on molecular information carried by the Raman light. This demonstrates the feasibility of using Raman spectroscopy for quantitative measurements of biomolecular contents in highly light-scattering and absorbing media.

The hallmarks of breast cancer by Raman spectroscopy

NASA Astrophysics Data System (ADS)

Abramczyk, H.; Surmacki, J.; Brożek-Płuska, B.; Morawiec, Z.; Tazbir, M.

2009-04-01

This paper presents new biological results on ex vivo breast tissue based on Raman spectroscopy and demonstrates its power as diagnostic tool with the key advantage in breast cancer research. The results presented here demonstrate the ability of Raman spectroscopy to accurately characterize cancer tissue and distinguish between normal, malignant and benign types. The goal of the paper is to develop the diagnostic ability of Raman spectroscopy in order to find an optical marker of cancer in the breast tissue. Applications of Raman spectroscopy in breast cancer research are in the early stages of development in the world. To the best of our knowledge, this paper is one of the most statistically reliable reports (1100 spectra, 99 patients) on Raman spectroscopy-based diagnosis of breast cancers among the world women population.

Raman spectroscopy in astrobiology.

PubMed

Jorge Villar, Susana E; Edwards, Howell G M

2006-01-01

Raman spectroscopy is proposed as a valuable analytical technique for planetary exploration because it is sensitive to organic and inorganic compounds and able to unambiguously identify key spectral markers in a mixture of biological and geological components; furthermore, sample manipulation is not required and any size of sample can be studied without chemical or mechanical pretreatment. NASA and ESA are considering the adoption of miniaturised Raman spectrometers for inclusion in suites of analytical instrumentation to be placed on robotic landers on Mars in the near future to search for extinct or extant life signals. In this paper we review the advantages and limitations of Raman spectroscopy for the analysis of complex specimens with relevance to the detection of bio- and geomarkers in extremophilic organisms which are considered to be terrestrial analogues of possible extraterrestial life that could have developed on planetary surfaces.

Mid-infrared Raman amplification and wavelength conversion in dispersion engineered silicon-on-sapphire waveguides

NASA Astrophysics Data System (ADS)

Wang, Zhaolu; Liu, Hongjun; Huang, Nan; Sun, Qibing; Li, Xuefeng

2014-01-01

Raman amplification based on stimulated Stokes Raman scattering (SSRS) and wavelength conversion based on coherent anti-Stokes Raman scattering (CARS) are theoretically investigated in silicon-on-sapphire (SOS) waveguides in the mid-infrared (IR) region. When the linear phase mismatch Δk is close to zero, the Stokes gain and conversion efficiency drop down quickly due to the effect of parametric gain suppression when the Stokes-pump input ratio is sufficiently large. The Stokes gain increases with the increase of Δk, whereas efficient wavelength conversion needs appropriate Δk under different pump intensities. The conversion efficiency at exact linear phase matching (Δk = 0) is smaller than that at optimal linear phase mismatch by a factor of about 28 dB when the pump intensity is 2 GW cm-2.

Split-probe hybrid femtosecond/picosecond rotational CARS for time-domain measurement of S-branch Raman linewidths within a single laser shot.

PubMed

Patterson, Brian D; Gao, Yi; Seeger, Thomas; Kliewer, Christopher J

2013-11-15

We introduce a multiplex technique for the single-laser-shot determination of S-branch Raman linewidths with high accuracy and precision by implementing hybrid femtosecond (fs)/picosecond (ps) rotational coherent anti-Stokes Raman spectroscopy (CARS) with multiple spatially and temporally separated probe beams derived from a single laser pulse. The probe beams scatter from the rotational coherence driven by the fs pump and Stokes pulses at four different probe pulse delay times spanning 360 ps, thereby mapping collisional coherence dephasing in time for the populated rotational levels. The probe beams scatter at different folded BOXCARS angles, yielding spatially separated CARS signals which are collected simultaneously on the charge coupled device camera. The technique yields a single-shot standard deviation (1σ) of less than 3.5% in the determination of Raman linewidths and the average linewidth values obtained for N(2) are within 1% of those previously reported. The presented technique opens the possibility for correcting CARS spectra for time-varying collisional environments in operando.

Multimodal coherent anti-Stokes Raman scattering microscopy reveals microglia-associated myelin and axonal dysfunction in multiple sclerosis-like lesions in mice

PubMed Central

Imitola, Jaime; Côté, Daniel; Rasmussen, Stine; Xie, X. Sunney; Liu, Yingru; Chitnis, Tanuja; Sidman, Richard L.; Lin, Charles. P.; Khoury, Samia J.

2011-01-01

Myelin loss and axonal degeneration predominate in many neurological disorders; however, methods to visualize them simultaneously in live tissue are unavailable. We describe a new imaging strategy combining video rate reflectance and fluorescence confocal imaging with coherent anti-Stokes Raman scattering (CARS) microscopy tuned to CH2 vibration of myelin lipids, applied in live tissue of animals with chronic experimental autoimmune encephalomyelitis (EAE). Our method allows monitoring over time of demyelination and neurodegeneration in brain slices with high spatial resolution and signal-to-noise ratio. Local areas of severe loss of lipid signal indicative of demyelination and loss of the reflectance signal from axons were seen in the corpus callosum and spinal cord of EAE animals. Even in myelinated areas of EAE mice, the intensity of myelin lipid signals is significantly reduced. Using heterozygous knock-in mice in which green fluorescent protein replaces the CX3CR1 coding sequence that labels central nervous system microglia, we find areas of activated microglia colocalized with areas of altered reflectance and CARS signals reflecting axonal injury and demyelination. Our data demonstrate the use of multimodal CARS microscopy for characterization of demyelinating and neurodegenerative pathology in a mouse model of multiple sclerosis, and further confirm the critical role of microglia in chronic inflammatory neurodegeneration. PMID:21361672

Raman spectroscopy of oral bacteria

NASA Astrophysics Data System (ADS)

Berger, Andrew J.; Zhu, Qingyuan; Quivey, Robert G.

2003-10-01

Raman spectroscopy has been employed to measure the varying concentrations of two oral bacteria in simple mixtures. Evaporated droplets of centrifuged mixtures of Streptococcus sanguis and Streptococcus mutans were analyzed via Raman microspectroscopy. The concentration of s. sanguis was determined based upon the measured Raman spectrum, using partial least squares cross-validation, with an r2 value of 0.98.

Micro-mirror arrays for Raman spectroscopy

NASA Astrophysics Data System (ADS)

Duncan, W. M.

2015-03-01

In this research we study Raman and fluorescence spectroscopies as non-destructive and noninvasive methods for probing biological material and "living systems." Particularly for a living material any probe need be non-destructive and non-invasive, as well as provide real time measurement information and be cost effective to be generally useful. Over the past few years the components needed to measure weak and complex processes such as Raman scattering have evolved substantially with the ready availability of lasers, dichroic filters, low noise and sensitive detectors, digitizers and signal processors. A Raman spectrum consists of a wavelength or frequency spectrum that corresponds to the inelastic (Raman) photon signal that results from irradiating a "Raman active" material. Raman irradiation of a material usually and generally uses a single frequency laser. The Raman fingerprint spectrum that results from a Raman interaction can be determined from the frequencies scattered and received by an appropriate detector. Spectra are usually "digitized" and numerically matched to a reference sample or reference material spectra in performing an analysis. Fortunately today with the many "commercial off-the-shelf" components that are available, weak intensity effects such as Raman and fluorescence spectroscopy can be used for a number of analysis applications. One of the experimental limitations in Raman measurement is the spectrometer itself. The spectrometer is the section of the system that either by interference plus detection or by dispersion plus detection that "signal" amplitude versus energy/frequency signals are measured. Particularly in Raman spectroscopy, optical signals carrying desired "information" about the analyte are extraordinarily weak and require special considerations when measuring. We will discuss here the use of compact spectrometers and a micro-mirror array system (used is the digital micro-mirror device (DMD) supplied by the DLP® Products group of

Applications of Raman spectroscopy to gemology.

PubMed

Bersani, Danilo; Lottici, Pier Paolo

2010-08-01

Being nondestructive and requiring short measurement times, a low amount of material, and no sample preparation, Raman spectroscopy is used for routine investigation in the study of gemstone inclusions and treatments and for the characterization of mounted gems. In this work, a review of the use of laboratory Raman and micro-Raman spectrometers and of portable Raman systems in the gemology field is given, focusing on gem identification and on the evaluation of the composition, provenance, and genesis of gems. Many examples are shown of the use of Raman spectroscopy as a tool for the identification of imitations, synthetic gems, and enhancement treatments in natural gemstones. Some recent developments are described, with particular attention being given to the semiprecious stone jade and to two important organic materials used in jewelry, i.e., pearls and corals.

Contributed Review: Experimental characterization of inverse piezoelectric strain in GaN HEMTs via micro-Raman spectroscopy

NASA Astrophysics Data System (ADS)

Bagnall, Kevin R.; Wang, Evelyn N.

2016-06-01

Micro-Raman thermography is one of the most popular techniques for measuring local temperature rise in gallium nitride (GaN) high electron mobility transistors with high spatial and temporal resolution. However, accurate temperature measurements based on changes in the Stokes peak positions of the GaN epitaxial layers require properly accounting for the stress and/or strain induced by the inverse piezoelectric effect. It is common practice to use the pinched OFF state as the unpowered reference for temperature measurements because the vertical electric field in the GaN buffer that induces inverse piezoelectric stress/strain is relatively independent of the gate bias. Although this approach has yielded temperature measurements that agree with those derived from the Stokes/anti-Stokes ratio and thermal models, there has been significant difficulty in quantifying the mechanical state of the GaN buffer in the pinched OFF state from changes in the Raman spectra. In this paper, we review the experimental technique of micro-Raman thermography and derive expressions for the detailed dependence of the Raman peak positions on strain, stress, and electric field components in wurtzite GaN. We also use a combination of semiconductor device modeling and electro-mechanical modeling to predict the stress and strain induced by the inverse piezoelectric effect. Based on the insights gained from our electro-mechanical model and the best values of material properties in the literature, we analyze changes in the E2 high and A1 (LO) Raman peaks and demonstrate that there are major quantitative discrepancies between measured and modeled values of inverse piezoelectric stress and strain. We examine many of the hypotheses offered in the literature for these discrepancies but conclude that none of them satisfactorily resolves these discrepancies. Further research is needed to determine whether the electric field components could be affecting the phonon frequencies apart from the inverse

Contributed Review: Experimental characterization of inverse piezoelectric strain in GaN HEMTs via micro-Raman spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bagnall, Kevin R.; Wang, Evelyn N.

2016-06-15

Micro-Raman thermography is one of the most popular techniques for measuring local temperature rise in gallium nitride (GaN) high electron mobility transistors with high spatial and temporal resolution. However, accurate temperature measurements based on changes in the Stokes peak positions of the GaN epitaxial layers require properly accounting for the stress and/or strain induced by the inverse piezoelectric effect. It is common practice to use the pinched OFF state as the unpowered reference for temperature measurements because the vertical electric field in the GaN buffer that induces inverse piezoelectric stress/strain is relatively independent of the gate bias. Although this approachmore » has yielded temperature measurements that agree with those derived from the Stokes/anti-Stokes ratio and thermal models, there has been significant difficulty in quantifying the mechanical state of the GaN buffer in the pinched OFF state from changes in the Raman spectra. In this paper, we review the experimental technique of micro-Raman thermography and derive expressions for the detailed dependence of the Raman peak positions on strain, stress, and electric field components in wurtzite GaN. We also use a combination of semiconductor device modeling and electro-mechanical modeling to predict the stress and strain induced by the inverse piezoelectric effect. Based on the insights gained from our electro-mechanical model and the best values of material properties in the literature, we analyze changes in the E{sub 2} high and A{sub 1} (LO) Raman peaks and demonstrate that there are major quantitative discrepancies between measured and modeled values of inverse piezoelectric stress and strain. We examine many of the hypotheses offered in the literature for these discrepancies but conclude that none of them satisfactorily resolves these discrepancies. Further research is needed to determine whether the electric field components could be affecting the phonon frequencies apart

Assessment of liver steatosis and fibrosis in rats using integrated coherent anti-Stokes Raman scattering and multiphoton imaging technique

NASA Astrophysics Data System (ADS)

Lin, Jian; Lu, Fake; Zheng, Wei; Xu, Shuoyu; Tai, Dean; Yu, Hanry; Huang, Zhiwei

2011-11-01

We report the implementation of a unique integrated coherent anti-Stokes Raman scattering (CARS), second-harmonic generation (SHG), and two-photon excitation fluorescence (TPEF) microscopy imaging technique developed for label-free monitoring of the progression of liver steatosis and fibrosis generated in a bile duct ligation (BDL) rat model. Among the 21 adult rats used in this study, 18 rats were performed with BDL surgery and sacrificed each week from weeks 1 to 6 (n = 3 per week), respectively; whereas 3 rats as control were sacrificed at week 0. Colocalized imaging of the aggregated hepatic fats, collagen fibrils, and hepatocyte morphologies in liver tissue is realized by using the integrated CARS, SHG, and TPEF technique. The results show that there are significant accumulations of hepatic lipid droplets and collagen fibrils associated with severe hepatocyte necrosis in BDL rat liver as compared to a normal liver tissue. The volume of normal hepatocytes keeps decreasing and the fiber collagen content in BDL rat liver follows a growing trend until week 6; whereas the hepatic fat content reaches a maximum in week 4 and then appears to stop growing in week 6, indicating that liver steatosis and fibrosis induced in a BDL rat liver model may develop at different rates. This work demonstrates that the integrated CARS and multiphoton microscopy imaging technique has the potential to provide an effective means for early diagnosis and detection of liver steatosis and fibrosis without labeling.

Assessment of liver steatosis and fibrosis in rats using integrated coherent anti-Stokes Raman scattering and multiphoton imaging technique.

PubMed

Lin, Jian; Lu, Fake; Zheng, Wei; Xu, Shuoyu; Tai, Dean; Yu, Hanry; Huang, Zhiwei

2011-11-01

We report the implementation of a unique integrated coherent anti-Stokes Raman scattering (CARS), second-harmonic generation (SHG), and two-photon excitation fluorescence (TPEF) microscopy imaging technique developed for label-free monitoring of the progression of liver steatosis and fibrosis generated in a bile duct ligation (BDL) rat model. Among the 21 adult rats used in this study, 18 rats were performed with BDL surgery and sacrificed each week from weeks 1 to 6 (n = 3 per week), respectively; whereas 3 rats as control were sacrificed at week 0. Colocalized imaging of the aggregated hepatic fats, collagen fibrils, and hepatocyte morphologies in liver tissue is realized by using the integrated CARS, SHG, and TPEF technique. The results show that there are significant accumulations of hepatic lipid droplets and collagen fibrils associated with severe hepatocyte necrosis in BDL rat liver as compared to a normal liver tissue. The volume of normal hepatocytes keeps decreasing and the fiber collagen content in BDL rat liver follows a growing trend until week 6; whereas the hepatic fat content reaches a maximum in week 4 and then appears to stop growing in week 6, indicating that liver steatosis and fibrosis induced in a BDL rat liver model may develop at different rates. This work demonstrates that the integrated CARS and multiphoton microscopy imaging technique has the potential to provide an effective means for early diagnosis and detection of liver steatosis and fibrosis without labeling.

The Impact of Array Detectors on Raman Spectroscopy

ERIC Educational Resources Information Center

Denson, Stephen C.; Pommier, Carolyn J. S.; Denton, M. Bonner

2007-01-01

The impact of array detectors in the field of Raman spectroscopy and all low-light-level spectroscopic techniques is examined. The high sensitivity of array detectors has allowed Raman spectroscopy to be used to detect compounds at part per million concentrations and to perform Raman analyses at advantageous wavelengths.

Manipulation of coherent Stokes light by transient stimulated Raman scattering in gas filled hollow-core PCF.

PubMed

Chugreev, Alexey; Nazarkin, Alexander; Abdolvand, Amir; Nold, Johannes; Podlipensky, Alexander; Russell, Philip St J

2009-05-25

Transient stimulated Raman scattering is investigated in methane-filled hollow-core photonic crystal fiber. Using frequency-chirped ps-pulses at 1.06 microm as pump and tunable CW-radiation as Stokes seed, the vibrational excitation of the CH(4) molecules can be controlled on the sub T(2) time-scale. In this way the generated Stokes pulse can be phase-locked to the pump pulse and its spectrum manipulated.

Chemical analysis of acoustically levitated drops by Raman spectroscopy.

PubMed

Tuckermann, Rudolf; Puskar, Ljiljana; Zavabeti, Mahta; Sekine, Ryo; McNaughton, Don

2009-07-01

An experimental apparatus combining Raman spectroscopy with acoustic levitation, Raman acoustic levitation spectroscopy (RALS), is investigated in the field of physical and chemical analytics. Whereas acoustic levitation enables the contactless handling of microsized samples, Raman spectroscopy offers the advantage of a noninvasive method without complex sample preparation. After carrying out some systematic tests to probe the sensitivity of the technique to drop size, shape, and position, RALS has been successfully applied in monitoring sample dilution and preconcentration, evaporation, crystallization, an acid-base reaction, and analytes in a surface-enhanced Raman spectroscopy colloidal suspension.

Raman spectroscopy of saliva as a perspective method for periodontitis diagnostics Raman spectroscopy of saliva

NASA Astrophysics Data System (ADS)

Gonchukov, S.; Sukhinina, A.; Bakhmutov, D.; Minaeva, S.

2012-01-01

In view of its potential for biological tissues analyses at a molecular level, Raman spectroscopy in optical range has been the object of biomedical research for the last years. The main aim of this work is the development of Raman spectroscopy for organic content identifying and determination of biomarkers of saliva at a molecular level for periodontitis diagnostics. Four spectral regions were determined: 1155 and 1525 cm-1, 1033 and 1611 cm-1, which can be used as biomarkers of this widespread disease.

Coherent anti-Stokes Raman scattering microscope with a high-signal-to-noise ratio, high stability, and high-speed imaging for live cell observation

NASA Astrophysics Data System (ADS)

Hayashi, Shinichi; Takimoto, Shinichi; Hashimoto, Takeshi

2007-02-01

Coherent anti-Stokes Raman scattering (CARS) microscopy, which can produce images of specific molecules without staining, has attracted the attention of researchers, as it matches the need for molecular imaging and pathway analysis of live cells. In particular, there have been an increasing number of CARS experimental results regarding lipids in live cells, which cannot be fluorescently tagged while keeping the cells alive. One of the important applications of lipid research is for the metabolic syndrome. Since the metabolic syndrome is said to be related to the lipids in lipocytes, blood, arterial vessels, and so on, the CARS technique is expected to find application in this field. However, CARS microscopy requires a pair of picosecond laser pulses, which overlap both temporally and spatially. This makes the optical adjustments of a CARS microscope challenging. The authors developed a CARS unit that includes optics for easy and stable adjustment of the overlap of these laser pulses. Adding the CARS unit to a laser scanning microscope provides CARS images of a high signal-to-noise ratio, with an acquisition rate as high as 2 microseconds per pixel. Thus, images of fast-moving lipid droplets in Hela cells were obtained.

Determining the Authenticity of Gemstones Using Raman Spectroscopy

NASA Astrophysics Data System (ADS)

Aponick, Aaron; Marchozzi, Emedio; Johnston, Cynthia R.; Wigal, Carl T.

1998-04-01

The benefits of laser spectroscopy in the undergraduate curriculum have been the focus of several recent articles in this journal. Raman spectroscopy has been of particular interest since the similarities of Raman to conventional infrared spectroscopy make the interpretation of spectral data well within undergraduate comprehension. In addition, the accessibility to this technology is now within the reach of most undergraduate institutions. This paper reports the development of an experiment using Raman spectroscopy which determines the authenticity of both diamonds and pearls. The resulting spectra provide an introduction to vibrational spectroscopy and can be used in a variety of laboratory courses ranging from introductory chemistry to instrumental analysis.

Rapid identification of staphylococci by Raman spectroscopy.

PubMed

Rebrošová, Katarína; Šiler, Martin; Samek, Ota; Růžička, Filip; Bernatová, Silvie; Holá, Veronika; Ježek, Jan; Zemánek, Pavel; Sokolová, Jana; Petráš, Petr

2017-11-01

Clinical treatment of the infections caused by various staphylococcal species differ depending on the actual cause of infection. Therefore, it is necessary to develop a fast and reliable method for identification of staphylococci. Raman spectroscopy is an optical method used in multiple scientific fields. Recent studies showed that the method has a potential for use in microbiological research, too. Our work here shows a possibility to identify staphylococci by Raman spectroscopy. We present a method that enables almost 100% successful identification of 16 of the clinically most important staphylococcal species directly from bacterial colonies grown on a Mueller-Hinton agar plate. We obtained characteristic Raman spectra of 277 staphylococcal strains belonging to 16 species from a 24-hour culture of each strain grown on the Mueller-Hinton agar plate using the Raman instrument. The results show that it is possible to distinguish among the tested species using Raman spectroscopy and therefore it has a great potential for use in routine clinical diagnostics.

Near-field Raman spectroscopy

NASA Astrophysics Data System (ADS)

Ayars, Eric James

2000-10-01

The purpose of this research is to investigate differences observed between Raman spectra when seen through a Near-field Scanning Optical Microscope (NSOM) and spectra of the same materials in conventional Raman or micro-Raman configurations. One source of differences in the observed spectra is a strong z polarized component in the near-field radiation; observations of the magnitude of this effect are compared with theoretical predictions for the field intensity near an NSOM tip. Large electric field gradients near the sharp NSOM probe may be another source of differences. This Gradient-Field Raman (GFR) effect was observed, and there is good evidence that it plays a significant role in Surface-Enhanced Raman Spectroscopy (SERS). The NSOM data seen, however, are not sufficient to prove conclusively that the spectral variations seen are due to the field gradients.

High-order Stokes generation in a KTP Raman laser pumped by a passively Q-switched ND:YLF laser

NASA Astrophysics Data System (ADS)

Wang, Maorong; Zhong, Kai; Mei, Jialin; Guo, Shibei; Xu, Degang; Yao, Jianquan

2015-12-01

High-order Stokes wave was observed in an x-cut KTP crystal based on stimulated Raman scattering (SRS) pumped by a passively Q-switched Nd:YLF laser with a Cr4+:YAG saturable absorber. Output spectra including the fundamental wave at 1047 nm and six Stokes wavelengths at 1077 nm, 1110 nm, 1130 nm, 1143 nm, 1164 nm, 1180 nm based on two Raman frequency shift at 267.4 cm-1 and 693.0 cm-1 were obtained simultaneously. We also detected green light generation with output power of 12 mW from self frequency mixing in the KTP crystal. The maximum total output power reached 452 mW at the repetition frequency of 8.1 kHz, corresponding to the optical-to-optical conversion efficiency of 4.61% and pump-to-Raman conversion efficiency of 3.6%.

Three-beam double stimulated Raman scatterings: Cascading configuration

NASA Astrophysics Data System (ADS)

Rao, B. Jayachander; Cho, Minhaeng

2018-03-01

Two-beam stimulated Raman scattering (SRS) has been used in diverse label-free spectroscopy and imaging applications of live cells, biological tissues, and functional materials. Recently, we developed a theoretical framework for the three-beam double SRS processes that involve pump, Stokes, and depletion beams, where the pump-Stokes and pump-depletion SRS processes compete with each other. It was shown that the net Stokes gain signal can be suppressed by increasing the depletion beam intensity. The theoretical prediction has been experimentally confirmed recently. In the previous scheme for a selective suppression of one SRS by making it compete with another SRS, the two SRS processes occur in a parallel manner. However, there is another possibility of three-beam double SRS scheme that can be of use to suppress either Raman gain of the Stokes beam or Raman loss of the pump beam by depleting the Stokes photons with yet another SRS process induced by the pair of Stokes and another (second) Stokes beam. This three-beam double SRS process resembles a cascading energy transfer process from the pump beam to the first Stokes beam (SRS-1) and subsequently from the first Stokes beam to the second Stokes beam (SRS-2). Here, the two stimulated Raman gain-loss processes are associated with two different Raman-active vibrational modes of solute molecule. In the present theory, both the radiation and the molecules are treated quantum mechanically. We then show that the cascading-type three-beam double SRS can be described by coupled differential equations for the photon numbers of the pump and Stokes beams. From the approximate solutions as well as exact numerical calculation results for the coupled differential equations, a possibility of efficiently suppressing the stimulated Raman loss of the pump beam by increasing the second Stokes beam intensity is shown and discussed. To further prove a potential use of this scheme for developing a super-resolution SRS microscopy, we

Detection of anions by normal Raman spectroscopy and surface-enhanced Raman spectroscopy of cationic-coated substrates.

PubMed

Mosier-Boss, P A; Lieberman, S H

2003-09-01

The use of normal Raman spectroscopy and surface-enhanced Raman spectroscopy (SERS) of cationic-coated silver and gold substrates to detect polyatomic anions in aqueous environments is examined. For normal Raman spectroscopy, using near-infrared excitation, linear concentration responses were observed. Detection limits varied from 84 ppm for perchlorate to 2600 ppm for phosphate. In general, detection limits in the ppb to ppm concentration range for the polyatomic anions were achieved using cationic-coated SERS substrates. Adsorption of the polyatomic anions on the cationic-coated SERS substrates was described by a Frumkin isotherm. The SERS technique could not be used to detect dichromate, as this anion reacted with the coatings to form thiol esters. A competitive complexation method was used to evaluate the interaction of chloride ion with the cationic coatings. Hydrogen bonding and pi-pi interactions play significant roles in the selectivity of the cationic coatings.

Hyper-Raman spectroscopy of Earth related materials

NASA Astrophysics Data System (ADS)

Hellwig, H.

2004-12-01

Raman and infrared spectroscopy proved extremely successful in obtaining structural information and thermodynamic data on samples under high pressure conditions in a diamond anvil cell [1,2]. With substantial advances in CCD detector technology and the possibility to focus visible laser light down to several microns, Raman spectroscopy can nowadays be regarded one of the standard techniques for diamond anvil cell investigations. Nevertheless, Raman scattering suffers from often strong fluorescence and the strong Raman signal of the diamonds. Infrared spectroscopy is limited by the sample size and the diffraction limit of mid- or far-infrared radiation. With increasing pressure, diamonds also show strong infrared activity, which can interfere with the signal from the sample. Detectors in the mid- and far-infrared are inherently noisy, often leading to low signal-to-noise ratios for infrared measurements. With new techniques and instrumentation available, such as low noise CCD cameras and stable diode-pumped solid state laser systems, more demanding techniques become feasible as well. Especially hyper-Raman scattering, a nonlinear optical variant of infrared spectroscopy, can be used on a more routine basis for the first time. Pioneering work in the 70s and 80s have explored some of the capabilities of Hyper-Raman spectroscopy [3]. Unlike infrared spectroscopy, Hyper-Raman is not limited by the diffraction limit of mid- or far-infrared radiation, typically restricting the lower frequency limit to several hundred wave numbers. The major advantages of hyper-Raman are essentially background free spectra and the use of wavelengths in the near-infrared and visible, making possible micro focusing and taking advantage of high efficiencies, low noise, and smooth wavelength dependencies of CCD detectors. Hyper-Raman does not suffer from saturation caused by strong absorption in the infrared and is therefore less sensitive to surface effects. For centrosymmetric materials

Raman spectroscopy of bone metastasis

NASA Astrophysics Data System (ADS)

Esmonde-White, Karen A.; Sottnik, Joseph; Morris, Michael; Keller, Evan

2012-02-01

Raman spectroscopy of bone has been used to characterize chemical changes occurring in diseases such as osteoporosis, osteoarthritis and osteomyelitis. Metastasis of cancer into bone causes changes to bone quality that are similar to those observed in osteoporosis, such as decreased bone strength, but with an accelerated timeframe. In particular, osteolytic (bone degrading) lesions in bone metastasis have a marked effect on patient quality of life because of increased risk of fractures, pain, and hypercalcemia. We use Raman spectroscopy to examine bone from two different mouse models of osteolytic bone metastasis. Raman spectroscopy measures physicochemical information which cannot be obtained through standard biochemical and histological measurements. This study was reviewed and approved by the University of Michigan University Committee on the Care and Use of Animals. Two mouse models of prostate cancer bone metastasis, RM1 (n=3) and PC3-luc (n=4) were examined. Tibiae were injected with RM1 or PC3-luc cancer cells, while the contralateral tibiae received a placebo injection for use as controls. After 2 weeks of incubation, the mice were sacrificed and the tibiae were examined by Raman microspectroscopy (λ=785 nm). Spectroscopic markers corresponding to mineral stoichiometry, bone mineralization, and mineral crystallinity were compared in spectra from the cancerous and control tibiae. X-ray imaging of the tibia confirmed extensive osteolysis in the RM1 mice, with tumor invasion into adjoining soft tissue and moderate osteolysis in the PC3-luc mice. Raman spectroscopic markers indicate that osteolytic lesions are less mineralized than normal bone tissue, with an altered mineral stoichiometry and crystallinity.

Time- and frequency-dependent model of time-resolved coherent anti-Stokes Raman scattering (CARS) with a picosecond-duration probe pulse

NASA Astrophysics Data System (ADS)

Stauffer, Hans U.; Miller, Joseph D.; Slipchenko, Mikhail N.; Meyer, Terrence R.; Prince, Benjamin D.; Roy, Sukesh; Gord, James R.

2014-01-01

The hybrid femtosecond/picosecond coherent anti-Stokes Raman scattering (fs/ps CARS) technique presents a promising alternative to either fs time-resolved or ps frequency-resolved CARS in both gas-phase thermometry and condensed-phase excited-state dynamics applications. A theoretical description of time-dependent CARS is used to examine this recently developed probe technique, and quantitative comparisons of the full time-frequency evolution show excellent accuracy in predicting the experimental vibrational CARS spectra obtained for two model systems. The interrelated time- and frequency-domain spectral signatures of gas-phase species produced by hybrid fs/ps CARS are explored with a focus on gas-phase N2 vibrational CARS, which is commonly used as a thermometric diagnostic of combusting flows. In particular, we discuss the merits of the simple top-hat spectral filter typically used to generate the ps-duration hybrid fs/ps CARS probe pulse, including strong discrimination against non-resonant background that often contaminates CARS signal. It is further demonstrated, via comparison with vibrational CARS results on a time-evolving solvated organic chromophore, that this top-hat probe-pulse configuration can provide improved spectral resolution, although the degree of improvement depends on the dephasing timescales of the observed molecular modes and the duration and timing of the narrowband final pulse. Additionally, we discuss the virtues of a frequency-domain Lorentzian probe-pulse lineshape and its potential for improving the hybrid fs/ps CARS technique as a diagnostic in high-pressure gas-phase thermometry applications.

Time- and frequency-dependent model of time-resolved coherent anti-Stokes Raman scattering (CARS) with a picosecond-duration probe pulse.

PubMed

Stauffer, Hans U; Miller, Joseph D; Slipchenko, Mikhail N; Meyer, Terrence R; Prince, Benjamin D; Roy, Sukesh; Gord, James R

2014-01-14

The hybrid femtosecond∕picosecond coherent anti-Stokes Raman scattering (fs∕ps CARS) technique presents a promising alternative to either fs time-resolved or ps frequency-resolved CARS in both gas-phase thermometry and condensed-phase excited-state dynamics applications. A theoretical description of time-dependent CARS is used to examine this recently developed probe technique, and quantitative comparisons of the full time-frequency evolution show excellent accuracy in predicting the experimental vibrational CARS spectra obtained for two model systems. The interrelated time- and frequency-domain spectral signatures of gas-phase species produced by hybrid fs∕ps CARS are explored with a focus on gas-phase N2 vibrational CARS, which is commonly used as a thermometric diagnostic of combusting flows. In particular, we discuss the merits of the simple top-hat spectral filter typically used to generate the ps-duration hybrid fs∕ps CARS probe pulse, including strong discrimination against non-resonant background that often contaminates CARS signal. It is further demonstrated, via comparison with vibrational CARS results on a time-evolving solvated organic chromophore, that this top-hat probe-pulse configuration can provide improved spectral resolution, although the degree of improvement depends on the dephasing timescales of the observed molecular modes and the duration and timing of the narrowband final pulse. Additionally, we discuss the virtues of a frequency-domain Lorentzian probe-pulse lineshape and its potential for improving the hybrid fs∕ps CARS technique as a diagnostic in high-pressure gas-phase thermometry applications.

Ultrafast and nonlinear surface-enhanced Raman spectroscopy.

PubMed

Gruenke, Natalie L; Cardinal, M Fernanda; McAnally, Michael O; Frontiera, Renee R; Schatz, George C; Van Duyne, Richard P

2016-04-21

Ultrafast surface-enhanced Raman spectroscopy (SERS) has the potential to study molecular dynamics near plasmonic surfaces to better understand plasmon-mediated chemical reactions such as plasmonically-enhanced photocatalytic or photovoltaic processes. This review discusses the combination of ultrafast Raman spectroscopic techniques with plasmonic substrates for high temporal resolution, high sensitivity, and high spatial resolution vibrational spectroscopy. First, we introduce background information relevant to ultrafast SERS: the mechanisms of surface enhancement in Raman scattering, the characterization of plasmonic materials with ultrafast techniques, and early complementary techniques to study molecule-plasmon interactions. We then discuss recent advances in surface-enhanced Raman spectroscopies with ultrafast pulses with a focus on the study of molecule-plasmon coupling and molecular dynamics with high sensitivity. We also highlight the challenges faced by this field by the potential damage caused by concentrated, highly energetic pulsed fields in plasmonic hotspots, and finally the potential for future ultrafast SERS studies.

Scanning Angle Raman spectroscopy in polymer thin film characterization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nguyen, Vy H.T.

The focus of this thesis is the application of Raman spectroscopy for the characterization of thin polymer films. Chapter 1 provides background information and motivation, including the fundamentals of Raman spectroscopy for chemical analysis, scanning angle Raman scattering and scanning angle Raman scattering for applications in thin polymer film characterization. Chapter 2 represents a published manuscript that focuses on the application of scanning angle Raman spectroscopy for the analysis of submicron thin films with a description of methodology for measuring the film thickness and location of an interface between two polymer layers. Chapter 3 provides an outlook and future directionsmore » for the work outlined in this thesis. Appendix A, contains a published manuscript that outlines the use of Raman spectroscopy to aid in the synthesis of heterogeneous catalytic systems. Appendix B and C contain published manuscripts that set a foundation for the work presented in Chapter 2.« less

Nanosecond retinal structure changes in K-590 during the room-temperature bacteriorhodopsin photocycle: picosecond time-resolved coherent anti-stokes Raman spectroscopy.

PubMed

Weidlich, O; Ujj, L; Jäger, F; Atkinson, G H

1997-05-01

Time-resolved vibrational spectra are used to elucidate the structural changes in the retinal chromophore within the K-590 intermediate that precedes the formation of the L-550 intermediate in the room-temperature (RT) bacteriorhodopsin (BR) photocycle. Measured by picosecond time-resolved coherent anti-Stokes Raman scattering (PTR/CARS), these vibrational data are recorded within the 750 cm-1 to 1720 cm-1 spectral region and with time delays of 50-260 ns after the RT/BR photocycle is optically initiated by pulsed (< 3 ps, 1.75 nJ) excitation. Although K-590 remains structurally unchanged throughout the 50-ps to 1-ns time interval, distinct structural changes do appear over the 1-ns to 260-ns period. Specifically, comparisons of the 50-ps PTR/CARS spectra with those recorded with time delays of 1 ns to 260 ns reveal 1) three types of changes in the hydrogen-out-of-plane (HOOP) region: the appearance of a strong, new feature at 984 cm-1; intensity decreases for the bands at 957 cm-1, 952 cm-1, and 939 cm-1; and small changes intensity and/or frequency of bands at 855 cm-1 and 805 cm-1; and 2) two types of changes in the C-C stretching region: the intensity increase in the band at 1196 cm-1 and small intensity changes and/or frequency shifts for bands at 1300 cm-1 and 1362 cm-1. No changes are observed in the C = C stretching region, and no bands assignable to the Schiff base stretching mode (C = NH+) mode are found in any of the PTR/CARS spectra assignable to K-590. These PTR/CARS data are used, together with vibrational mode assignments derived from previous work, to characterize the retinal structural changes in K-590 as it evolves from its 3.5-ps formation (ps/K-590) through the nanosecond time regime (ns/K-590) that precedes the formation of L-550. The PTR/CARS data suggest that changes in the torsional modes near the C14-C15 = N bonds are directly associated with the appearance of ns/K-590, and perhaps with the KL intermediate proposed in earlier studies. These

Raman spectra and DFT calculations for botryococcene and methylsqualene hydrocarbons from the B race of the green microalga Botryococcus braunii

NASA Astrophysics Data System (ADS)

Tatli, Mehmet; Chun, Hye Jin; Camp, Charles H.; Li, Jingting; Cicerone, Marcus T.; Shih, Wei-Chuan; Laane, Jaan; Devarenne, Timothy P.

2017-11-01

Botryococcus braunii, a green colonial microalga, is a prodigious producer of liquid hydrocarbon oils that can be used as renewable feedstocks for producing combustion engine fuels. The B race of B. braunii mainly produces the triterpene hydrocarbons known as botryococcenes, which have over twenty known structures. Minor hydrocarbons in the B race include the triterpene methylsqualenes. Here we report an examination of the molecular structure for ten botryococcenes and five methylsqualenes using Raman spectroscopy and density functional theory (DFT) calculations in an effort to distinguish between these structurally similar molecules by spectroscopic approaches. The DFT calculations show that these molecules have between 243 and 271 vibrational frequencies. A comparison of the experimental Raman spectroscopy and DFT calculations indicates several spectral regions such as those for ν(Cdbnd C) stretching, CH2/CH3 bending, and ring bending can be used to distinguish between these molecules. In an extension of this analysis, a broadband coherent anti-Stokes Raman spectroscopy (BCARS) analysis was used to clearly distinguish between several botryococcenes isomers.

Micro-Raman spectroscopy for meat type detection

NASA Astrophysics Data System (ADS)

De Biasio, M.; Stampfer, P.; Leitner, R.; Huck, C. W.; Wiedemair, V.; Balthasar, D.

2015-06-01

The recent horse meat scandal in Europe increased the demand for optical sensors that can identify meat type. Micro-Raman spectroscopy is a promising technique for the discrimination of meat types. Here, we present micro-Raman measurements of chicken, pork, turkey, mutton, beef and horse meat test samples. The data was analyzed with different combinations of data normalization and classification approaches. Our results show that Raman spectroscopy can discriminate between different meat types. Red and white meat are easily discriminated, however a sophisticated chemometric model is required to discriminate species within these groups.

Three-dimensional spectroscopy of vibrational energy in liquids: nitromethane and acetonitrile.

PubMed

Sun, Yuxiao; Pein, Brandt C; Dlott, Dana D

2013-12-12

We introduce a novel type of three-dimensional (3D) spectroscopy to study vibrational energy transfer, where an IR pulse tunable through the CH-stretching and CD-stretching regions was used to create parent vibrational excitations in liquids and a visible probe pulse was used to generate both Stokes and anti-Stokes Raman spectra as a function of delay time. The Raman spectra determine how much vibrational excitation was present in each probed state. The three dimensions are the wavenumber of the pumped state, the wavenumber of the probed state, and the time interval. The technique was used to study nitromethane (NM) and acetonitrile (ACN) and their deuterated analogues at ambient temperature. The 3D spectra were quite complicated. Three types of artifacts due to nonlinear light scattering were observed. Along the diagonal were two fundamental CH-stretch (or CD-stretch) transitions and several weaker combination bands or overtone transitions. Because Raman spectroscopy allows us to simultaneously probe a wide wavenumber region, for every diagonal peak, there were ∼10 off-diagonal peaks. The cross-peaks at shorter delay times reveal the nature of the initial excitation by showing which lower-wavenumber excitations were produced along with the pumped CH-stretch or CD-stretch. The longer-time spectra characterized vibrational energy relaxation processes, and showed how daughter vibrations were generated by different parent excitations.

Raman spectroscopy as a process analytical technology for pharmaceutical manufacturing and bioprocessing.

PubMed

Esmonde-White, Karen A; Cuellar, Maryann; Uerpmann, Carsten; Lenain, Bruno; Lewis, Ian R

2017-01-01

Adoption of Quality by Design (QbD) principles, regulatory support of QbD, process analytical technology (PAT), and continuous manufacturing are major factors effecting new approaches to pharmaceutical manufacturing and bioprocessing. In this review, we highlight new technology developments, data analysis models, and applications of Raman spectroscopy, which have expanded the scope of Raman spectroscopy as a process analytical technology. Emerging technologies such as transmission and enhanced reflection Raman, and new approaches to using available technologies, expand the scope of Raman spectroscopy in pharmaceutical manufacturing, and now Raman spectroscopy is successfully integrated into real-time release testing, continuous manufacturing, and statistical process control. Since the last major review of Raman as a pharmaceutical PAT in 2010, many new Raman applications in bioprocessing have emerged. Exciting reports of in situ Raman spectroscopy in bioprocesses complement a growing scientific field of biological and biomedical Raman spectroscopy. Raman spectroscopy has made a positive impact as a process analytical and control tool for pharmaceutical manufacturing and bioprocessing, with demonstrated scientific and financial benefits throughout a product's lifecycle.

Principles and applications of Raman spectroscopy in pharmaceutical drug discovery and development.

PubMed

Gala, Urvi; Chauhan, Harsh

2015-02-01

In recent years, Raman spectroscopy has become increasingly important as an analytical technique in various scientific areas of research and development. This is partly due to the technological advancements in Raman instrumentation and partly due to detailed fingerprinting that can be derived from Raman spectra. Its versatility of applications, rapidness of collection and easy analysis have made Raman spectroscopy an attractive analytical tool. The following review describes Raman spectroscopy and its application within the pharmaceutical industry. The authors explain the theory of Raman scattering and its variations in Raman spectroscopy. The authors also highlight how Raman spectra are interpreted, providing examples. Raman spectroscopy has a number of potential applications within drug discovery and development. It can be used to estimate the molecular activity of drugs and to establish a drug's physicochemical properties such as its partition coefficient. It can also be used in compatibility studies during the drug formulation process. Raman spectroscopy's immense potential should be further investigated in future.

Periodontitis diagnostics using resonance Raman spectroscopy on saliva

NASA Astrophysics Data System (ADS)

Gonchukov, S.; Sukhinina, A.; Bakhmutov, D.; Biryukova, T.; Tsvetkov, M.; Bagratashvily, V.

2013-07-01

In view of its wealth of molecular information, Raman spectroscopy has been the subject of active biomedical research. The aim of this work is Raman spectroscopy (RS) application for the determination of molecular biomarkers in saliva with the objective of early periodontitis detection. As was shown in our previous study, carotenoids contained in saliva can be molecular fingerprint information for the periodontitis level. It is shown here that the carotenoid RS lines at wavenumbers of 1156 and 1524 cm-1 can be easily detected and serve as reliable biomarkers of periodontitis using resonance Raman spectroscopy of dry saliva.

Raman Spectroscopy of Microbial Pigments

PubMed Central

Edwards, Howell G. M.; Oren, Aharon

2014-01-01

Raman spectroscopy is a rapid nondestructive technique providing spectroscopic and structural information on both organic and inorganic molecular compounds. Extensive applications for the method in the characterization of pigments have been found. Due to the high sensitivity of Raman spectroscopy for the detection of chlorophylls, carotenoids, scytonemin, and a range of other pigments found in the microbial world, it is an excellent technique to monitor the presence of such pigments, both in pure cultures and in environmental samples. Miniaturized portable handheld instruments are available; these instruments can be used to detect pigments in microbiological samples of different types and origins under field conditions. PMID:24682303

Approximate chemical analysis of volcanic glasses using Raman spectroscopy

PubMed Central

Morgavi, Daniele; Hess, Kai‐Uwe; Neuville, Daniel R.; Borovkov, Nikita; Perugini, Diego; Dingwell, Donald B.

2015-01-01

The effect of chemical composition on the Raman spectra of a series of natural calcalkaline silicate glasses has been quantified by performing electron microprobe analyses and obtaining Raman spectra on glassy filaments (~450 µm) derived from a magma mingling experiment. The results provide a robust compositionally‐dependent database for the Raman spectra of natural silicate glasses along the calcalkaline series. An empirical model based on both the acquired Raman spectra and an ideal mixing equation between calcalkaline basaltic and rhyolitic end‐members is constructed enabling the estimation of the chemical composition and degree of polymerization of silicate glasses using Raman spectra. The model is relatively insensitive to acquisition conditions and has been validated using the MPI‐DING geochemical standard glasses1 as well as further samples. The methods and model developed here offer several advantages compared with other analytical and spectroscopic methods such as infrared spectroscopy, X‐ray fluorescence spectroscopy, electron and ion microprobe analyses, inasmuch as Raman spectroscopy can be performed with a high spatial resolution (1 µm2) without the need for any sample preparation as a nondestructive technique. This study represents an advance in efforts to provide the first database of Raman spectra for natural silicate glasses and yields a new approach for the treatment of Raman spectra, which allows us to extract approximate information about the chemical composition of natural silicate glasses using Raman spectroscopy. We anticipate its application in handheld in situ terrestrial field studies of silicate glasses under extreme conditions (e.g. extraterrestrial and submarine environments). © 2015 The Authors Journal of Raman Spectroscopy Published by John Wiley & Sons Ltd PMID:27656038

Modulated Raman Spectroscopy for Enhanced Cancer Diagnosis at the Cellular Level

PubMed Central

De Luca, Anna Chiara; Dholakia, Kishan; Mazilu, Michael

2015-01-01

Raman spectroscopy is emerging as a promising and novel biophotonics tool for non-invasive, real-time diagnosis of tissue and cell abnormalities. However, the presence of a strong fluorescence background is a key issue that can detract from the use of Raman spectroscopy in routine clinical care. The review summarizes the state-of-the-art methods to remove the fluorescence background and explores recent achievements to address this issue obtained with modulated Raman spectroscopy. This innovative approach can be used to extract the Raman spectral component from the fluorescence background and improve the quality of the Raman signal. We describe the potential of modulated Raman spectroscopy as a rapid, inexpensive and accurate clinical tool to detect the presence of bladder cancer cells. Finally, in a broader context, we show how this approach can greatly enhance the sensitivity of integrated Raman spectroscopy and microfluidic systems, opening new prospects for portable higher throughput Raman cell sorting. PMID:26110401

Vibrational spectrum of the K-590 intermediate in the bacteriorhodopsin photocycle at room temperature: picosecond time-resolved resonance coherent anti-Raman spectroscopy

NASA Astrophysics Data System (ADS)

Ujj, L.; Jäger, F.; Popp, A.; Atkinson, G. H.

1996-12-01

The vibrational spectrum of the K-590 intermediate, thought to contribute significantly to the energy storage and transduction mechanism in the bacteriorhodopsin (BR) photocycle, is measured at room temperature using picosecond time-resolved resonance coherent anti-Stokes Raman scattering (PTR/CARS). The room-temperature BR photocycle is initiated by the 3 ps, 570 nm excitation of the ground-state species, BR-570, prepared in both H 2O and D 2O suspensions of BR. PTR/CARS data, recorded 50 ps after BR-570 excitation, at which time only BR-570 and K-590 are present, have an excellent S/N which provides a significantly more detailed view of the K-590 vibrational degrees of freedom than previously available. Two picosecond (6 ps FWHM) laser pulses, ω1 (633.4 nm) and ωS (675-700 nm), are used to record PTR/CARS data via electronic resonance enhancement in both BR-570 and K-590, each of which contains a distinct retinal structure (assigned as 13- rans, 15- anti, 13- cis, respectively). To obtain the vibrational spectrum of K-590 separately, the PTR/CARS spectra from the mixture of isomeric retinals is quantitatively analyzed in terms of third-order susceptibility ( η(3)) relationships. PTR/CARS spectra of K-590 recorded from both H 2O and D 2O suspensions of BR are compared with the analogous vibrational data obtained via spontaneous resonance Raman (RR) scattering at both low (77 K) and room temperature. Analyses of these vibrational spectra identify temperature-dependent effects and changes assignable to the substitution of deuterium at the Schiff-base nitrogen not previously reported.

Raman analysis of phonon modes in a short period AlN/GaN superlattice

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sarkar, Ketaki; Datta, Debopam; Gosztola, David J.

AlN/GaN-based optoelectronic devices have been the subject of intense research underlying the commercialization of efficient devices. Areas of considerable interest are the study of their lattice dynamics, phonon transport, and electron-phonon interactions specific to the interface of these heterostructures which results in additional optical phonon modes known as interface phonon modes. In this study, the framework of the dielectric continuum model (DCM) has been used to compare and analyze the optical phonon modes obtained from experimental Raman scattering measurements on AlN/GaN short-period superlattices. We have observed the localized E2(high), A1(LO) and the E1(TO) modes in superlattice measurements at frequencies shiftedmore » from their bulk values. To the best of our knowledge, the nanostructures used in these studies are among the smallest yielding useful Raman signatures for the interface modes. In addition, we have also identified an additional spread of interface phonon modes in the TO range resulting from the superlattice periodicity. The Raman signature contribution from the underlying AlxGa1-xN ternary has also been observed and analyzed. A temperature calibrationwas done based on Stokes/anti-Stokes ratio of A1(LO) using Raman spectroscopy in a broad operating temperature range. Good agreement between the experimental results and theoretically calculated calibration plot predicted using Bose-Einstein statistics was obtained.« less

Raman analysis of phonon modes in a short period AlN/GaN superlattice

NASA Astrophysics Data System (ADS)

Sarkar, Ketaki; Datta, Debopam; Gosztola, David J.; Shi, Fengyuan; Nicholls, Alan; Stroscio, Michael A.; Dutta, Mitra

2018-03-01

AlN/GaN-based optoelectronic devices have been the subject of intense research underlying the commercialization of efficient devices. Areas of considerable interest are the study of their lattice dynamics, phonon transport, and electron-phonon interactions specific to the interface of these heterostructures which results in additional optical phonon modes known as interface phonon modes. In this study, the framework of the dielectric continuum model (DCM) has been used to compare and analyze the optical phonon modes obtained from experimental Raman scattering measurements on AlN/GaN short-period superlattices. We have observed the localized E2(high), A1(LO) and the E1(TO) modes in superlattice measurements at frequencies shifted from their bulk values. To the best of our knowledge, the nanostructures used in these studies are among the smallest yielding useful Raman signatures for the interface modes. In addition, we have also identified an additional spread of interface phonon modes in the TO range resulting from the superlattice periodicity. The Raman signature contribution from the underlying AlxGa1-xN ternary has also been observed and analyzed. A temperature calibration was done based on Stokes/anti-Stokes ratio of A1(LO) using Raman spectroscopy in a broad operating temperature range. Good agreement between the experimental results and theoretically calculated calibration plot predicted using Bose-Einstein statistics was obtained.

Raman scattering measurements in flames using a tunable KrF excimer laser

NASA Technical Reports Server (NTRS)

Wehrmeyer, Joseph A.; Cheng, Tsarng-Sheng; Pitz, Robert W.

1992-01-01

A narrow-band tunable KrF excimer laser is used as a spontaneous vibrational Raman scattering source to demonstrate that single-pulse concentration and temperature measurements, with only minimal fluorescence interference, are possible for all major species (O2, N2, H2O, and H2) at all stoichiometries (fuel-lean to fuel rich) of H2-air flames. Photon-statistics-limited precisions in these instantaneous and spatially resolved single-pulse measurements are typically 5 percent, which are based on the relative standard deviations of single-pulse probability distributions. In addition to the single-pulse N2 Stokes/anti-Stokes ratio temperature measurement technique, a time-averaged temperature measurement technique is presented that matches the N2 Stokes Raman spectrum to theoretical spectra by using a single intermediate state frequency to account for near-resonance enhancement. Raman flame spectra in CH4-air flames are presented that have good signal-to-noise characteristics and show promise for single-pulse UV Raman measurements in hydrocarbon flames.

Raman Spectroscopy of Optically Trapped Single Biological Micro-Particles

PubMed Central

Redding, Brandon; Schwab, Mark J.; Pan, Yong-le

2015-01-01

The combination of optical trapping with Raman spectroscopy provides a powerful method for the study, characterization, and identification of biological micro-particles. In essence, optical trapping helps to overcome the limitation imposed by the relative inefficiency of the Raman scattering process. This allows Raman spectroscopy to be applied to individual biological particles in air and in liquid, providing the potential for particle identification with high specificity, longitudinal studies of changes in particle composition, and characterization of the heterogeneity of individual particles in a population. In this review, we introduce the techniques used to integrate Raman spectroscopy with optical trapping in order to study individual biological particles in liquid and air. We then provide an overview of some of the most promising applications of this technique, highlighting the unique types of measurements enabled by the combination of Raman spectroscopy with optical trapping. Finally, we present a brief discussion of future research directions in the field. PMID:26247952

Joint analyses by laser-induced breakdown spectroscopy (LIBS) and Raman spectroscopy at stand-off distances.

PubMed

Wiens, Roger C; Sharma, Shiv K; Thompson, Justin; Misra, Anupam; Lucey, Paul G

2005-08-01

Raman spectroscopy and laser-induced breakdown spectroscopy (LIBS) of solid samples have both been shown to be feasible with sample-to-instrument distances of many meters. The two techniques are very useful together, as the combination of elemental compositions from LIBS and molecular vibrational information from Raman spectroscopy strongly complement each other. Remote LIBS and Raman spectroscopy spectra were taken together on a number of mineral samples including sulfates, carbonates and silicates at a distance of 8.3 m. The complementary nature of these spectra is highlighted and discussed. A factor of approximately 20 difference in intensity was observed between the brightest Raman line of calcite, at optimal laser power, and the brighter Ca I LIBS emission line measured with 55 mJ/pulse laser power. LIBS and Raman spectroscopy have several obstacles to devising a single instrument capable of both techniques. These include the differing spectral ranges and required detection sensitivity. The current state of technology in these areas is discussed.

Raman and Photoluminescence Spectroscopy in Mineral Identification

NASA Astrophysics Data System (ADS)

Kuehn, J. W.

2014-06-01

Raman spectroscopy is particularly useful for rapid identification of minerals and gemstones. Raman spectrometers also allow PL studies for authentication of samples and geological provenance, diamond type screening and detection of HPHT treatments.

Remote Pulsed Laser Raman Spectroscopy System for Detecting Qater, Ice, and Hydrous Minerals

NASA Technical Reports Server (NTRS)

Garcia, Christopher S.; Abedin, M. Nuraul; Sharma, Shiv K.; Misra, Anupam K.; Ismail, Syed; Singh, Upendra; Refaat, Tamer F.; Elsayed-Ali, Hani; Sandford, Steve

2006-01-01

For exploration of planetary surfaces, detection of water and ice is of great interest in supporting existence of life on other planets. Therefore, a remote Raman spectroscopy system was demonstrated at NASA Langley Research Center in collaboration with University of Hawaii for detecting ice-water and hydrous minerals on planetary surfaces. In this study, a 532 nm pulsed laser is utilized as an excitation source to allow detection in high background radiation conditions. The Raman scattered signal is collected by a 4-inch telescope positioned in front of a spectrograph. The Raman spectrum is analyzed using a spectrograph equipped with a holographic super notch filter to eliminate Rayleigh scattering, and a holographic transmission grating that simultaneously disperses two spectral tracks onto the detector for higher spectral range. To view the spectrum, the spectrograph is coupled to an intensified charge-coupled device (ICCD), which allows detection of very weak Stokes line. The ICCD is operated in gated mode to further suppress effects from background radiation and long-lived fluorescence. The sample is placed at 5.6 m from the telescope, and the laser is mounted on the telescope in a coaxial geometry to achieve maximum performance. The system was calibrated using the spectral lines of a Neon lamp source. To evaluate the system, Raman standard samples such as calcite, naphthalene, acetone, and isopropyl alcohol were analyzed. The Raman evaluation technique was used to analyze water, ice and other hydrous minerals and results from these species are presented.

Application of Raman spectroscopy technology to studying Sudan I

NASA Astrophysics Data System (ADS)

Li, Gang; Zhang, Guoping; Chen, Chen

2006-06-01

Being an industrial dye, the Sudan I may have a toxic effect after oral intake on the body, and has recently been shown to cause cancer in rats, mice and rabbits. Because China and some other countries have detected the Sudan I in samples of the hot chilli powder and the chilli products, it is necessary to study the characteristics of this dye. As one kind of molecule scattering spectroscopy, Raman spectroscopy is characterized by the frequency excursion caused by interactions of molecules and photons. The frequency excursion reflects the margin between certain two vibrational or rotational energy states, and shows the information of the molecule. Because Raman spectroscopy can provides quick, easy, reproducible, and non-destructive analysis, both qualitative and quantitative, with no sample preparation required, Raman spectroscopy has been a particularly promising technique for analyzing the characteristics and structures of molecules, especially organic ones. Now, it has a broad application in biological, chemical, environmental and industrial applications. This paper firstly introduces Sudan I dye and the Raman spectroscopy technology, and then describes its application to the Sudan I. Secondly, the fingerprint spectra of the Sudan I are respectively assigned and analyzed in detail. Finally, the conclusion that the Raman spectroscopy technology is a powerful tool to determine the Sudan I is drawn.

Laser Diagnostics for combustion temperature and species measurements

NASA Technical Reports Server (NTRS)

Eckbreth, Alan C.

1988-01-01

Laser optical diagnostic techniques for the measurement of combustion gaseous-phase temperatures and, or species concentrations are discussed. The techniques fall into two classes: incoherent (Rayleigh scattering, spontaneous Raman scattering, laser induced fluorescence spectroscopy) and coherent (coherent anti-Stokes Raman spectroscopy). The advantages, disadvantages and applicability of each method are outlined.

Kerr-gated picosecond Raman spectroscopy and Raman photon migration of equine bone tissue with 400-nm excitation

NASA Astrophysics Data System (ADS)

Morris, Michael D.; Goodship, Allen E.; Draper, Edward R. C.; Matousek, Pavel; Towrie, Michael; Parker, Anthony W.

2004-07-01

We show that Raman spectroscopy with visible lasers, even in the deep blue is possible with time-gated Raman spectroscopy. A 4 picosec time gate allows efficient fluorescence rejection, up to 1000X, and provides almost background-free Raman spectra with low incident laser power. The technology enables spectroscopy with better than 10X higher scattering efficiency than is possible with the NIR (785 nm and 830 nm) lasers that are conventionally used. Raman photon migration is shown to allow depth penetration. We show for the first time that Kerr-gated Raman spectra of bone tissue with blue laser excitation enables both fluorescence rejection and depth penetration.

Surface-enhanced Raman spectroscopy of urine by an ingenious near-infrared Raman spectrometer

NASA Astrophysics Data System (ADS)

Feng, Shangyuan; Chen, Weiwei; Li, Yongzeng; Chen, Guannan; Huang, Zufang; Liao, Xiaohua; Xie, Zhiming; Chen, Rong

2007-11-01

This paper demonstrates the potential of an elaborately devised near-infrared Raman system in analysis of urine. The broad band in the long-wavelength region of the electronic absorption spectra of the sol with added adsorbent at certain concentrations has been explained in terms of the aggregation of the colloidal silver particles. We have reported the surface-enhanced Raman (SERS) spectra of urine, and studied the silver solution enhanced effects on the urine Raman scattering. The Raman bands of human's urine was assigned to certain molecule vibrations. We have found that different donators have dissimilar SERS of urine in different physiological condition. Comparatively few studies have explored the ability of Raman spectroscopy for the analysis of urine acid. In the present report, we investigated the ability of surface enhanced Raman spectroscopy to measure uric acid in the human urine. The results suggested that the present Raman system holds considerable promise for practical use. Practical applications such as the quantitative medical examination of urine metabolites may also be feasible in the near future.

Instant detection and identification of concealed explosive-related compounds: Induced Stokes Raman versus infrared.

PubMed

Elbasuney, Sherif; El-Sherif, Ashraf F

2017-01-01

The instant detection of explosives and explosive-related compounds has become an urgent priority in recent years for homeland security and counter-terrorism applications. Modern techniques should offer enhancement in selectivity, sensitivity, and standoff distances. Miniaturisation, portability, and field-ruggedisation are crucial requirements. This study reports on instant and standoff identification of concealed explosive-related compounds using customized Raman technique. Stokes Raman spectra of common explosive-related compounds were generated and spectrally resolved to create characteristic finger print spectra. The scattered Raman emissions over the band 400:2000cm -1 were compared to infrared absorption using FTIR. It has been demonstrated that the two vibrational spectroscopic techniques were opposite and completing each other. Molecular vibrations with strong absorption in infrared (those involve strong change in dipole moments) induced weak signals in Raman and vice versa. The tailored Raman offered instant detection, high sensitivity, and standoff detection capabilities. Raman demonstrated characteristic fingerprint spectra with stable baseline and sharp intense peaks. Complete correlations of absorption/scattered signals to certain molecular vibrations were conducted to generate an entire spectroscopic profile of explosive-related compounds. This manuscript shades the light on Raman as one of the prevailing technologies for instantaneous detection of explosive-related compounds. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

Four-wave-mixing and nonlinear cavity dumping of 280 picosecond 2nd Stokes pulse at 1.3 μm from Nd:SrMoO4 self-Raman laser

NASA Astrophysics Data System (ADS)

Smetanin, S. N.; Jelínek, M., Jr.; Kubeček, V.; Jelínková, H.; Ivleva, L. I.; Shurygin, A. S.

2016-01-01

The 280 picosecond 2nd Stokes Raman pulses at 1.3 μm were generated directly from the miniature diode-pumped Nd:SrMoO4 self-Raman laser. Using the 90° phase matching insensitive to the angular mismatch, the self-Raman laser allowed for the achievement of the four-wave-mixing generation of the 2nd Stokes Raman pulse directly in the active Nd:SrMoO4 crystal at stimulated Raman scattering (SRS) self-conversion of the laser radiation. The passive Cr:YAG Q-switching and nonlinear cavity dumping was used without any phase locking device.

Intrinsic Raman spectroscopy for quantitative biological spectroscopy Part II

PubMed Central

Bechtel, Kate L.; Shih, Wei-Chuan; Feld, Michael S.

2009-01-01

We demonstrate the effectiveness of intrinsic Raman spectroscopy (IRS) at reducing errors caused by absorption and scattering. Physical tissue models, solutions of varying absorption and scattering coefficients with known concentrations of Raman scatterers, are studied. We show significant improvement in prediction error by implementing IRS to predict concentrations of Raman scatterers using both ordinary least squares regression (OLS) and partial least squares regression (PLS). In particular, we show that IRS provides a robust calibration model that does not increase in error when applied to samples with optical properties outside the range of calibration. PMID:18711512

Analysis of polyethylene wear debris using micro-Raman spectroscopy: a report on the presence of beta-carotene.

PubMed

Hahn, D W; Wolfarth, D L; Parks, N L

1997-04-01

This paper describes micro-Raman spectroscopy of ultra-high molecular weight polyethylene wear debris isolated from revised knee replacements. The novel application of micro-Raman spectroscopy to the analysis of in vivo-generated wear debris was used to evaluate the chemical nature of individual, retrieved polyethylene particles. The analysis revealed the presence of beta-carotene on particles from both synovial fluid and tissue samples. Raman analysis of retrieved polyethylene tibial inserts also revealed localized beta-carotene signals within the primary wear region. In this paper, a mechanism is suggested that may account for the coupling of beta-carotene and polyethylene wear debris. We also discuss the origin of beta-carotene within the implanted joint and the implications that beta-carotene, an anti-oxidant, has for the overall host response to polyethylene orthopedic components.

Transcutaneous monitoring of steroid-induced osteoporosis with Raman spectroscopy

NASA Astrophysics Data System (ADS)

Maher, Jason R.; Inzana, Jason; Takahata, Masahiko; Awad, Hani A.; Berger, Andrew J.

2012-01-01

Although glucocorticoids are among the most frequently prescribed anti-inflammatory agents used in the treatment of rheumatoid arthritis, extended exposure to this steroid hormone is the leading cause of iatrogenic osteoporosis. Recently, Raman spectroscopy has been utilized to exploit biochemical differences between osteoporotic and normal bones in order to predict fracture risk. In this presentation, we report the results of ongoing research in our laboratory towards the clinical translation of this technique. We will discuss strategies for the transcutaneous acquisition of spectra from the tibiae of mice that are of sufficient quality to generate accurate predictions of fracture risk.

Sensitivity of Raman spectroscopy to normal patient variability

NASA Astrophysics Data System (ADS)

Vargis, Elizabeth; Byrd, Teresa; Logan, Quinisha; Khabele, Dineo; Mahadevan-Jansen, Anita

2011-11-01

Many groups have used Raman spectroscopy for diagnosing cervical dysplasia; however, there have been few studies looking at the effect of normal physiological variations on Raman spectra. We assess four patient variables that may affect normal Raman spectra: Race/ethnicity, body mass index (BMI), parity, and socioeconomic status. Raman spectra were acquired from a diverse population of 75 patients undergoing routine screening for cervical dysplasia. Classification of Raman spectra from patients with a normal cervix is performed using sparse multinomial logistic regression (SMLR) to determine if any of these variables has a significant effect. Results suggest that BMI and parity have the greatest impact, whereas race/ethnicity and socioeconomic status have a limited effect. Incorporating BMI and obstetric history into classification algorithms may increase sensitivity and specificity rates of disease classification using Raman spectroscopy. Studies are underway to assess the effect of these variables on disease.

Near-infrared-excited confocal Raman spectroscopy advances in vivo diagnosis of cervical precancer.

PubMed

Duraipandian, Shiyamala; Zheng, Wei; Ng, Joseph; Low, Jeffrey J H; Ilancheran, Arunachalam; Huang, Zhiwei

2013-06-01

Raman spectroscopy is a unique optical technique that can probe the changes of vibrational modes of biomolecules associated with tissue premalignant transformation. This study evaluates the clinical utility of confocal Raman spectroscopy over near-infrared (NIR) autofluorescence (AF) spectroscopy and composite NIR AF/Raman spectroscopy for improving early diagnosis of cervical precancer in vivo at colposcopy. A rapid NIR Raman system coupled with a ball-lens fiber-optic confocal Raman probe was utilized for in vivo NIR AF/Raman spectral measurements of the cervix. A total of 1240 in vivo Raman spectra [normal (n=993), dysplasia (n=247)] were acquired from 84 cervical patients. Principal components analysis (PCA) and linear discriminant analysis (LDA) together with a leave-one-patient-out, cross-validation method were used to extract the diagnostic information associated with distinctive spectroscopic modalities. The diagnostic ability of confocal Raman spectroscopy was evaluated using the PCA-LDA model developed from the significant principal components (PCs) [i.e., PC4, 0.0023%; PC5, 0.00095%; PC8, 0.00022%, (p<0.05)], representing the primary tissue Raman features (e.g., 854, 937, 1095, 1253, 1311, 1445, and 1654 cm(-1)). Confocal Raman spectroscopy coupled with PCA-LDA modeling yielded the diagnostic accuracy of 84.1% (a sensitivity of 81.0% and a specificity of 87.1%) for in vivo discrimination of dysplastic cervix. The receiver operating characteristic curves further confirmed that the best classification was achieved using confocal Raman spectroscopy compared to the composite NIR AF/Raman spectroscopy or NIR AF spectroscopy alone. This study illustrates that confocal Raman spectroscopy has great potential to improve early diagnosis of cervical precancer in vivo during clinical colposcopy.

Raman scattering in single-crystal sapphire at elevated temperatures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Thapa, Juddha; Liu, Bo; Woodruff, Steven D.

Sapphire is a widely used high-temperature material and this work presents thorough characterization of all the measurable Raman scattering modes in sapphire and their temperature dependencies. Here, Raman scattering in bulk sapphire rods is measured from room temperature to 1081 °C and is illustrated as a method of noncontact temperature measurement. A single-line argon ion laser at 488 nm was used to excite the sapphire rods inside a cylindrical furnace. All the anti-Stokes peaks (or lines) were observable through the entire temperature range of interest, while Stokes peaks were observable until they were obscured by background thermal emission. Temperature measurementsmore » were found to be most reliable for A 1g and E g modes using the peaks at ±418, ±379, +578, +645, and, +750 cm -1 (+ and – are designated for Stokes and anti-Stokes peaks respectively). The 418 cm -1 peak was found to be the most intense peak. The temperature dependence of peak position, peak width, and peak area of the ±418 and ±379 peaks is presented. For +578, +645 and +750, the temperature dependence of peak position is presented. The peaks’ spectral positions provide the most precise temperature information within the experimental temperature range. Finally, the resultant temperature calibration curves are given, which indicate that sapphire can be used in high-temperature Raman thermometry with an accuracy of about 1.38°C average standard deviation over the entire >1000°C temperature range.« less

Raman scattering in single-crystal sapphire at elevated temperatures

DOE PAGES

Thapa, Juddha; Liu, Bo; Woodruff, Steven D.; ...

2017-10-25

Sapphire is a widely used high-temperature material and this work presents thorough characterization of all the measurable Raman scattering modes in sapphire and their temperature dependencies. Here, Raman scattering in bulk sapphire rods is measured from room temperature to 1081 °C and is illustrated as a method of noncontact temperature measurement. A single-line argon ion laser at 488 nm was used to excite the sapphire rods inside a cylindrical furnace. All the anti-Stokes peaks (or lines) were observable through the entire temperature range of interest, while Stokes peaks were observable until they were obscured by background thermal emission. Temperature measurementsmore » were found to be most reliable for A 1g and E g modes using the peaks at ±418, ±379, +578, +645, and, +750 cm -1 (+ and – are designated for Stokes and anti-Stokes peaks respectively). The 418 cm -1 peak was found to be the most intense peak. The temperature dependence of peak position, peak width, and peak area of the ±418 and ±379 peaks is presented. For +578, +645 and +750, the temperature dependence of peak position is presented. The peaks’ spectral positions provide the most precise temperature information within the experimental temperature range. Finally, the resultant temperature calibration curves are given, which indicate that sapphire can be used in high-temperature Raman thermometry with an accuracy of about 1.38°C average standard deviation over the entire >1000°C temperature range.« less

Application of Raman Spectroscopy for Nondestructive Evaluation of Composite Materials

NASA Technical Reports Server (NTRS)

Washer, Glenn A.; Brooks, Thomas M. B.; Saulsberry, Regor

2007-01-01

This paper will present an overview of efforts to investigate the application of Raman spectroscopy for the characterization of Kevlar materials. Raman spectroscopy is a laser technique that is sensitive to molecular interactions in materials such as Kevlar, graphite and carbon used in composite materials. The overall goal of this research reported here is to evaluate Raman spectroscopy as a potential nondestructive evaluation (NDE) tool for the detection of stress rupture in Kevlar composite over-wrapped pressure vessels (COPVs). Characterization of the Raman spectra of Kevlar yarn and strands will be presented and compared with analytical models provided in the literature. Results of testing to investigate the effects of creep and high-temperature aging on the Raman spectra will be presented.

Spatially offset Raman spectroscopy based on a line-scan hyperspectral Raman system

USDA-ARS?s Scientific Manuscript database

Spatially offset Raman spectroscopy (SORS) is a technique that can obtain subsurface layered information by collecting Raman spectra from a series of surface positions laterally offset from the excitation laser. The current methods of SORS measurement are typically either slow due to mechanical move...

Stokes solitons in optical microcavities

NASA Astrophysics Data System (ADS)

Yang, Qi-Fan; Yi, Xu; Yang, Ki Youl; Vahala, Kerry

2017-01-01

Solitons are wave packets that resist dispersion through a self-induced potential well. They are studied in many fields, but are especially well known in optics on account of the relative ease of their formation and control in optical fibre waveguides. Besides their many interesting properties, solitons are important to optical continuum generation, in mode-locked lasers, and have been considered as a natural way to convey data over great distances. Recently, solitons have been realized in microcavities, thereby bringing the power of microfabrication methods to future applications. This work reports a soliton not previously observed in optical systems, the Stokes soliton. The Stokes soliton forms and regenerates by optimizing its Raman interaction in space and time within an optical potential well shared with another soliton. The Stokes and the initial soliton belong to distinct transverse mode families and benefit from a form of soliton trapping that is new to microcavities and soliton lasers in general. The discovery of a new optical soliton can impact work in other areas of photonics, including nonlinear optics and spectroscopy.

[Application of Raman Spectroscopy Technique to Agricultural Products Quality and Safety Determination].

PubMed

Liu, Yan-de; Jin, Tan-tan

2015-09-01

The quality and safety of agricultural products and people health are inseparable. Using the conventional chemical methods which have so many defects, such as sample pretreatment, complicated operation process and destroying the samples. Raman spectroscopy as a powerful tool of analysing and testing molecular structure, can implement samples quickly without damage, qualitative and quantitative detection analysis. With the continuous improvement and the scope of the application of Raman spectroscopy technology gradually widen, Raman spectroscopy technique plays an important role in agricultural products quality and safety determination, and has wide application prospects. There have been a lot of related research reports based on Raman spectroscopy detection on agricultural product quality safety at present. For the understanding of the principle of detection and the current development situation of Raman spectroscopy, as well as tracking the latest research progress both at home and abroad, the basic principles and the development of Raman spectroscopy as well as the detection device were introduced briefly. The latest research progress of quality and safety determination in fruits and vegetables, livestock and grain by Raman spectroscopy technique were reviewed deeply. Its technical problems for agricultural products quality and safety determination were pointed out. In addition, the text also briefly introduces some information of Raman spectrometer and the application for patent of the portable Raman spectrometer, prospects the future research and application.

Surface-Enhanced Raman Spectroscopy.

ERIC Educational Resources Information Center

Garrell, Robin L.

1989-01-01

Reviews the basis for the technique and its experimental requirements. Describes a few examples of the analytical problems to which surface-enhanced Raman spectroscopy (SERS) has been and can be applied. Provides a perspective on the current limitations and frontiers in developing SERS as an analytical technique. (MVL)

Polarized Raman spectroscopy of bone tissue: watch the scattering

NASA Astrophysics Data System (ADS)

Raghavan, Mekhala; Sahar, Nadder D.; Wilson, Robert H.; Mycek, Mary-Ann; Pleshko, Nancy; Kohn, David H.; Morris, Michael D.

2010-02-01

Polarized Raman spectroscopy is widely used in the study of molecular composition and orientation in synthetic and natural polymer systems. Here, we describe the use of Raman spectroscopy to extract quantitative orientation information from bone tissue. Bone tissue poses special challenges to the use of polarized Raman spectroscopy for measurement of orientation distribution functions because the tissue is turbid and birefringent. Multiple scattering in turbid media depolarizes light and is potentially a source of error. Using a Raman microprobe, we show that repeating the measurements with a series of objectives of differing numerical apertures can be used to assess the contributions of sample turbidity and depth of field to the calculated orientation distribution functions. With this test, an optic can be chosen to minimize the systematic errors introduced by multiple scattering events. With adequate knowledge of the optical properties of these bone tissues, we can determine if elastic light scattering affects the polarized Raman measurements.

Raman scattering spectroscopy for explosives identification

NASA Astrophysics Data System (ADS)

Nagli, L.; Gaft, M.

2007-04-01

Real time detection and identification of explosives at a standoff distance is a major issue in efforts to develop defense against so-called Improvised Explosive Devices (IED). It is recognized that the only technique, which is potentially capable to standoff detection of minimal amounts of explosives is laser-based spectroscopy. LDS technique belongs to trace detection, namely to its micro-particles variety. We applied gated Raman and time-resolved luminescence spectroscopy for detection of main explosive materials, both factory and homemade. Raman system was developed and tested by LDS for field remote detection and identification of minimal amounts of explosives on relevant surfaces at a distance of up to 30 meters.

[Research Progress of Raman Spectroscopy on Dyestuff Identification of Ancient Relics and Artifacts].

PubMed

He, Qiu-ju; Wang, Li-qin

2016-02-01

As the birthplace of Silk Road, China has a long dyeing history. The valuable information about the production time, the source of dyeing material, dyeing process and preservation status were existed in organic dyestuff deriving from cultural relics and artifacts. However, because of the low contents, complex compositions and easily degraded of dyestuff, it is always a challenging task to identify the dyestuff in relics analyzing field. As a finger-print spectrum, Raman spectroscopy owns unique superiorities in dyestuff identification. Thus, the principle, characteristic, limitation, progress and development direction of micro-Raman spectroscopy (MRS/µ-Raman), near infrared reflection and Fourier transform Raman spectroscopy (NIR-FT-Raman), surface-enhanced Raman spectroscopy (SERS) and resonance raman spectroscopy (RRS) have been introduced in this paper. Furthermore, the features of Raman spectra of gardenia, curcumin and other natural dyestuffs were classified by MRS technology, and then the fluorescence phenomena of purpurin excitated with different wavelength laser was compared and analyzed. At last, gray green silver colloidal particles were made as the base, then the colorant of madder was identified combining with thin layer chromatography (TLC) separation technology and SERS, the result showed that the surface enhancement effect of silver colloidal particles could significantly reduce fluorescence background of the Raman spectra. It is pointed out that Raman spectroscopy is a rapid and convenient molecular structure qualitative methodology, which has broad application prospect in dyestuff analysis of cultural relics and artifacts. We propose that the combination of multi-Raman spectroscopy, separation technology and long distance transmission technology are the development trends of Raman spectroscopy.

Fiber bundle based endomicroscopy prototype with two collection channels for simultaneous coherent anti-Stokes Raman scattering and second harmonic generation imaging

NASA Astrophysics Data System (ADS)

Liu, Zhengfan; Satira, Zachary A.; Wang, Xi; Xu, Xiaoyun; Chen, Xu; Wong, Kelvin; Chen, Shufen; Xin, Jianguo; Wong, Stephen T. C.

2014-02-01

Label-free multiphoton imaging is promising for replacing biopsy and could offer new strategies for intraoperative or surgical applications. Coherent anti-Stokes Raman scattering (CARS) imaging could provide lipid-band contrast, and second harmonic generation (SHG) imaging is useful for imaging collagen, tendon and muscle fibers. A combination of these two imaging modalities could provide rich information and this combination has been studied by researchers to investigate diseases through microscopy imaging. The combination of these two imaging modalities in endomicroscopy imaging has been rarely investigated. In this research, a fiber bundle consisted of one excitation fiber and 18 collection fibers was developed in our endomicroscopy prototype. The 18 collection fibers were divided into two collection channels with 9 fibers in each channel. These two channels could be used together as one channel for effective signal collection or used separately for simplifying detection part of the system. Differences of collection pattern of these two channels were investigated. Collection difference of central excitation fiber and surrounding 18 fibers was also investigated, which reveals the potential ability of this system to measure forward to backward (F/B) ratio in SHG imaging. CARS imaging of mouse adipocyte and SHG imaging of mouse tail tendon were performed to demonstrate the CARS and SHG tissue imaging performance of this system. Simultaneous CARS and SHG imaging ability of this system was demonstrated by mouse tail imaging. This fiber bundle based endomicroscopy imaging prototype, offers a promising platform for constructing efficient fiber-based CARS and SHG multimodal endomicroscopes for label free intraoperative imaging applications.

In vivo single human sweat gland activity monitoring using coherent anti-Stokes Raman scattering and two-photon excited autofluorescence microscopy.

PubMed

Chen, X; Gasecka, P; Formanek, F; Galey, J-B; Rigneault, H

2016-04-01

Eccrine sweat secretion is of central importance for control of body temperature. Although the incidence of sweat gland dysfunction might appear of minor importance, it can be a real concern for people with either hypohidrosis or hyperhidrosis. However, sweat gland function remains relatively poorly explored. To investigate the function of single human sweat glands. We describe a new approach for noninvasive imaging of single sweat gland activity in human palms in vivo up to a depth of 100 μm, based on nonlinear two-photon excited autofluorescence (TPEF) and coherent anti-Stokes Raman scattering (CARS). These techniques appear to be useful compared with approaches already described for imaging single sweat gland activity, as they allow better three-dimensional spatial resolution of sweat pore inner morphology and real-time monitoring of individual sweat events. By filling the sweat pore with oil and tuning the CARS contrast at 2845 cm(-1) , we imaged the ejection of sweat droplets from a single sweat gland when oil is pushed out by sweat flow. On average, sweat events lasted for about 30 s every 3 min under the conditions studied. On the other hand, about 20% of sweat glands were found inactive. TPEF and CARS were also used to study, at the single pore level, the antiperspirant action of aluminium chlorohydrate (ACH) and to reveal, for the first time in vivo, the formation of a plug at the pore entrance, in agreement with reported ACH antiperspirant mechanisms. Although data were acquired on human palms, these techniques show great promise for a better understanding of sweat secretion physiology and should be helpful to improve the efficacy of antiperspirant formulations. © 2015 British Association of Dermatologists.

Validating in vivo Raman spectroscopy of bone in human subjects

NASA Astrophysics Data System (ADS)

Esmonde-White, Francis W. L.; Morris, Michael D.

2013-03-01

Raman spectroscopy can non-destructively measure properties of bone related to mineral density, mineral composition, and collagen composition. Bone properties can be measured through the skin in animal and human subjects, but correlations between the transcutaneous and exposed bone measurements have only been reported for human cadavers. In this study, we examine human subjects to collect measurements transcutaneously, on surgically exposed bone, and on recovered bone fragments. This data will be used to demonstrate in vivo feasibility and to compare transcutaneous and exposed Raman spectroscopy of bone. A commercially available Raman spectrograph and optical probe operating at 785 nm excitation are used for the in vivo measurements. Requirements for applying Raman spectroscopy during a surgery are also discussed.

Transcutaneous Raman Spectroscopy of Bone

NASA Astrophysics Data System (ADS)

Maher, Jason R.

Clinical diagnoses of bone health and fracture risk typically rely upon measurements of bone density or structure, but the strength of a bone is also dependent upon its chemical composition. One technology that has been used extensively in ex vivo, exposed-bone studies to measure the chemical composition of bone is Raman spectroscopy. This spectroscopic technique provides chemical information about a sample by probing its molecular vibrations. In the case of bone tissue, Raman spectra provide chemical information about both the inorganic mineral and organic matrix components, which each contribute to bone strength. To explore the relationship between bone strength and chemical composition, our laboratory has contributed to ex vivo, exposed-bone animal studies of rheumatoid arthritis, glucocorticoid-induced osteoporosis, and prolonged lead exposure. All of these studies suggest that Raman-based predictions of biomechanical strength may be more accurate than those produced by the clinically-used parameter of bone mineral density. The utility of Raman spectroscopy in ex vivo, exposed-bone studies has inspired attempts to perform bone spectroscopy transcutaneously. Although the results are promising, further advancements are necessary to make non-invasive, in vivo measurements of bone that are of sufficient quality to generate accurate predictions of fracture risk. In order to separate the signals from bone and soft tissue that contribute to a transcutaneous measurement, we developed an overconstrained extraction algorithm that is based upon fitting with spectral libraries derived from separately-acquired measurements of the underlying tissue components. This approach allows for accurate spectral unmixing despite the fact that similar chemical components (e.g., type I collagen) are present in both soft tissue and bone and was applied to experimental data in order to transcutaneously detect, to our knowledge for the first time, age- and disease-related spectral

Planetary Surface Exploration Using Raman Spectroscopy on Rovers and Landers

NASA Astrophysics Data System (ADS)

Blacksberg, Jordana; Alerstam, E.; Maruyama, Y.; Charbon, E.; Rossman, G. R.

2013-10-01

Planetary surface exploration using laser induced breakdown spectroscopy (LIBS) to probe the composition of rocks has recently become a reality with the operation of the mast-mounted ChemCam instrument onboard the Curiosity rover. Following this success, Raman spectroscopy has steadily gained support as a means for using laser spectroscopy to identify not just composition but mineral phases, without the need for sample preparation. The RLS Raman Spectrometer is included on the payload for the ExoMars mission, and a Raman spectrometer has been included in an example strawman payload for NASA’s Mars 2020 mission. Raman spectroscopy has been identified by the community as a feasible means for pre-selection of samples on Mars for subsequent return to Earth. We present a next-generation instrument that builds on the widely used green-Raman technique to provide a means for performing Raman spectroscopy without the background noise that is often generated by fluorescence of minerals and organics. Microscopic Raman spectroscopy with a laser spot size smaller than the grains of interest can provide surface mapping of mineralogy while preserving morphology. A very small laser spot size 1 µm) is often necessary to identify minor phases that are often of greater interest than the matrix phases. In addition to the difficulties that can be posed by fine-grained material, fluorescence interference from the very same material is often problematic. This is particularly true for many of the minerals of interest that form in environments of aqueous alteration and can be highly fluorescent. We use time-resolved laser spectroscopy to eliminate fluorescence interference that can often make it difficult or impossible to obtain Raman spectra. We will discuss significant advances leading to the feasibility of a compact time-resolved spectrometer, including the development of a new solid-state detector capable of sub-ns time resolution. We will present results on planetary analog

Resonance Raman spectroscopy in malaria research.

PubMed

Wood, Bayden R; McNaughton, Don

2006-10-01

In recent years, the field of Raman spectroscopy has witnessed a surge in technological development, with the incorporation of ultrasensitive, charge-coupled devices, improved laser sources and precision Rayleigh-filter systems. This has led to the development of sensitive confocal micro-Raman spectrometers and imaging spectrometers that are capable of obtaining high spatial-resolution spectra and images of subcellular components within single living cells. This review reports on the application of resonance micro-Raman spectroscopy to the study of malaria pigment (hemozoin), a by-product of hemoglobin catabolization by the malaria parasite, which is an important target site for antimalarial drugs. The review aims to briefly describe recent studies on the application of this technology, elucidate molecular and electronic properties of the malaria pigment and its synthetic analog beta-hematin, provide insight into the mechanism of hemozoin formation within the food vacuole of the parasite, and comment on developing strategies for using this technology in drug-screening protocols.

Accuracy Enhancement of Raman Spectroscopy Using Complementary Laser-Induced Breakdown Spectroscopy (LIBS) with Geologically Mixed Samples.

PubMed

Choi, Soojin; Kim, Dongyoung; Yang, Junho; Yoh, Jack J

2017-04-01

Quantitative Raman analysis was carried out with geologically mixed samples that have various matrices. In order to compensate the matrix effect in Raman shift, laser-induced breakdown spectroscopy (LIBS) analysis was performed. Raman spectroscopy revealed the geological materials contained in the mixed samples. However, the analysis of a mixture containing different matrices was inaccurate due to the weak signal of the Raman shift, interference, and the strong matrix effect. On the other hand, the LIBS quantitative analysis of atomic carbon and calcium in mixed samples showed high accuracy. In the case of the calcite and gypsum mixture, the coefficient of determination of atomic carbon using LIBS was 0.99, while the signal using Raman was less than 0.9. Therefore, the geological composition of the mixed samples is first obtained using Raman and the LIBS-based quantitative analysis is then applied to the Raman outcome in order to construct highly accurate univariate calibration curves. The study also focuses on a method to overcome matrix effects through the two complementary spectroscopic techniques of Raman spectroscopy and LIBS.

Optical trapping and Raman spectroscopy of single nanostructures using standing-wave Raman tweezers

NASA Astrophysics Data System (ADS)

Wu, Mu-ying; He, Lin; Chen, Gui-hua; Yang, Guang; Li, Yong-qing

2017-08-01

Optical tweezers integrated with Raman spectroscopy allows analyzing a single trapped micro-particle, but is generally less effective for individual nano-sized objects in the 10-100 nm range. The main challenge is the weak gradient force on nanoparticles that is insufficient to overcome the destabilizing effect of scattering force and Brownian motion. Here, we present standing-wave Raman tweezers for stable trapping and sensitive characterization of single isolated nanostructures with a low laser power by combining a standing-wave optical trap (SWOT) with confocal Raman spectroscopy. This scheme has stronger intensity gradients and balanced scattering forces, and thus is more stable and sensitive in measuring nanoparticles in liquid with 4-8 fold increase in the Raman signals. It can be used to analyze many nanoparticles that cannot be measured with single-beam Raman tweezers, including individual single-walled carbon nanotubes (SWCNT), graphene flakes, biological particles, polystyrene beads (100 nm), SERS-active metal nanoparticles, and high-refractive semiconductor nanoparticles with a low laser power of a few milliwatts. This would enable sorting and characterization of specific SWCNTs and other nanoparticles based on their increased Raman fingerprints.

Tip-enhanced Raman spectroscopy and near-field polarization

NASA Astrophysics Data System (ADS)

Saito, Yuika; Mino, Toshihiro; Verma, Prabhat

2015-12-01

Tip-enhanced Raman spectroscopy (TERS) is a powerful tool for High-resolution Raman spectroscopy. In this method, a metal coated nano-tip acts as a plasmonic antenna to enhance the originally weak Raman scattering from a nanometric volume of a sample. The technique enables to detect Raman scattering light from nano-scale area and also enhance the light intensity with combination of near-filed light and localized surface plasmon generated at a metallized tip apex. Nowadays TERS is used to investigate various nano-scale samples, for examples, carbon nanotubes, graphenes DNA and biomaterials. As the TERS developed, there is high demand to investigate the properties of near-field light e.g. polarization properties. We have analyzed the polarization properties of near-field light in TERS and successfully realized the quantitative nano-imaging by visible light.

Two-photon-excited fluorescence spectroscopy of atomic fluorine at 170 nm

NASA Technical Reports Server (NTRS)

Herring, G. C.; Dyer, Mark J.; Jusinski, Leonard E.; Bischel, William K.

1988-01-01

Two-photon-excited fluorescence spectroscopy of atomic fluorine is reported. A doubled dye laser at 286-nm is Raman shifted in H2 to 170 nm (sixth anti-Stokes order) to excite ground-state 2P(0)J fluorine atoms to the 2D(0)J level. The fluorine atoms are detected by one of two methods: observing the fluorescence decay to the 2PJ level or observing F(+) production through the absorption of an additional photon by the excited atoms. Relative two-photon absorption cross sections to and the radiative lifetimes of the 2D(0)J states are measured.

Raman spectroscopy of triolein under high pressures

NASA Astrophysics Data System (ADS)

Tefelski, D. B.; Jastrzębski, C.; Wierzbicki, M.; Siegoczyński, R. M.; Rostocki, A. J.; Wieja, K.; Kościesza, R.

2010-03-01

This article presents results of the high pressure Raman spectroscopy of triolein. Triolein, a triacylglyceride (TAG) of oleic acid, is an unsaturated fat, present in natural oils such as olive oil. As a basic food component and an energy storage molecule, it has considerable importance for food and fuel industries. To generate pressure in the experiment, we used a high-pressure cylindrical chamber with sapphire windows, presented in (R.M. Siegoczyński, R. Kościesza, D.B. Tefelski, and A. Kos, Molecular collapse - modification of the liquid structure induced by pressure in oleic acid, High Press. Res. 29 (2009), pp. 61-66). Pressure up to 750 MPa was applied. A Raman spectrometer in "macro"-configuration was employed. Raman spectroscopy provides information on changes of vibrational modes related to structural changes of triolein under pressure. Interesting changes in the triglyceride C‒H stretching region at 2650-3100 cm-1 were observed under high-pressures. Changes were also observed in the ester carbonyl (C˭ O) stretching region 1700-1780 cm-1 and the C‒C stretching region at 1050-1150 cm-1. The overall luminescence of the sample decreased under pressure, making it possible to set longer spectrum acquisition time and obtain more details of the spectrum. The registered changes suggest that the high-pressure solid phase of triolein is organized as β-polymorphic, as was reported in (C. Akita, T. Kawaguchi, and F. Kaneko, Structural study on polymorphism of cis-unsaturated triacylglycerol: Triolein, J. Phys. Chem. B 110 (2006), pp. 4346-4353; E. Da Silva and D. Rousseau, Molecular order and thermodynamics of the solid-liquid transition in triglycerides via Raman spectroscopy, Phys. Chem. Chem. Phys. 10 (2008), pp. 4606-4613) (with temperature-induced phase transitions). The research has shown that Raman spectroscopy in TAGs under pressure reveals useful information about its structural changes.

Perspective: Two-dimensional resonance Raman spectroscopy

NASA Astrophysics Data System (ADS)

Molesky, Brian P.; Guo, Zhenkun; Cheshire, Thomas P.; Moran, Andrew M.

2016-11-01

Two-dimensional resonance Raman (2DRR) spectroscopy has been developed for studies of photochemical reaction mechanisms and structural heterogeneity in complex systems. The 2DRR method can leverage electronic resonance enhancement to selectively probe chromophores embedded in complex environments (e.g., a cofactor in a protein). In addition, correlations between the two dimensions of the 2DRR spectrum reveal information that is not available in traditional Raman techniques. For example, distributions of reactant and product geometries can be correlated in systems that undergo chemical reactions on the femtosecond time scale. Structural heterogeneity in an ensemble may also be reflected in the 2D spectroscopic line shapes of both reactive and non-reactive systems. In this perspective article, these capabilities of 2DRR spectroscopy are discussed in the context of recent applications to the photodissociation reactions of triiodide and myoglobin. We also address key differences between the signal generation mechanisms for 2DRR and off-resonant 2D Raman spectroscopies. Most notably, it has been shown that these two techniques are subject to a tradeoff between sensitivity to anharmonicity and susceptibility to artifacts. Overall, recent experimental developments and applications of the 2DRR method suggest great potential for the future of the technique.

Identification of anisodamine tablets by Raman and near-infrared spectroscopy with chemometrics.

PubMed

Li, Lian; Zang, Hengchang; Li, Jun; Chen, Dejun; Li, Tao; Wang, Fengshan

2014-06-05

Vibrational spectroscopy including Raman and near-infrared (NIR) spectroscopy has become an attractive tool for pharmaceutical analysis. In this study, effective calibration models for the identification of anisodamine tablet and its counterfeit and the distinguishment of manufacturing plants, based on Raman and NIR spectroscopy, were built, respectively. Anisodamine counterfeit tablets were identified by Raman spectroscopy with correlation coefficient method, and the results showed that the predictive accuracy was 100%. The genuine anisodamine tablets from 5 different manufacturing plants were distinguished by NIR spectroscopy using partial least squares discriminant analysis (PLS-DA) models based on interval principal component analysis (iPCA) method. And the results showed the recognition rate and rejection rate were 100% respectively. In conclusion, Raman spectroscopy and NIR spectroscopy combined with chemometrics are feasible and potential tools for rapid pharmaceutical tablet discrimination. Copyright © 2014 Elsevier B.V. All rights reserved.

Forensic and homeland security applications of modern portable Raman spectroscopy.

PubMed

Izake, Emad L

2010-10-10

Modern detection and identification of chemical and biological hazards within the forensic and homeland security contexts may well require conducting the analysis in field while adapting a non-contact approach to the hazard. Technological achievements on both surface and resonance enhancement Raman scattering re-developed Raman spectroscopy to become the most adaptable spectroscopy technique for stand-off and non-contact analysis of hazards. On the other hand, spatially offset Raman spectroscopy proved to be very valuable for non-invasive chemical analysis of hazards concealed within non-transparent containers and packaging. Copyright © 2010 Elsevier Ireland Ltd. All rights reserved.

Improved multiple-pass Raman spectrometer

NASA Astrophysics Data System (ADS)

Kc, Utsav; Silver, Joel A.; Hovde, David C.; Varghese, Philip L.

2011-08-01

An improved Raman gain spectrometer for flame measurements of gas temperature and species concentrations is described. This instrument uses a multiple-pass optical cell to enhance the incident light intensity in the measurement volume. The Raman signal is 83 times larger than from a single pass, and the Raman signal-to-noise ratio (SNR) in room-temperature air of 153 is an improvement over that from a single-pass cell by a factor of 9.3 when the cell is operated with 100 passes and the signal is integrated over 20 laser shots. The SNR improvement with the multipass cell is even higher for flame measurements at atmospheric pressure, because detector readout noise is more significant for single-pass measurements when the gas density is lower. Raman scattering is collected and dispersed in a spectrograph with a transmission grating and recorded with a fast gated CCD array detector to help eliminate flame interferences. The instrument is used to record spontaneous Raman spectra from N2, CO2, O2, and CO in a methane--air flame. Curve fits of the recorded Raman spectra to detailed simulations of nitrogen spectra are used to determine the flame temperature from the shapes of the spectral signatures and from the ratio of the total intensities of the Stokes and anti-Stokes signals. The temperatures measured are in good agreement with radiation-corrected thermocouple measurements for a range of equivalence ratios.

Raman spectroscopy of shocked gypsum from a meteorite impact crater

NASA Astrophysics Data System (ADS)

Brolly, Connor; Parnell, John; Bowden, Stephen

2017-07-01

Impact craters and associated hydrothermal systems are regarded as sites within which life could originate on Earth, and on Mars. The Haughton impact crater, one of the most well preserved craters on Earth, is abundant in Ca-sulphates. Selenite, a transparent form of gypsum, has been colonized by viable cyanobacteria. Basement rocks, which have been shocked, are more abundant in endolithic organisms, when compared with un-shocked basement. We infer that selenitic and shocked gypsum are more suitable for microbial colonization and have enhanced habitability. This is analogous to many Martian craters, such as Gale Crater, which has sulphate deposits in a central layered mound, thought to be formed by post-impact hydrothermal springs. In preparation for the 2020 ExoMars mission, experiments were conducted to determine whether Raman spectroscopy can distinguish between gypsum with different degrees of habitability. Ca-sulphates were analysed using Raman spectroscopy and results show no significant statistical difference between gypsum that has experienced shock by meteorite impact and gypsum, which has been dissolved and re-precipitated as an evaporitic crust. Raman spectroscopy is able to distinguish between selenite and unaltered gypsum. This shows that Raman spectroscopy can identify more habitable forms of gypsum, and demonstrates the current capabilities of Raman spectroscopy for the interpretation of gypsum habitability.

Raman Spectroscopy: An Emerging Tool in Neurodegenerative Disease Research and Diagnosis.

PubMed

Devitt, George; Howard, Kelly; Mudher, Amrit; Mahajan, Sumeet

2018-03-21

The pathogenesis underlining many neurodegenerative diseases remains incompletely understood. The lack of effective biomarkers and disease preventative medicine demands the development of new techniques to efficiently probe the mechanisms of disease and to detect early biomarkers predictive of disease onset. Raman spectroscopy is an established technique that allows the label-free fingerprinting and imaging of molecules based on their chemical constitution and structure. While analysis of isolated biological molecules has been widespread in the chemical community, applications of Raman spectroscopy to study clinically relevant biological species, disease pathogenesis, and diagnosis have been rapidly increasing since the past decade. The growing number of biomedical applications has shown the potential of Raman spectroscopy for detection of novel biomarkers that could enable the rapid and accurate screening of disease susceptibility and onset. Here we provide an overview of Raman spectroscopy and related techniques and their application to neurodegenerative diseases. We further discuss their potential utility in research, biomarker detection, and diagnosis. Challenges to routine use of Raman spectroscopy in the context of neuroscience research are also presented.

Coherent Raman spectroscopy for supersonic flow measurments

NASA Technical Reports Server (NTRS)

She, C. Y.

1986-01-01

In collaboration with NASA/Langley Research Center, a truly nonintrusive and nonseeding method for measuring supersonic molecular flow parameters was proposed and developed at Colorado State University. The feasibility of this Raman Doppler Velocimetry (RDV), currently operated in a scanning mode, was demonstrated not only in a laboratory environment at Colorado State University, but also in a major wind tunnel at NASA/Langley Research Center. The research progress of the RDV development is summarized. In addition, methods of coherent Rayleigh-Brillouin spectroscopy and single-pulse coherent Raman spectroscopy are investigated, respectively, for measurements of high-pressure and turbulent flows.

Picosecond vibrational spectroscopy of shocked energetic materials

NASA Astrophysics Data System (ADS)

Franken, Jens; Hambir, Selezion A.; Dlott, Dana D.

1998-07-01

The dynamic response of a thin film of the insensitive high explosive 5-nitro-2,4-dihydro-3H-1,2,4-triazol-3-one (NTO) to ultrafast shock compression has been investigated by picosecond coherent anti-Stokes Raman spectroscopy (CARS). Vibrational spectra were obtained in the 1200 cm-1 to 1450 cm-1 region with a time resolution on the order of 100 ps. The frequency shifts and widths of the two vibrational transitions in this region show an entirely different behavior when subjected to a shock load of about 5 GPa. An additional weak band at 1293 cm-1 appears temporarily while the shock front is within the NTO layer.

Raman spectroscopy: Watching a molecule breathe

NASA Astrophysics Data System (ADS)

Piatkowski, Lukasz; Hugall, James T.; van Hulst, Niek F.

2014-08-01

Marrying the single-molecule detection ability of surface-enhanced Raman scattering with the extreme time resolution of ultrafast coherent spectroscopy enables the vibrations of a single molecule to be observed.

Nanostructure-based plasmon-enhanced Raman spectroscopy for surface analysis of materials

NASA Astrophysics Data System (ADS)

Ding, Song-Yuan; Yi, Jun; Li, Jian-Feng; Ren, Bin; Wu, De-Yin; Panneerselvam, Rajapandiyan; Tian, Zhong-Qun

2016-06-01

Since 2000, there has been an explosion of activity in the field of plasmon-enhanced Raman spectroscopy (PERS), including surface-enhanced Raman spectroscopy (SERS), tip-enhanced Raman spectroscopy (TERS) and shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS). In this Review, we explore the mechanism of PERS and discuss PERS hotspots — nanoscale regions with a strongly enhanced local electromagnetic field — that allow trace-molecule detection, biomolecule analysis and surface characterization of various materials. In particular, we discuss a new generation of hotspots that are generated from hybrid structures combining PERS-active nanostructures and probe materials, which feature a strong local electromagnetic field on the surface of the probe material. Enhancement of surface Raman signals up to five orders of magnitude can be obtained from materials that are weakly SERS active or SERS inactive. We provide a detailed overview of future research directions in the field of PERS, focusing on new PERS-active nanomaterials and nanostructures and the broad application prospect for materials science and technology.

Near-infrared Raman spectroscopy of single optically trapped biological cells

NASA Astrophysics Data System (ADS)

Xie, Changan; Dinno, Mumtaz A.; Li, Yong-Qing

2002-02-01

We report on the development and testing of a compact laser tweezers Raman spectroscopy (LTRS) system. The system combines optical trapping and near-infrared Raman spectroscopy for manipulation and identification of single biological cells in solution. A low-power diode laser at 785 nm was used for both trapping and excitation for Raman spectroscopy of the suspended microscopic particles. The design of the LTRS system provides high sensitivity and permits real-time spectroscopic measurements of the biological sample. The system was calibrated by use of polystyrene microbeads and tested on living blood cells and on both living and dead yeast cells. As expected, different images and Raman spectra were observed for the different cells. The LTRS system may provide a valuable tool for the study of fundamental cellular processes and the diagnosis of cellular disorders.

Application of laser Raman spectroscopy to dental diagnosis

NASA Astrophysics Data System (ADS)

Izawa, Takahiro; Wakaki, Moriaki

2005-03-01

The aim of this research is related with the diagnosis of caries by use of a laser. We study the fundamental characterization of the diagnosis method using both fluorescence and Raman scattering spectroscopy. We try to evaluate the possibility of the caries diagnosis using Raman spectroscopy and its clinical application. We focus on the PO34- ion that flows out with the dissolution of hydroxyapatite (HAp), and the fluorescence that increases in connection with caries. The Raman line of P-O vibration is overlapped on the continuous, background spectrum by fluorescence. Consequently, we try to find out the correlation between a healthy part and a carious part by analyzing both fluorescence and Raman spectra. It was found that Raman intensity of HAp at carious lesion was weaker than those of healthy parts and the florescence intensity at the same portions was stronger. We have obtained the feasibility to estimate the degree of caries and health condition by deriving the ratio between Raman and florescence intensity. And the trial measurements in vivo were carried out to verify the availability of the method by using a fiber probe type multi channel Raman spectrometer. The process of remineralization is under researching for the development of preventive medicine.

Stress Analysis of SiC MEMS Using Raman Spectroscopy

NASA Astrophysics Data System (ADS)

Ness, Stanley J.; Marciniak, M. A.; Lott, J. A.; Starman, L. A.; Busbee, J. D.; Melzak, J. M.

2003-03-01

During the fabrication of Micro-Electro-Mechanical Systems (MEMS), residual stress is often induced in the thin films that are deposited to create these systems. These stresses can cause the device to fail due to buckling, curling, or fracture. Industry is looking for ways to characterize the stress during the deposition of thin films in order to reduce or eliminate device failure. Micro-Raman spectroscopy has been successfully used to characterize poly-Si MEMS devices made with the MUMPS® process. Raman spectroscopy was selected because it is nondestructive, fast and has the potential for in situ stress monitoring. This research attempts to use Raman spectroscopy to analyze the stress in SiC MEMS made with the MUSiC® process. Raman spectroscopy is performed on 1-2-micron-thick SiC thin films deposited on silicon, silicon nitride, and silicon oxide substrates. The most common poly-type of SiC found in thin film MEMS made with the MUSiC® process is 3C-SiC. Research also includes baseline spectra of 6H, 4H, and 15R poly-types of bulk SiC.

Raman Spectroscopy Study of Prostatic Adenocarcinoma Bulk Tissues

NASA Astrophysics Data System (ADS)

Devpura, S.; Dai, H.; Thakur, J. S.; Naik, R.; Cao, A.; Pandya, A.; Auner, G. W.; Sarkar, F.; Sakr, W.; Naik, V.

2009-03-01

Prostate cancer is one of the most common types of cancer among men. The mortality rate for this disease can be dramatically reduced if it can be diagnosed in its early stages. Raman spectroscopy is one of the optical techniques which can provide fingerprints of a disease in terms of its molecular composition which changes due to the onset of disease. The aim of this project is to investigate the differences in the Raman spectra to identify benign epithelium (BE), prostatic intraepithelial neoplasia (PIN) and adenocarcinoma of various Gleason grades in archived bulk tissues embedded in paraffin wax. For each tissue, two adjacent tissue sections were cut and dewaxed, where one of the sections was stained using haematoxylin and eosin for histological examination and the other unstained adjacent section was used for Raman spectroscopic studies. We have collected Raman spectra from 10 prostatic adenocarcinoma dewaxed tissue sections using Raman microscope (785 nm excitation laser). The data were analyzed using statistical methods of principal component analysis and discriminant function analysis to classify the tissue regions. The results indicate that Raman Spectroscopy can differentiate between BE, PIN and Cancer regions.

Microcavity Enhanced Raman Scattering

NASA Astrophysics Data System (ADS)

Petrak, Benjamin J.

Raman scattering can accurately identify molecules by their intrinsic vibrational frequencies, but its notoriously weak scattering efficiency for gases presents a major obstacle to its practical application in gas sensing and analysis. This work explores the use of high finesse (≈50 000) Fabry-Perot microcavities as a means to enhance Raman scattering from gases. A recently demonstrated laser ablation method, which carves out a micromirror template on fused silica--either on a fiber tip or bulk substrates-- was implemented, characterized, and optimized to fabricate concave micromirror templates ˜10 mum diameter and radius of curvature. The fabricated templates were coated with a high-reflectivity dielectric coating by ion-beam sputtering and were assembled into microcavities ˜10 mum long and with a mode volume ˜100 mum 3. A novel gas sensing technique that we refer to as Purcell enhanced Raman scattering (PERS) was demonstrated using the assembled microcavities. PERS works by enhancing the pump laser's intensity through resonant recirculation at one longitudinal mode, while simultaneously, at a second mode at the Stokes frequency, the Purcell effect increases the rate of spontaneous Raman scattering by a change to the intra-cavity photon density of states. PERS was shown to enhance the rate of spontaneous Raman scattering by a factor of 107 compared to the same volume of sample gas in free space scattered into the same solid angle subtended by the cavity. PERS was also shown capable of resolving several Raman bands from different isotopes of CO2 gas for application to isotopic analysis. Finally, the use of the microcavity to enhance coherent anti-Stokes Raman scattering (CARS) from CO2 gas was demonstrated.

Integrated Raman spectroscopy and trimodal wide-field imaging techniques for real-time in vivo tissue Raman measurements at endoscopy.

PubMed

Huang, Zhiwei; Teh, Seng Khoon; Zheng, Wei; Mo, Jianhua; Lin, Kan; Shao, Xiaozhuo; Ho, Khek Yu; Teh, Ming; Yeoh, Khay Guan

2009-03-15

We report an integrated Raman spectroscopy and trimodal (white-light reflectance, autofluorescence, and narrow-band) imaging techniques for real-time in vivo tissue Raman measurements at endoscopy. A special 1.8 mm endoscopic Raman probe with filtering modules is developed, permitting effective elimination of interference of fluorescence background and silica Raman in fibers while maximizing tissue Raman collections. We demonstrate that high-quality in vivo Raman spectra of upper gastrointestinal tract can be acquired within 1 s or subseconds under the guidance of wide-field endoscopic imaging modalities, greatly facilitating the adoption of Raman spectroscopy into clinical research and practice during routine endoscopic inspections.

Fabricating a UV-Vis and Raman Spectroscopy Immunoassay Platform.

PubMed

Hanson, Cynthia; Israelsen, Nathan D; Sieverts, Michael; Vargis, Elizabeth

2016-11-10

Immunoassays are used to detect proteins based on the presence of associated antibodies. Because of their extensive use in research and clinical settings, a large infrastructure of immunoassay instruments and materials can be found. For example, 96- and 384-well polystyrene plates are available commercially and have a standard design to accommodate ultraviolet-visible (UV-Vis) spectroscopy machines from various manufacturers. In addition, a wide variety of immunoglobulins, detection tags, and blocking agents for customized immunoassay designs such as enzyme-linked immunosorbent assays (ELISA) are available. Despite the existing infrastructure, standard ELISA kits do not meet all research needs, requiring individualized immunoassay development, which can be expensive and time-consuming. For example, ELISA kits have low multiplexing (detection of more than one analyte at a time) capabilities as they usually depend on fluorescence or colorimetric methods for detection. Colorimetric and fluorescent-based analyses have limited multiplexing capabilities due to broad spectral peaks. In contrast, Raman spectroscopy-based methods have a much greater capability for multiplexing due to narrow emission peaks. Another advantage of Raman spectroscopy is that Raman reporters experience significantly less photobleaching than fluorescent tags 1 . Despite the advantages that Raman reporters have over fluorescent and colorimetric tags, protocols to fabricate Raman-based immunoassays are limited. The purpose of this paper is to provide a protocol to prepare functionalized probes to use in conjunction with polystyrene plates for direct detection of analytes by UV-Vis analysis and Raman spectroscopy. This protocol will allow researchers to take a do-it-yourself approach for future multi-analyte detection while capitalizing on pre-established infrastructure.

Combination ring cavity and backward Raman waveguide amplifier

DOEpatents

Kurnit, Norman A.

1983-01-01

A combination regenerative ring and backward Raman waveguide amplifier and a combination regenerative ring oscillator and backward Raman waveguide amplifier which produce Raman amplification, pulse compression, and efficient energy extraction from the CO.sub.2 laser pump signal for conversion into a Stokes radiation signal. The ring cavity configuration allows the CO.sub.2 laser pump signal and Stokes signal to copropagate through the Raman waveguide amplifier. The backward Raman waveguide amplifier configuration extracts a major portion of the remaining energy from the CO.sub.2 laser pump signal for conversion to Stokes radiation. Additionally, the backward Raman amplifier configuration produces a Stokes radiation signal which has a high intensity and a short duration. Adjustment of the position of overlap of the Stokes signal and the CO.sub.2 laser pump signal in the backward Raman waveguide amplifiers alters the amount of pulse compression which can be achieved.

Coupled photonic crystal micro-cavities with ultra-low threshold power for stimulated Raman scattering.

PubMed

Liu, Qiang; Ouyang, Zhengbiao; Albin, Sacharia

2011-02-28

We propose coupled cavities to realize a strong enhancement of the Raman scattering. Five sub cavities are embedded in the photonic crystals. Simulations through finite-difference time-domain (FDTD) method demonstrate that one cavity, which is used to propagate the pump beam at the optical-communication wavelength, has a Q factor as high as 
1.254×10⁸ and modal volume as small as 0.03 μm3 (0.3192(λ/n)3). These parameters result in ultra-small threshold lasing power~17.7 nW and 2.58 nW for Stokes and anti-Stokes respectively. The cavities are designed to support the required Stokes and anti-Stokes modal spacing in silicon. The proposed structure has the potential for sensor devices, especially for biological and medical diagnoses.

On the Contribution of Raman Spectroscopy to Forensic Science

NASA Astrophysics Data System (ADS)

Buzzini, Patrick; Massonnet, Genevieve

2010-08-01

Raman spectroscopy has only recently sparked interest from forensic laboratories. The Raman technique has demonstrated important advantages such as its nondestructive nature, its fast analysis time, and especially the possibility of performing microscopical in situ analyses. In forensic applications, it is a versatile technique that covers a wide spectrum of substances such as trace evidence, illicit drugs and inks. An overview of the recent developments of Raman spectroscopy in forensic science will be discussed. Also, the requirements for an analytical technique for the examination of physical evidence will be described. Examples of casework will be depicted.

Metal-dielectric-CNT nanowires for surface-enhanced Raman spectroscopy

DOEpatents

Bond, Tiziana C.; Altun, Ali; Park, Hyung Gyu

2017-10-03

A sensor with a substrate includes nanowires extending vertically from the substrate, a hafnia coating on the nanowires that provides hafnia coated nanowires, and a noble metal coating on the hafnia coated nanowires. The top of the hafnia and noble metal coated nanowires bent onto one another to create a canopy forest structure. There are numerous randomly arranged holes that let through scattered light. The many points of contact, hot spots, amplify signals. The methods include the steps of providing a Raman spectroscopy substrate, introducing nano crystals to the Raman spectroscopy substrate, growing a forest of nanowires from the nano crystals on the Raman spectroscopy substrate, coating the nanowires with hafnia providing hafnia coated nanowires, and coating the hafnia coated nanowires with a noble metal or other metal.

Evaluation of bone quality in osteoporosis model mice by Raman spectroscopy

NASA Astrophysics Data System (ADS)

Ishimaru, Yasumitsu; Oshima, Yusuke; Imai, Yuuki; Iimura, Tadahiro; Takanezawa, Sota; Hino, Kazunori; Miura, Hiromasa

2017-04-01

To evaluate the bone quality in the osteoporosis, we generated sciatic nerve resection (NX) mice as an osteoporosis model and analyzed by Raman spectroscopy. Raman spectra were measured in anterior cortical surface of the proximal tibia at 5 points in each bone. After that, the samples were fixed with 70% ethanol. We then performed DXA and μCT measurement. Raman peak intensity ratios were significantly different between NX and Control. Those changes in the Raman peak intensity ratios may reflect loss of bone quality in the osteoporosis model. Raman spectroscopy is a promising technique for measuring the bone quality and bone strength.

Intraoperative Raman Spectroscopy of Soft Tissue Sarcomas

PubMed Central

Nguyen, John Q.; Gowani, Zain S.; O’Connor, Maggie; Pence, Isaac J.; Nguyen, The-Quyen; Holt, Ginger E.; Schwartz, Herbert S.; Halpern, Jennifer L.; Mahadevan-Jansen, Anita

2017-01-01

Background and Objective Soft tissue sarcomas (STS) are a rare and heterogeneous group of malignant tumors that are often treated through surgical resection. Current intraoperative margin assessment methods are limited and highlight the need for an improved approach with respect to time and specificity. Here we investigate the potential of near-infrared Raman spectroscopy for the intraoperative differentiation of STS from surrounding normal tissue. Materials and Methods In vivo Raman measurements at 785 nm excitation were intraoperatively acquired from subjects undergoing STS resection using a probe based spectroscopy system. A multivariate classification algorithm was developed in order to automatically identify spectral features that can be used to differentiate STS from the surrounding normal muscle and fat. The classification algorithm was subsequently tested using leave-one-subject-out cross-validation. Results With the exclusion of well-differentiated liposarcomas, the algorithm was able to classify STS from the surrounding normal muscle and fat with a sensitivity and specificity of 89.5% and 96.4%, respectively. Conclusion These results suggest that single point near-infrared Raman spectroscopy could be utilized as a rapid and non-destructive surgical guidance tool for identifying abnormal tissue margins in need of further excision. PMID:27454580

Optimization of Sample Preparation processes of Bone Material for Raman Spectroscopy.

PubMed

Chikhani, Madelen; Wuhrer, Richard; Green, Hayley

2018-03-30

Raman spectroscopy has recently been investigated for use in the calculation of postmortem interval from skeletal material. The fluorescence generated by samples, which affects the interpretation of Raman data, is a major limitation. This study compares the effectiveness of two sample preparation techniques, chemical bleaching and scraping, in the reduction of fluorescence from bone samples during testing with Raman spectroscopy. Visual assessment of Raman spectra obtained at 1064 nm excitation following the preparation protocols indicates an overall reduction in fluorescence. Results demonstrate that scraping is more effective at resolving fluorescence than chemical bleaching. The scraping of skeletonized remains prior to Raman analysis is a less destructive method and allows for the preservation of a bone sample in a state closest to its original form, which is beneficial in forensic investigations. It is recommended that bone scraping supersedes chemical bleaching as the preferred method for sample preparation prior to Raman spectroscopy. © 2018 American Academy of Forensic Sciences.

Polarized micro Raman spectroscopy of bilayer graphene

NASA Astrophysics Data System (ADS)

Moon, Hyerim; Yoon, Duhee; Son, Young-Woo; Cheong, Hyeonsik

2009-03-01

The frequency of Raman 2D band of the graphite depends on the excitation laser energy. This phenomenon is explained with double resonance Raman process. In polarized micro-Raman spectroscopy of single layer graphene, Raman G band (˜1586 cm-1) is isotropic, and 2D band (˜2686 cm-1) strongly depends on relative polarizations of the incident and scattered photons. This strong polarization dependence originates from inhomogeneous optical absorption and emission mediated by resonant electron-phonon interaction. In bi-layer graphene, Raman 2D band can be decomposed into four Lorenztian peaks which can be interpreted in terms of the four transition paths in the double resonance Raman process. We investigated the polarization dependence of each Lorenztian peak in the Raman 2D band of bi-layer graphene for different excitation laser energies. Strong polarization dependence of the Raman 2D band, similar to the case of single layer graphene, is observed. The excitation energy dependence of the polarized Raman scattering is analyzed in terms of the band structure of bi-layer graphene.

Parallelism between gradient temperature raman spectroscopy and differential scanning calorimetry results

USDA-ARS?s Scientific Manuscript database

Temperature dependent Raman spectroscopy (TDR) applies the temperature gradients utilized in differential scanning calorimetry (DSC) to Raman spectroscopy, providing a straightforward technique to identify molecular rearrangements that occur just prior to phase transitions. Herein we apply TDR and D...

Quantitative determinations using portable Raman spectroscopy.

PubMed

Navin, Chelliah V; Tondepu, Chaitanya; Toth, Roxana; Lawson, Latevi S; Rodriguez, Jason D

2017-03-20

A portable Raman spectrometer was used to develop chemometric models to determine percent (%) drug release and potency for 500mg ciprofloxacin HCl tablets. Parallel dissolution and chromatographic experiments were conducted alongside Raman experiments to assess and compare the performance and capabilities of portable Raman instruments in determining critical drug attributes. All batches tested passed the 30min dissolution specification and the Raman model for drug release was able to essentially reproduce the dissolution profiles obtained by ultraviolet spectroscopy at 276nm for all five batches of the 500mg ciprofloxacin tablets. The five batches of 500mg ciprofloxacin tablets also passed the potency (assay) specification and the % label claim for the entire set of tablets run were nearly identical, 99.4±5.1 for the portable Raman method and 99.2±1.2 for the chromatographic method. The results indicate that portable Raman spectrometers can be used to perform quantitative analysis of critical product attributes of finished drug products. The findings of this study indicate that portable Raman may have applications in the areas of process analytical technology and rapid pharmaceutical surveillance. Published by Elsevier B.V.

Quantitative Analysis of Microbicide Concentrations in Fluids, Gels and Tissues Using Confocal Raman Spectroscopy

PubMed Central

Chuchuen, Oranat; Henderson, Marcus H.; Sykes, Craig; Kim, Min Sung; Kashuba, Angela D. M.; Katz, David F.

2013-01-01

Topical vaginal anti-HIV microbicides are an important focus in female-based strategies to prevent the sexual transmission of HIV. Understanding microbicide pharmacokinetics is essential to development, characterization and implementation of efficacious microbicide drug delivery formulations. Current methods to measure drug concentrations in tissue (e.g., LC-MS/MS, liquid chromatography coupled with tandem mass spectrometry) are highly sensitive, but destructive and complex. This project explored the use of confocal Raman spectroscopy to detect microbicide drugs and to measure their local concentrations in fluids, drug delivery gels, and tissues. We evaluated three candidate microbicide drugs: tenofovir, Dapivirine and IQP-0528. Measurements were performed in freshly excised porcine buccal tissue specimens, gel vehicles and fluids using two Horiba Raman microscopes, one of which is confocal. Characteristic spectral peak calibrations for each drug were obtained using serial dilutions in the three matrices. These specific Raman bands demonstrated strong linear concentration dependences in the matrices and were characterized with respect to their unique vibrational signatures. At least one specific Raman feature was identified for each drug as a marker band for detection in tissue. Sensitivity of detection was evaluated in the three matrices. A specific peak was also identified for tenofovir diphosphate, the anti-HIV bioactive product of tenofovir after phosphorylation in host cells. Z-scans of drug concentrations vs. depth in excised tissue specimens, incubated under layers of tenofovir solution in a Transwell assay, showed decreasing concentration with depth from the surface into the tissue. Time-dependent concentration profiles were obtained from tissue samples incubated in the Transwell assay, for times ranging 30 minutes - 6 hours. Calibrations and measurements from tissue permeation studies for tenofovir showed good correlation with gold standard LC-MS/MS data

The substrate matters in the Raman spectroscopy analysis of cells

PubMed Central

Mikoliunaite, Lina; Rodriguez, Raul D.; Sheremet, Evgeniya; Kolchuzhin, Vladimir; Mehner, Jan; Ramanavicius, Arunas; Zahn, Dietrich R.T.

2015-01-01

Raman spectroscopy is a powerful analytical method that allows deposited and/or immobilized cells to be evaluated without complex sample preparation or labeling. However, a main limitation of Raman spectroscopy in cell analysis is the extremely weak Raman intensity that results in low signal to noise ratios. Therefore, it is important to seize any opportunity that increases the intensity of the Raman signal and to understand whether and how the signal enhancement changes with respect to the substrate used. Our experimental results show clear differences in the spectroscopic response from cells on different surfaces. This result is partly due to the difference in spatial distribution of electric field at the substrate/cell interface as shown by numerical simulations. We found that the substrate also changes the spatial location of maximum field enhancement around the cells. Moreover, beyond conventional flat surfaces, we introduce an efficient nanostructured silver substrate that largely enhances the Raman signal intensity from a single yeast cell. This work contributes to the field of vibrational spectroscopy analysis by providing a fresh look at the significance of the substrate for Raman investigations in cell research. PMID:26310910

The substrate matters in the Raman spectroscopy analysis of cells

NASA Astrophysics Data System (ADS)

Mikoliunaite, Lina; Rodriguez, Raul D.; Sheremet, Evgeniya; Kolchuzhin, Vladimir; Mehner, Jan; Ramanavicius, Arunas; Zahn, Dietrich R. T.

2015-08-01

Raman spectroscopy is a powerful analytical method that allows deposited and/or immobilized cells to be evaluated without complex sample preparation or labeling. However, a main limitation of Raman spectroscopy in cell analysis is the extremely weak Raman intensity that results in low signal to noise ratios. Therefore, it is important to seize any opportunity that increases the intensity of the Raman signal and to understand whether and how the signal enhancement changes with respect to the substrate used. Our experimental results show clear differences in the spectroscopic response from cells on different surfaces. This result is partly due to the difference in spatial distribution of electric field at the substrate/cell interface as shown by numerical simulations. We found that the substrate also changes the spatial location of maximum field enhancement around the cells. Moreover, beyond conventional flat surfaces, we introduce an efficient nanostructured silver substrate that largely enhances the Raman signal intensity from a single yeast cell. This work contributes to the field of vibrational spectroscopy analysis by providing a fresh look at the significance of the substrate for Raman investigations in cell research.

Raman-spectroscopy-based biosensing for applications in ophthalmology

NASA Astrophysics Data System (ADS)

Rusciano, Giulia; Capriglione, Paola; Pesce, Giuseppe; Zito, Gianluigi; Del Prete, Antonio; Cennamo, Giovanni; Sasso, Antonio

2013-05-01

Cell-based biosensors rely on the detection and identification of single cells as well as monitoring of changes induced by interaction with drugs and/or toxic agents. Raman spectroscopy is a powerful tool to reach this goal, being non-destructive analytical technique, allowing also measurements of samples in aqueous environment. In addition, micro-Raman measurements do not require preliminary sample preparation (as in fluorescence spectroscopy), show a finger-print spectral response, allow a spatial resolution below typical cell sizes, and are relatively fast (few s or even less). All these properties make micro-Raman technique particularly promising for high-throughput on-line analysis integrated in lab-on-a-chip devices. Herein, we demonstrate some applications of Raman analysis in ophthalmology. In particular, we demonstrate that Raman analysis can provide useful information for the therapeutic treatment of keratitis caused by Acanthamoeba Castellanii (A.), an opportunistic protozoan that is widely distributed in the environment and is known to produce blinding keratitis and fatal encephalitis. In particular, by combining Raman analysis with Principal Component Analysis (PCA), we have demonstrated that is possible to distinguish between live and dead cells, enabling, therefore to establish the effectiveness of therapeutic strategies to vanquish the protozoa. As final step, we have analyzed the presence of biochemical differences in the conjunctival epithelial tissues of patients affected by keratitis with respect to healthy people. As a matter of facts, it is possible to speculate some biochemical alterations of the epithelial tissues, rendering more favorable the binding of the protozoan. The epithelial cells were obtained by impression cytology from eyes of both healthy and keratitis-affected individuals. All the samples were analyzed by Raman spectroscopy within a few hours from cells removal from eyes. The results of this analysis are discussed.

[Rapid identification of potato cultivars using NIR-excited fluorescence and Raman spectroscopy].

PubMed

Dai, Fen; Bergholt, Mads Sylvest; Benjamin, Arnold Julian Vinoj; Hong, Tian-Sheng; Zhiwei, Huang

2014-03-01

Potato is one of the most important food in the world. Rapid and noninvasive identification of potato cultivars plays a important role in the better use of varieties. In this study, The identification ability of optical spectroscopy techniques, including near-infrared (NIR) Raman spectroscopy and NIR fluorescence spectroscopy, for invasive detection of potato cultivars was evaluated. A rapid NIR Raman spectroscopy system was applied to measure the composite Raman and NIR fluorescence spectroscopy of 3 different species of potatoes (98 samples in total) under 785 nm laser light excitation. Then pure Raman and NIR fluorescence spectroscopy were abstracted from the composite spectroscopy, respectively. At last, the partial least squares-discriminant analysis (PLS-DA) was utilized to analyze and classify Raman spectra of 3 different types of potatoes. All the samples were divided into two sets at random: the calibration set (74samples) and prediction set (24 samples), the model was validated using a leave-one-out, cross-validation method. The results showed that both the NIR-excited fluorescence spectra and pure Raman spectra could be used to identify three cultivars of potatoes. The fluorescence spectrum could distinguish the Favorita variety well (sensitivity: 1, specificity: 0.86 and accuracy: 0.92), but the result for Diamant (sensitivity: 0.75, specificity: 0.75 and accuracy: 0. 75) and Granola (sensitivity: 0.16, specificity: 0.89 and accuracy: 0.71) cultivars identification were a bit poorer. We demonstrated that Raman spectroscopy uncovered the main biochemical compositions contained in potato species, and provided a better classification sensitivity, specificity and accuracy (sensitivity: 1, specificity: 1 and accuracy: 1 for all 3 potato cultivars identification) among the three types of potatoes as compared to fluorescence spectroscopy.

Evaluation of Shifted Excitation Raman Difference Spectroscopy and Comparison to Computational Background Correction Methods Applied to Biochemical Raman Spectra.

PubMed

Cordero, Eliana; Korinth, Florian; Stiebing, Clara; Krafft, Christoph; Schie, Iwan W; Popp, Jürgen

2017-07-27

Raman spectroscopy provides label-free biochemical information from tissue samples without complicated sample preparation. The clinical capability of Raman spectroscopy has been demonstrated in a wide range of in vitro and in vivo applications. However, a challenge for in vivo applications is the simultaneous excitation of auto-fluorescence in the majority of tissues of interest, such as liver, bladder, brain, and others. Raman bands are then superimposed on a fluorescence background, which can be several orders of magnitude larger than the Raman signal. To eliminate the disturbing fluorescence background, several approaches are available. Among instrumentational methods shifted excitation Raman difference spectroscopy (SERDS) has been widely applied and studied. Similarly, computational techniques, for instance extended multiplicative scatter correction (EMSC), have also been employed to remove undesired background contributions. Here, we present a theoretical and experimental evaluation and comparison of fluorescence background removal approaches for Raman spectra based on SERDS and EMSC.

Perspective: Echoes in 2D-Raman-THz spectroscopy.

PubMed

Hamm, Peter; Shalit, Andrey

2017-04-07

Recently, various spectroscopic techniques have been developed, which can measure the 2D response of the inter-molecular degrees of freedom of liquids in the THz regime. By employing hybrid Raman-THz pulse sequences, the inherent experimental problems of 2D-Raman spectroscopy are circumvented completely, culminating in the recent measurement of the 2D-Raman-THz responses of water and aqueous salt solutions. This review article focuses on the possibility to observe echoes in such experiments, which would directly reveal the inhomogeneity of the typically extremely blurred THz bands of liquids, and hence the heterogeneity of local structures that are transiently formed, in particular, in a hydrogen-bonding liquid such as water. The generation mechanisms of echoes in 2D-Raman-THz spectroscopy are explained, which differ from those in "conventional" 2D-IR spectroscopy in a subtle but important manner. Subsequently, the circumstances are discussed, under which echoes are expected, revealing a physical picture of the information content of an echo. That is, the echo decay reflects the lifetime of local structures in the liquid on a length scale that equals the delocalization length of the intermolecular modes. Finally, recent experimental results are reviewed from an echo perspective.

Detecting changes during pregnancy with Raman spectroscopy

NASA Astrophysics Data System (ADS)

Vargis, Elizabeth; Robertson, Kesha; Al-Hendy, Ayman; Reese, Jeff; Mahadevan-Jansen, Anita

2010-02-01

Preterm labor is the second leading cause of neonatal mortality and leads to a myriad of complications like delayed development and cerebral palsy. Currently, there is no way to accurately predict preterm labor, making its prevention and treatment virtually impossible. While there are some at-risk patients, over half of all preterm births do not fall into any high-risk category. This study seeks to predict and prevent preterm labor by using Raman spectroscopy to detect changes in the cervix during pregnancy. Since Raman spectroscopy has been used to detect cancers in vivo in organs like the cervix and skin, it follows that spectra will change over the course of pregnancy. Previous studies have shown that fluorescence decreased during pregnancy and increased during post-partum exams to pre-pregnancy levels. We believe significant changes will occur in the Raman spectra obtained during the course of pregnancy. In this study, Raman spectra from the cervix of pregnant mice and women will be acquired. Specific changes that occur due to cervical softening or changes in hormonal levels will be observed to understand the likelihood that a female mouse or a woman will enter labor.

Raman Spectroscopy for Analysis of Thorium Compounds

DOE Office of Scientific and Technical Information (OSTI.GOV)

Su, Yin-Fong; Johnson, Timothy J.; Olsen, Khris B.

2016-05-12

The thorium fuel cycle is an alternative to the uranium fuel cycle in that when 232Th is irradiated with neutrons it is converted to 233U, another fissile isotope. There are several chemical forms of thorium which are used in the Th fuel cycle. Recently, Raman spectroscopy has become a very portable and facile analytical technique useful for many applications, including e.g. determining the chemical composition of different materials such as for thorium compounds. The technique continues to improve with the development of ever-more sensitive instrumentation and better software. Using a laboratory Fourier-transform (FT)-Raman spectrometer with a 785 nm wavelength laser,more » we were able to obtain Raman spectra from a series of thorium-bearing compounds of unknown origin. These spectra were compared to the spectra of in-stock-laboratory thorium compounds including ThO2, ThF4, Th(CO3)2 and Th(C2O4)2. The unknown spectra showed very good agreement to the known standards, demonstrating the applicability of Raman spectroscopy for detection and identification of these nuclear materials.« less

Raman Spectroscopy Detects Cardiac Allograft Rejection with Molecular Specificity

PubMed Central

Chung, Yoon Gi; Tu, Qiang; Cao, Dianjun; Harada, Shuko; Eisen, Howard J; Chang, Chang

2009-01-01

Abstract Spatially resolved Raman spectroscopy is shown here to be capable of molecular‐specific detection without exogenous labeling. This molecular specificity is achieved by detecting the strong and characteristic Raman spectral signature of an indole derivative, serotonin, whose selective existence in rejected heart transplants serves as the biomarker. The study also corroborates the increasingly recognized role of serotonin receptors in various immune responses, including cardiac allograft rejection. Combining both medical and physical sciences, this work demonstrates the potential use of Raman spectroscopy in replacing the invasive endomyocardial biopsy as the standard for post‐transplantation rejection surveillance and presents a new paradigm in advancing clinical care through interdisciplinary studies. PMID:20443894

Vibrational Energy Transfer from Heme through Atomic Contacts in Proteins.

PubMed

Yamashita, Satoshi; Mizuno, Misao; Tran, Duy Phuoc; Dokainish, Hisham M; Kitao, Akio; Mizutani, Yasuhisa

2018-05-10

A pathway of vibrational energy flow in myoglobin was studied by time-resolved anti-Stokes ultraviolet resonance Raman spectroscopy combined with site-directed mutagenesis. Our previous study suggested that atomic contacts in proteins provide the dominant pathway for energy transfer while covalent bonds do not. In the present study, we directly examined the contributions of covalent bonds and atomic contacts to the pathway of vibrational energy flow by comparing the anti-Stokes resonance Raman spectra of two myoglobin mutants: one lacked a covalent bond between heme and the polypeptide chain and the other retained the intact bond. The two mutants showed no significant difference in temporal changes in the anti-Stokes Raman intensities of the tryptophan bands, implying that the dominant channel of vibrational energy transfer is not through the covalent bond but rather through van der Waals atomic contacts between heme and the protein moiety. The obtained insights contribute to our general understanding of energy transfer in the condensed phase.

[Current views on surface enhanced Raman spectroscopy in microbiology].

PubMed

Jia, Xiaoxiao; Li, Jing; Qin, Tian; Deng, Aihua; Liu, Wenjun

2015-05-01

Raman spectroscopy has generated many branches during the development for more than 90 years. Surface enhanced Raman spectroscopy (SERS) improves SNR by using the interaction between tested materials and the surface of rough metal, as to quickly get higher sensitivity and precision spectroscopy without sample pretreatment. This article describes the characteristic and classification of SERS, and updates the theory and clinical application of SERS. It also summarizes the present status and progress of SERS in various disciplines and illustrates the necessity and urgency of its research, which provides rationale for the application for SERS in microbiology.

Dual-modal cancer detection based on optical pH sensing and Raman spectroscopy.

PubMed

Kim, Soogeun; Lee, Seung Ho; Min, Sun Young; Byun, Kyung Min; Lee, Soo Yeol

2017-10-01

A dual-modal approach using Raman spectroscopy and optical pH sensing was investigated to discriminate between normal and cancerous tissues. Raman spectroscopy has demonstrated the potential for in vivo cancer detection. However, Raman spectroscopy has suffered from strong fluorescence background of biological samples and subtle spectral differences between normal and disease tissues. To overcome those issues, pH sensing is adopted to Raman spectroscopy as a dual-modal approach. Based on the fact that the pH level in cancerous tissues is lower than that in normal tissues due to insufficient vasculature formation, the dual-modal approach combining the chemical information of Raman spectrum and the metabolic information of pH level can improve the specificity of cancer diagnosis. From human breast tissue samples, Raman spectra and pH levels are measured using fiber-optic-based Raman and pH probes, respectively. The pH sensing is based on the dependence of pH level on optical transmission spectrum. Multivariate statistical analysis is performed to evaluate the classification capability of the dual-modal method. The analytical results show that the dual-modal method based on Raman spectroscopy and optical pH sensing can improve the performance of cancer classification. (2017) COPYRIGHT Society of Photo-Optical Instrumentation Engineers (SPIE).

Dual-modal cancer detection based on optical pH sensing and Raman spectroscopy

NASA Astrophysics Data System (ADS)

Kim, Soogeun; Lee, Seung Ho; Min, Sun Young; Byun, Kyung Min; Lee, Soo Yeol

2017-10-01

A dual-modal approach using Raman spectroscopy and optical pH sensing was investigated to discriminate between normal and cancerous tissues. Raman spectroscopy has demonstrated the potential for in vivo cancer detection. However, Raman spectroscopy has suffered from strong fluorescence background of biological samples and subtle spectral differences between normal and disease tissues. To overcome those issues, pH sensing is adopted to Raman spectroscopy as a dual-modal approach. Based on the fact that the pH level in cancerous tissues is lower than that in normal tissues due to insufficient vasculature formation, the dual-modal approach combining the chemical information of Raman spectrum and the metabolic information of pH level can improve the specificity of cancer diagnosis. From human breast tissue samples, Raman spectra and pH levels are measured using fiber-optic-based Raman and pH probes, respectively. The pH sensing is based on the dependence of pH level on optical transmission spectrum. Multivariate statistical analysis is performed to evaluate the classification capability of the dual-modal method. The analytical results show that the dual-modal method based on Raman spectroscopy and optical pH sensing can improve the performance of cancer classification.

Evaluation of Shifted Excitation Raman Difference Spectroscopy and Comparison to Computational Background Correction Methods Applied to Biochemical Raman Spectra

PubMed Central

Cordero, Eliana; Korinth, Florian; Stiebing, Clara; Krafft, Christoph; Schie, Iwan W.; Popp, Jürgen

2017-01-01

Raman spectroscopy provides label-free biochemical information from tissue samples without complicated sample preparation. The clinical capability of Raman spectroscopy has been demonstrated in a wide range of in vitro and in vivo applications. However, a challenge for in vivo applications is the simultaneous excitation of auto-fluorescence in the majority of tissues of interest, such as liver, bladder, brain, and others. Raman bands are then superimposed on a fluorescence background, which can be several orders of magnitude larger than the Raman signal. To eliminate the disturbing fluorescence background, several approaches are available. Among instrumentational methods shifted excitation Raman difference spectroscopy (SERDS) has been widely applied and studied. Similarly, computational techniques, for instance extended multiplicative scatter correction (EMSC), have also been employed to remove undesired background contributions. Here, we present a theoretical and experimental evaluation and comparison of fluorescence background removal approaches for Raman spectra based on SERDS and EMSC. PMID:28749450

Raman spectroscopy of CNC-and CNF-based nanocomposites

Treesearch

Umesh P. Agarwal

2017-01-01

In this chapter, applications of Raman spectroscopy to nanocelluloses and nanocellulose composites are reviewed, and it is shown how use of various techniques in Raman can provide unique information. Some of the most important uses consisted of identification of cellulose nanomaterials, estimation of cellulose crystallinity, study of dispersion of cellulose...

New Applications of Portable Raman Spectroscopy in Agri-Bio-Photonics

NASA Astrophysics Data System (ADS)

Voronine, Dmitri; Scully, Rob; Sanders, Virgil

2014-03-01

Modern optical techniques based on Raman spectroscopy are being used to monitor and analyze the health of cattle, crops and their natural environment. These optical tools are now available to perform fast, noninvasive analysis of live animals and plants in situ. We will report new applications of a portable handheld Raman spectroscopy to identification and taxonomy of plants. In addition, detection of organic food residues will be demonstrated. Advantages and limitations of current portable instruments will be discussed with suggestions for improved performance by applying enhanced Raman spectroscopic schemes.

Raman spectroscopy of biomedical polyethylenes.

PubMed

Pezzotti, Giuseppe

2017-06-01

With the development of three-dimensional Raman algorithms for local mapping of oxidation and plastic strain, and the ability to resolve molecular orientation patterns with microscopic spatial resolution, there is an opportunity to re-examine many of the foundations on which our understanding of biomedical grade ultra-high molecular weight polyethylenes (UHMWPEs) are based. By implementing polarized Raman spectroscopy into an automatized tool with an improved precision in non-destructively resolving Euler angles, oxidation levels, and microscopic strain, we become capable to make accurate and traceable measurements of the in vitro and in vivo tribological responses of a variety of commercially available UHMWPE bearings for artificial hip and knee joints. In this paper, we first review the foundations and the main algorithms for Raman analyses of oxidation and strain of biomedical polyethylene. Then, we critically re-examine a large body of Raman data previously collected on different polyethylene joint components after in vitro testing or in vivo service, in order to shed new light on an area of particular importance to joint orthopedics: the microscopic nature of UHMWPE surface degradation in the human body. A complex scenario of physical chemistry appears from the Raman analyses, which highlights the importance of molecular-scale phenomena besides mere microstructural changes. The availability of the Raman microscopic probe for visualizing oxidation patterns unveiled striking findings related to the chemical contribution to wear degradation: chain-breaking and subsequent formation of carboxylic acid sites preferentially occur in correspondence of third-phase regions, and they are triggered by emission of dehydroxylated oxygen from ceramic oxide counterparts. These findings profoundly differ from more popular (and simplistic) notions of mechanistic tribology adopted in analyzing joint simulator data. Statement of Significance This review was dedicated to the

Raman Spectroscopy of Ocular Tissue

NASA Astrophysics Data System (ADS)

Ermakov, Igor V.; Sharifzadeh, Mohsen; Gellermann, Warner

The optically transparent nature of the human eye has motivated numerous Raman studies aimed at the non-invasive optical probing of ocular tissue components critical to healthy vision. Investigations include the qualitative and quantitative detection of tissue-specific molecular constituents, compositional changes occurring with development of ocular pathology, and the detection and tracking of ocular drugs and nutritional supplements. Motivated by a better understanding of the molecular mechanisms leading to cataract formation in the aging human lens, a great deal of work has centered on the Raman detection of proteins and water content in the lens. Several protein groups and the hydroxyl response are readily detectable. Changes of protein compositions can be studied in excised noncataractous tissue versus aged tissue preparations as well as in tissue samples with artificially induced cataracts. Most of these studies are carried out in vitro using suitable animal models and conventional Raman techniques. Tissue water content plays an important role in optimum light transmission of the outermost transparent ocular structure, the cornea. Using confocal Raman spectroscopy techniques, it has been possible to non-invasively measure the water to protein ratio as a measure of hydration status and to track drug-induced changes of the hydration levels in the rabbit cornea at various depths. The aqueous humor, normally supplying nutrients to cornea and lens, has an advantageous anterior location for Raman studies. Increasing efforts are pursued to non-invasively detect the presence of glucose and therapeutic concentrations of antibiotic drugs in this medium. In retinal tissue, Raman spectroscopy proves to be an important tool for research into the causes of macular degeneration, the leading cause of irreversible vision disorders and blindness in the elderly. It has been possible to detect the spectral features of advanced glycation and advanced lipooxydation end products in

Raman spectroscopy of selected copper minerals of significance in corrosion.

PubMed

Frost, R L

2003-04-01

The Raman spectroscopy of selected minerals of the corrosion products has been measured including nantokite, eriochalcite, claringbullite, atacamite, paratacamite, clinoatacamite and brochantite and related minerals. The free energy of formation shows that each mineral is stable relative to copper metal. The mineral, which is formed in copper corrosion, depends on the kinetics and conditions of the reaction. Raman spectroscopy clearly identifies each mineral by its characteristic Raman spectrum. The Raman spectrum is related to the mineral structure and bands are assigned to CuCl stretching and bending modes and to SO stretching modes. Clinoatacamite is identified as the polymorph of atacamite and not paratacamite. Paratacamite is a separate mineral with a similar but different structure to that of atacamite.

Shell-Isolated Tip-Enhanced Raman and Fluorescence Spectroscopy.

PubMed

Huang, Ya-Ping; Huang, Sheng-Chao; Wang, Xiang-Jie; Bodappa, Nataraju; Li, Chao-Yu; Yin, Hao; Su, Hai-Sheng; Meng, Meng; Zhang, Hua; Ren, Bin; Yang, Zhi-Lin; Zenobi, Renato; Tian, Zhong-Qun; Li, Jian-Feng

2018-06-18

Tip-enhanced Raman spectroscopy can provide molecular fingerprint information with ultrahigh spatial resolution, but the tip will be easily contaminated, thus leading to artifacts. It also remains a great challenge to establish tip-enhanced fluorescence because of the quenching resulting from the proximity of the metal tip. Herein, we report shell-isolated tip-enhanced Raman and fluorescence spectroscopies by employing ultrathin shell-isolated tips fabricated by atomic layer deposition. Such shell-isolated tips not only show outstanding electromagnetic field enhancement in TERS but also exclude interference by contaminants, thus greatly promoting applications in solution. Tip-enhanced fluorescence has also been achieved using these shell-isolated tips, with enhancement factors of up to 1.7×10 3 , consistent with theoretical simulations. Furthermore, tip-enhanced Raman and fluorescence signals are acquired simultaneously, and their relative intensities can be manipulated by changing the shell thickness. This work opens a new avenue for ultrahigh resolution surface analysis using plasmon-enhanced spectroscopies. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Raman spectroscopy of synthetic and natural iowaite.

PubMed

Frost, Ray L; Adebajo, Moses O; Erickson, Kristy L

2005-02-01

The chemistry of a magnesium based hydrotalcite known as iowaite Mg6Fe2Cl2(OH)16.4H2O has been studied using Raman spectroscopy. Iowaite has chloride as the counter anion in the interlayer. The formula of synthetic iowaite was found to be Mg5.78Fe2.09(Cl,(CO3)0.5)(OH)16.4H2O. Oxidation of natural iowaite results in the formation of Mg4FeO(Cl,CO3) (OH)8.4H2O. X-ray diffraction (XRD) shows that the iowaite is a layered structure with a d(001) spacing of 8.0 angtsroms. For synthetic iowaite three Raman bands at 1376, 1194 and 1084 cm(-1) are attributed to CO3 stretching vibrations. These bands are not observed for the natural iowaite but are observed when the natural iowaite is exposed to air. The Raman spectrum of natural iowaite shows three bands at 708, 690 and 620 cm(-1) and upon exposure to air, two broad bands are found at 710 and 648 cm(-1). The Raman spectrum of synthetic iowaite has a very broad band at 712 cm(-1). The Raman spectrum of natural iowaite shows an intense band at 527 cm(-1). The air oxidized iowaite shows two bands at 547 and 484 cm(-1) attributed to the (CO3)(2-)nu2 bending mode. Raman spectroscopy has proven most useful for the study of the chemistry of iowaite and chemical changes induced in natural iowaite upon exposure to air.

Detecting Kerogen as a Biosignature Using Colocated UV Time-Gated Raman and Fluorescence Spectroscopy.

PubMed

Shkolyar, Svetlana; Eshelman, Evan J; Farmer, Jack D; Hamilton, David; Daly, Michael G; Youngbull, Cody

2018-04-01

The Mars 2020 mission will analyze samples in situ and identify any that could have preserved biosignatures in ancient habitable environments for later return to Earth. Highest priority targeted samples include aqueously formed sedimentary lithologies. On Earth, such lithologies can contain fossil biosignatures as aromatic carbon (kerogen). In this study, we analyzed nonextracted kerogen in a diverse suite of natural, complex samples using colocated UV excitation (266 nm) time-gated (UV-TG) Raman and laser-induced fluorescence spectroscopies. We interrogated kerogen and its host matrix in samples to (1) explore the capabilities of UV-TG Raman and fluorescence spectroscopies for detecting kerogen in high-priority targets in the search for possible biosignatures on Mars; (2) assess the effectiveness of time gating and UV laser wavelength in reducing fluorescence in Raman spectra; and (3) identify sample-specific issues that could challenge rover-based identifications of kerogen using UV-TG Raman spectroscopy. We found that ungated UV Raman spectroscopy is suited to identify diagnostic kerogen Raman bands without interfering fluorescence and that UV fluorescence spectroscopy is suited to identify kerogen. These results highlight the value of combining colocated Raman and fluorescence spectroscopies, similar to those obtainable by SHERLOC on Mars 2020, to strengthen the confidence of kerogen detection as a potential biosignature in complex natural samples. Key Words: Raman spectroscopy-Laser-induced fluorescence spectroscopy-Mars Sample Return-Mars 2020 mission-Kerogen-Biosignatures. Astrobiology 18, 431-453.

Intraoperative Raman spectroscopy of soft tissue sarcomas.

PubMed

Nguyen, John Q; Gowani, Zain S; O'Connor, Maggie; Pence, Isaac J; Nguyen, The-Quyen; Holt, Ginger E; Schwartz, Herbert S; Halpern, Jennifer L; Mahadevan-Jansen, Anita

2016-10-01

Soft tissue sarcomas (STS) are a rare and heterogeneous group of malignant tumors that are often treated through surgical resection. Current intraoperative margin assessment methods are limited and highlight the need for an improved approach with respect to time and specificity. Here we investigate the potential of near-infrared Raman spectroscopy for the intraoperative differentiation of STS from surrounding normal tissue. In vivo Raman measurements at 785 nm excitation were intraoperatively acquired from subjects undergoing STS resection using a probe based spectroscopy system. A multivariate classification algorithm was developed in order to automatically identify spectral features that can be used to differentiate STS from the surrounding normal muscle and fat. The classification algorithm was subsequently tested using leave-one-subject-out cross-validation. With the exclusion of well-differentiated liposarcomas, the algorithm was able to classify STS from the surrounding normal muscle and fat with a sensitivity and specificity of 89.5% and 96.4%, respectively. These results suggest that single point near-infrared Raman spectroscopy could be utilized as a rapid and non-destructive surgical guidance tool for identifying abnormal tissue margins in need of further excision. Lasers Surg. Med. 48:774-781, 2016. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

Combustion Temperature Measurement by Spontaneous Raman Scattering in a Jet-A Fueled Gas Turbine Combustor Sector

NASA Technical Reports Server (NTRS)

Hicks, Yolanda R.; DeGroot, Wilhelmus A.; Locke, Randy J.; Anderson, Robert C.

2002-01-01

Spontaneous vibrational Raman scattering was used to measure temperature in an aviation combustor sector burning jet fuel. The inlet temperature ranged from 670 K (750 F) to 756 K (900 F) and pressures from 13 to 55 bar. With the exception of a discrepancy that we attribute to soot, good agreement was seen between the Raman-derived temperatures and the theoretical temperatures calculated from the inlet conditions. The technique used to obtain the temperature uses the relationship between the N2 anti-Stokes and Stokes signals, within a given Raman spectrum. The test was performed using a NASA-concept fuel injector and Jet-A fuel over a range of fuel/air ratios. This work represents the first such measurements in a high-pressure, research aero-combustor facility.

In situ TEM Raman spectroscopy and laser-based materials modification.

PubMed

Allen, F I; Kim, E; Andresen, N C; Grigoropoulos, C P; Minor, A M

2017-07-01

We present a modular assembly that enables both in situ Raman spectroscopy and laser-based materials processing to be performed in a transmission electron microscope. The system comprises a lensed Raman probe mounted inside the microscope column in the specimen plane and a custom specimen holder with a vacuum feedthrough for a tapered optical fiber. The Raman probe incorporates both excitation and collection optics, and localized laser processing is performed using pulsed laser light delivered to the specimen via the tapered optical fiber. Precise positioning of the fiber is achieved using a nanomanipulation stage in combination with simultaneous electron-beam imaging of the tip-to-sample distance. Materials modification is monitored in real time by transmission electron microscopy. First results obtained using the assembly are presented for in situ pulsed laser ablation of MoS 2 combined with Raman spectroscopy, complimented by electron-beam diffraction and electron energy-loss spectroscopy. Copyright © 2016 Elsevier B.V. All rights reserved.

High vacuum tip-enhanced Raman spectroscope based on a scanning tunneling microscope.

PubMed

Fang, Yurui; Zhang, Zhenglong; Sun, Mengtao

2016-03-01

In this paper, we present the construction of a high-vacuum tip-enhanced Raman spectroscopy (HV-TERS) system that allows in situ sample preparation and measurement. A detailed description of the prototype instrument is presented with experimental validation of its use and novel ex situ experimental results using the HV-TERS system. The HV-TERS system includes three chambers held under a 10(-7) Pa vacuum. The three chambers are an analysis chamber, a sample preparation chamber, and a fast loading chamber. The analysis chamber is the core chamber and contains a scanning tunneling microscope (STM) and a Raman detector coupled with a 50 × 0.5 numerical aperture objective. The sample preparation chamber is used to produce single-crystalline metal and sub-monolayer molecular films by molecular beam epitaxy. The fast loading chamber allows ex situ preparation of samples for HV-TERS analysis. Atomic resolution can be achieved by the STM on highly ordered pyrolytic graphite. We demonstrate the measurement of localized temperature using the Stokes and anti-Stokes TERS signals from a monolayer of 1,2-benzenedithiol on a gold film using a gold tip. Additionally, plasmonic catalysis can be monitored label-free at the nanoscale using our device. Moreover, the HV-TERS experiments show simultaneously activated infrared and Raman vibrational modes, Fermi resonance, and some other non-linear effects that are not observed in atmospheric TERS experiments. The high spatial and spectral resolution and pure environment of high vacuum are beneficial for basic surface studies.

High vacuum tip-enhanced Raman spectroscope based on a scanning tunneling microscope

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fang, Yurui; Bionanophotonics, Department of Applied Physics, Chalmers University of Technology, Göteborg, SE 41296; Zhang, Zhenglong

2016-03-15

In this paper, we present the construction of a high-vacuum tip-enhanced Raman spectroscopy (HV-TERS) system that allows in situ sample preparation and measurement. A detailed description of the prototype instrument is presented with experimental validation of its use and novel ex situ experimental results using the HV-TERS system. The HV-TERS system includes three chambers held under a 10{sup −7} Pa vacuum. The three chambers are an analysis chamber, a sample preparation chamber, and a fast loading chamber. The analysis chamber is the core chamber and contains a scanning tunneling microscope (STM) and a Raman detector coupled with a 50 ×more » 0.5 numerical aperture objective. The sample preparation chamber is used to produce single-crystalline metal and sub-monolayer molecular films by molecular beam epitaxy. The fast loading chamber allows ex situ preparation of samples for HV-TERS analysis. Atomic resolution can be achieved by the STM on highly ordered pyrolytic graphite. We demonstrate the measurement of localized temperature using the Stokes and anti-Stokes TERS signals from a monolayer of 1,2-benzenedithiol on a gold film using a gold tip. Additionally, plasmonic catalysis can be monitored label-free at the nanoscale using our device. Moreover, the HV-TERS experiments show simultaneously activated infrared and Raman vibrational modes, Fermi resonance, and some other non-linear effects that are not observed in atmospheric TERS experiments. The high spatial and spectral resolution and pure environment of high vacuum are beneficial for basic surface studies.« less

Condition Assessment of Kevlar Composite Materials Using Raman Spectroscopy

NASA Technical Reports Server (NTRS)

Washer, Glenn; Brooks, Thomas; Saulsberry, Regor

2007-01-01

This viewgraph presentation includes the following main concepts. Goal: To evaluate Raman spectroscopy as a potential NDE tool for the detection of stress rupture in Kevlar. Objective: Test a series of strand samples that have been aged under various conditions and evaluate differences and trends in the Raman response. Hypothesis: Reduction in strength associated with stress rupture may manifest from changes in the polymer at a molecular level. If so, than these changes may effect the vibrational characteristics of the material, and consequently the Raman spectra produced from the material. Problem Statement: Kevlar composite over-wrapped pressure vessels (COPVs) on the space shuttles are greater than 25 years old. Stress rupture phenomena is not well understood for COPVs. Other COPVs are planned for hydrogen-fueled vehicles using Carbon composite material. Raman spectroscopy is being explored as an non-destructive evaluation (NDE) technique to predict the onset of stress rupture in Kevlar composite materials. Test aged Kevlar strands to discover trends in the Raman response. Strength reduction in Kevlar polymer will manifest itself on the Raman spectra. Conclusions: Raman spectroscopy has shown relative changes in the intensity and FWHM of the 1613 cm(exp -1) peak. Reduction in relative intensity for creep, fleet leader, and SIM specimens compared to the virgin strands. Increase in FWHM has been observed for the creep and fleet leader specimens compared to the virgin strands. Changes in the Raman spectra may result from redistributing loads within the material due to the disruption of hydrogen bonding between crystallites or defects in the crystallites from aging the Kevlar strands. Peak shifting has not been observed to date. Analysis is ongoing. Stress measurements may provide a tool in the short term.

Combination of laser-induced breakdown spectroscopy and Raman spectroscopy for multivariate classification of bacteria

NASA Astrophysics Data System (ADS)

Prochazka, D.; Mazura, M.; Samek, O.; Rebrošová, K.; Pořízka, P.; Klus, J.; Prochazková, P.; Novotný, J.; Novotný, K.; Kaiser, J.

2018-01-01

In this work, we investigate the impact of data provided by complementary laser-based spectroscopic methods on multivariate classification accuracy. Discrimination and classification of five Staphylococcus bacterial strains and one strain of Escherichia coli is presented. The technique that we used for measurements is a combination of Raman spectroscopy and Laser-Induced Breakdown Spectroscopy (LIBS). Obtained spectroscopic data were then processed using Multivariate Data Analysis algorithms. Principal Components Analysis (PCA) was selected as the most suitable technique for visualization of bacterial strains data. To classify the bacterial strains, we used Neural Networks, namely a supervised version of Kohonen's self-organizing maps (SOM). We were processing results in three different ways - separately from LIBS measurements, from Raman measurements, and we also merged data from both mentioned methods. The three types of results were then compared. By applying the PCA to Raman spectroscopy data, we observed that two bacterial strains were fully distinguished from the rest of the data set. In the case of LIBS data, three bacterial strains were fully discriminated. Using a combination of data from both methods, we achieved the complete discrimination of all bacterial strains. All the data were classified with a high success rate using SOM algorithm. The most accurate classification was obtained using a combination of data from both techniques. The classification accuracy varied, depending on specific samples and techniques. As for LIBS, the classification accuracy ranged from 45% to 100%, as for Raman Spectroscopy from 50% to 100% and in case of merged data, all samples were classified correctly. Based on the results of the experiments presented in this work, we can assume that the combination of Raman spectroscopy and LIBS significantly enhances discrimination and classification accuracy of bacterial species and strains. The reason is the complementarity in

Analysis of Individual Cells and Endospores by Micro-Raman Spectroscopy

NASA Astrophysics Data System (ADS)

Esposito, Anthony; Huser, Thomas; Talley, Chad; Hollars, Christopher; Balhorn, Rod; Lane, Stephen

2003-03-01

We have collected Raman spectra of individual sperm cells by confocal micro-Raman spectroscopy. The high spatial resolution of this technique allows for compositional analysis of different sections of the sperm cells. The relative intensities of protein and DNA Raman transitions allow one to define a protein-DNA ratio. We have also collected the Raman spectra of individual bacterial endospores from four species in the genus Bacillus. The spectra were generally dominated by scattering from calcium dipicolinate, although scattering assignable to protein bands was also observed. A small fraction of the spores did not exhibit Raman scattering from CaDPA, possibly due to incomplete sporulation. These examples demonstrate the applicability of micro-Raman spectroscopy as a non-invasive method for addressing variability in the composition of cells.* *This work was performed under the auspices of the U.S. Department of Energy by the University of California, Lawrence Livermore National Laboratory under contract number W-7405-Eng-48.

Dispersive Raman spectroscopy allows the identification and quantification of melanin types

PubMed Central

Galván, Ismael; Jorge, Alberto

2015-01-01

Melanins are the most prevalent pigments in animals and are involved in visual communication by producing colored traits that often evolve as intraspecific signals of quality. Identifying and quantifying melanins are therefore essential to understand the function and evolution of melanin-based signals. However, the analysis of melanins is difficult due to their insolubility and the lack of simple methods that allow the identification of their chemical forms. We recently proposed the use of Raman spectroscopy as a simple, noninvasive technique that can be used to identify and quantify melanins in feathers and hairs. Contrarily, other authors later stated that melanins are characterized by a lack of defined Raman signals. Here, we use confocal Raman microscopy to confirm previous analyses showing that the two main chemical forms of melanins (eumelanin and pheomelanin) exhibit distinct Raman signal and compare different excitation wavelengths to analyze synthetic pheomelanin and natural melanins in feathers of different species of birds. Our analyses indicate that only laser excitation wavelengths below 1064 nm are useful for the analysis of melanins by Raman spectroscopy, and only 780-nm laser in the case of melanins in feathers. These findings show that the capacity of Raman spectroscopy to distinguish different chemical forms of melanins depends on laser power and integration time. As a consequence, Raman spectroscopy should be applied after preliminar analyses using a range of these parameters, especially in fragile biological tissues such as feathers. PMID:25897382

Raman Spectroscopy of 3-D Printed Polymers

NASA Astrophysics Data System (ADS)

Espinoza, Vanessa; Wood, Erin; Hight Walker, Angela; Seppala, Jonathan; Kotula, Anthony

Additive manufacturing (AM) techniques, such as 3-D printing are becoming an innovative and efficient way to produce highly customized parts for applications ranging from automotive to biomedical. Polymer-based AM parts can be produced from a myriad of materials and processing conditions to enable application-specific products. However, bringing 3-D printing from prototype to production relies on understanding the effect of processing conditions on the final product. Raman spectroscopy is a powerful and non-destructive characterization technique that can assist in determining the chemical homogeneity and physical alignment of polymer chains in 3-D printed materials. Two polymers commonly used in 3-D printing, acrylonitrile butadiene styrene (ABS) and polycarbonate (PC), were investigated using 1- and 2-D hyperspectral Raman imaging. In the case of ABS, a complex thermoplastic, the homogeneity of the material through the weld zone was investigated by comparing Raman peaks from each of the three components. In order to investigate the effect of processing conditions on polymer chain alignment, polarized Raman spectroscopy was used. In particular, the print speed or shear rate and effect of strain on PC filaments was investigated with perpendicular and parallel polarizations. National Institute of Standards and Technology Gaithersburg, MD ; Society of Physics Students.

Coherent anti‐Stokes Raman scattering (CARS) spectroscopy in Caenorhabditis elegans and Globodera pallida: evidence for an ivermectin‐activated decrease in lipid stores

PubMed Central

Smus, Justyna P; Ludlow, Elizabeth; Dallière, Nicolas; Luedtke, Sarah; Monfort, Tual; Lilley, Catherine; Urwin, Peter; Walker, Robert J; O'Connor, Vincent

2017-01-01

Abstract BACKGROUND Macrocyclic lactones are arguably the most successful chemical class with efficacy against parasitic nematodes. Here we investigated the effect of the macrocyclic lactone ivermectin on lipid homeostasis in the plant parasitic nematode Globodera pallida and provide new insight into its mode of action. RESULTS A non‐invasive, non‐destructive, label‐free and chemically selective technique called Coherent anti‐Stokes Raman scattering (CARS) spectroscopy was used to study lipid stores in G. pallida. We optimised the protocol using the free‐living nematode Caenorhabditis elegans and then used CARS to quantify lipid stores in the pre‐parasitic, non‐feeding J2 stage of G. pallida. This revealed a concentration of lipid stores in the posterior region of J2 s within 24 h of hatching which decreased to undetectable levels over the course of 28 days. We tested the effect of ivermectin on J2 viability and lipid stores. Within 24 h, ivermectin paralysed J2 s. Counterintuitively, over the same time‐course ivermectin increased the rate of depletion of J2 lipid, suggesting that in ivermectin‐treated J2 s there is a disconnection between the energy requirements for motility and metabolic rate. This decrease in lipid stores would be predicted to negatively impact on J2 infective potential. CONCLUSION These data suggest that the benefit of macrocyclic lactones as seed treatments may be underpinned by a multilevel effect involving both neuromuscular inhibition and acceleration of lipid metabolism. © 2017 The Authors. Pest Management Science published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry. PMID:28834172

Continuous gradient temperature Raman spectroscopy of unsaturated fatty acids

USDA-ARS?s Scientific Manuscript database

A new innovative technique gradient temperature, Raman spectroscopy (GTRS), identifies Raman frequency shifts in solid or liquid samples, and correlates them with specific temperature ranges within which flexible structures absorb heat. GTRS can easily detect changes that occur within one celcius te...

Determination of glucose and ethanol after enzymatic hydrolysis and fermentation of biomass using Raman spectroscopy.

PubMed

Shih, Chien-Ju; Smith, Emily A

2009-10-27

Raman spectroscopy has been used for the quantitative determination of the conversion efficiency at each step in the production of ethanol from biomass. The method requires little sample preparation; therefore, it is suitable for screening large numbers of biomass samples and reaction conditions in a complex sample matrix. Dilute acid or ammonia-pretreated corn stover was used as a model biomass for these studies. Ammonia pretreatment was suitable for subsequent measurements with Raman spectroscopy, but dilute acid-pretreated corn stover generated a large background signal that surpassed the Raman signal. The background signal is attributed to lignin, which remains in the plant tissue after dilute acid pretreatment. A commercial enzyme mixture was used for the enzymatic hydrolysis of corn stover, and glucose levels were measured with a dispersive 785 nm Raman spectrometer. The glucose detection limit in hydrolysis liquor by Raman spectroscopy was 8 g L(-1). The mean hydrolysis efficiency for three replicate measurements obtained with Raman spectroscopy (86+/-4%) was compared to the result obtained using an enzymatic reaction with UV-vis spectrophotometry detection (78+/-8%). The results indicate good accuracy, as determined using a Student's t-test, and better precision for the Raman spectroscopy measurement relative to the enzymatic detection assay. The detection of glucose in hydrolysis broth by Raman spectroscopy showed no spectral interference, provided the sample was filtered to remove insoluble cellulose prior to analysis. The hydrolysate was further subjected to fermentation to yield ethanol. The detection limit for ethanol in fermentation broth by Raman spectroscopy was found to be 6 g L(-1). Comparison of the fermentation efficiencies measured by Raman spectroscopy (80+/-10%) and gas chromatography-mass spectrometry (87+/-9%) were statistically the same. The work demonstrates the utility of Raman spectroscopy for screening the entire conversion process to

Simultaneous Conoscopic Holography and Raman Spectroscopy

NASA Technical Reports Server (NTRS)

Schramm, Harry F.; Kaiser, Bruce

2005-01-01

A new instrument was developed for chemical characterization of surfaces that combines the analytical power of Raman spectroscopy with the three-dimensional topographic information provided by conoscopic holography. The figure schematically depicts the proposed hybrid instrument. The output of the conoscopic holographic portion of the instrument is a topographical map of the surface; the output of the Raman portion of the instrument is hyperspectral Raman data, from which the chemical and/or biological composition of the surface would be deduced. By virtue of the basic principles of design and operation of the instrument, the hyperspectral image data would be inherently spatially registered with the topographical data. In conoscopic holography, the object and reference beams of classical holography are replaced by the ordinary and extraordinary components generated by a single beam traveling through a birefringent, uniaxial crystal. In the basic conoscopic configuration, a laser light is projected onto a specimen and the resulting illuminated spot becomes a point source of diffuse light that propagates in every direction. The laser beam is rasterscanned in two dimensions (x and y) perpendicular to the beam axis (z), and at each x,y location, the pattern of interference between the ordinary and extraordinary rays is recorded. The recorded interferogram constitutes the conoscopic hologram. Of particular significance for the proposed instrument is that the conoscopic hologram contains information on the z coordinate (height) of the illuminated surface spot. Hence, a topographical map of the specimen is constructed point-by-point by rastering the laser beam in the x and y directions and correlating the x and y coordinates with the z information obtained from the interferograms. Conoscopic imaging is an established method, and conoscopic laboratory instruments for surface metrology are commercially available. In Raman spectroscopy of a surface, one measures the spectrum

Label-free pathological evaluation of grade 3 cancer using Stokes shift spectroscopy

NASA Astrophysics Data System (ADS)

Sordillo, Laura A.; Sordillo, Peter P.; Alfano, R. R.

2016-03-01

In this study, Stokes shift spectroscopy (S3) is used for measuring the aggressiveness of malignant tumors. S3 is an optical tool which utilizes the difference between the emission wavelength (λem) and the absorption wavelength (λabs) (the Stokes shift) to give a fixed wavelength shift (Δλs).Our analysis of tumor samples using S3 shows grade 3 (high grade) cancers consistently have increased relative tryptophan content compared to grade 1 or 2 tumors. This technique may be a useful tool in the evaluation of a patient's cancer.

Bladder cancer diagnosis during cystoscopy using Raman spectroscopy

NASA Astrophysics Data System (ADS)

Grimbergen, M. C. M.; van Swol, C. F. P.; Draga, R. O. P.; van Diest, P.; Verdaasdonk, R. M.; Stone, N.; Bosch, J. H. L. R.

2009-02-01

Raman spectroscopy is an optical technique that can be used to obtain specific molecular information of biological tissues. It has been used successfully to differentiate normal and pre-malignant tissue in many organs. The goal of this study is to determine the possibility to distinguish normal tissue from bladder cancer using this system. The endoscopic Raman system consists of a 6 Fr endoscopic probe connected to a 785nm diode laser and a spectral recording system. A total of 107 tissue samples were obtained from 54 patients with known bladder cancer during transurethral tumor resection. Immediately after surgical removal the samples were placed under the Raman probe and spectra were collected and stored for further analysis. The collected spectra were analyzed using multivariate statistical methods. In total 2949 Raman spectra were recorded ex vivo from cold cup biopsy samples with 2 seconds integration time. A multivariate algorithm allowed differentiation of normal and malignant tissue with a sensitivity and specificity of 78,5% and 78,9% respectively. The results show the possibility of discerning normal from malignant bladder tissue by means of Raman spectroscopy using a small fiber based system. Despite the low number of samples the results indicate that it might be possible to use this technique to grade identified bladder wall lesions during endoscopy.

Performance Improvement of Raman Distributed Temperature System by Using Noise Suppression

NASA Astrophysics Data System (ADS)

Li, Jian; Li, Yunting; Zhang, Mingjiang; Liu, Yi; Zhang, Jianzhong; Yan, Baoqiang; Wang, Dong; Jin, Baoquan

2018-06-01

In Raman distributed temperature system, the key factor for performance improvement is noise suppression, which seriously affects the sensing distance and temperature accuracy. Therefore, we propose and experimentally demonstrate dynamic noise difference algorithm and wavelet transform modulus maximum (WTMM) to de-noising Raman anti-Stokes signal. Experimental results show that the sensing distance can increase from 3 km to 11.5 km and the temperature accuracy increases to 1.58 °C at the sensing distance of 10.4 km.

A line-scan hyperspectral Raman system for spatially offset Raman spectroscopy

USDA-ARS?s Scientific Manuscript database

Conventional methods of spatially offset Raman spectroscopy (SORS) typically use single-fiber optical measurement probes to slowly and incrementally collect a series of spatially offset point measurements moving away from the laser excitation point on the sample surface, or arrays of multiple fiber ...

Comparison of Fresh and Aged TNT with Multiwavelength Raman Spectroscopy

DTIC Science & Technology

2014-12-04

Naval Research Laboratory Washington, DC 20375-5320 NRL/MR/6730--14-9572 Comparison of Fresh and Aged TNT with Multiwavelength Raman Spectroscopy...NUMBER OF PAGES 17. LIMITATION OF ABSTRACT Comparison of Fresh and Aged TNT with Multiwavelength Raman Spectroscopy Robert Lunsford, Jacob Grun, and...fresh and aged variants. This is particularly true of UV aging which had the greater effect on the sample of the two aging processes tested

Principle, system, and applications of tip-enhanced Raman spectroscopy

NASA Astrophysics Data System (ADS)

Zhang, MingQian; Wang, Rui; Wu, XiaoBin; Wang, Jia

2012-08-01

Raman spectroscopy is a powerful technique in chemical information characterization. However, this spectral method is subject to two obstacles in nano-material detection. One is diffraction limited spatial resolution, and the other is its inherent small Raman cross section and weak signaling. To resolve these problems, a new approach has been developed, denoted as tip-enhanced Raman spectroscopy (TERS). TERS is capable of high-resolution and high-sensitivity detection and demonstrated to be a promising spectroscopic and micro-topographic method to characterize nano-materials and nanostructures. In this paper, the principle and experimental system of TERS are discussed. The latest application of TERS in molecule detection, biological specimen identification, nanao-material characterization, and semi-conductor material determination with some specific experimental examples are presented.

In situ Raman spectroscopy of LiFePO4: size and morphology dependence during charge and self-discharge.

PubMed

Wu, Jing; Dathar, Gopi Krishna Phani; Sun, Chunwen; Theivanayagam, Murali G; Applestone, Danielle; Dylla, Anthony G; Manthiram, Arumugam; Henkelman, Graeme; Goodenough, John B; Stevenson, Keith J

2013-10-25

Previous studies of the size dependent properties of LiFePO4 have focused on the diffusion rate or phase transformation pathways by bulk analysis techniques such as x-ray diffraction (XRD), neutron diffraction and electrochemistry. In this work, in situ Raman spectroscopy was used to study the surface phase change during charge and self-discharge on a more localized scale for three morphologies of LiFePO4: (1) 25 ± 6 nm width nanorods, (2) 225 ± 6 nm width nanorods and (3) ∼2 μm porous microspheres. Both the large nanorod and microsphere geometries showed incomplete delithiation at the end of charge, which was most likely caused by anti-site defects along the 1D diffusion channels in the bulk of the larger particles. Based on the in situ Raman measurements, all of the morphologies studied exhibited self-discharge with time. Among them, the smallest FePO4 particles self-discharged (lithiated) the fastest. While nanostructuring LiFePO4 can offer advantages in terms of lowering anti-site defects within particles, it also creates new problems due to high surface energies that allow self-discharge. The in situ Raman spectroscopy also showed that carbon coating did not provide significant improvement to the stability of the lithiated particles.

Optimizing laser crater enhanced Raman spectroscopy.

PubMed

Lednev, V N; Sdvizhenskii, P A; Grishin, M Ya; Filichkina, V A; Shchegolikhin, A N; Pershin, S M

2018-03-20

Raman signal enhancement by laser crater production was systematically studied for 785 nm continuous wave laser pumping. Laser craters were produced in L-aspartic acid powder by a nanosecond pulsed solid state neodymium-doped yttrium aluminum garnet laser (532 nm, 8 ns, 1 mJ/pulse), while Raman spectra were then acquired by using a commercial spectrometer with 785 nm laser beam pumping. The Raman signal enhancement effect was studied in terms of the number of ablating pulses used, the lens-to-sample distance, and the crater-center-laser-spot offset. The influence of the experiment parameters on Raman signal enhancement was studied for different powder materials. Maximum Raman signal enhancement reached 11 fold for loose powders but decreased twice for pressed tablets. Raman signal enhancement was demonstrated for several diverse powder materials like gypsum or ammonium nitrate with better results achieved for the samples tending to give narrow and deep craters upon the laser ablation stage. Alternative ways of cavity production (steel needle tapping and hole drilling) were compared with the laser cratering technique in terms of Raman signal enhancement. Drilling was found to give the poorest enhancement of the Raman signal, while both laser ablation and steel needle tapping provided comparable results. Here, we have demonstrated for the first time, to the best of our knowledge, that a Raman signal can be enhanced 10 fold with the aid of simple cavity production by steel needle tapping in rough highly reflective materials. Though laser crater enhancement Raman spectroscopy requires an additional pulsed laser, this technique is more appropriate for automatization compared to the needle tapping approach.

Cone penetrometer fiber optic raman spectroscopy probe assembly

DOEpatents

Kyle, Kevin R.; Brown, Steven B.

2000-01-01

A chemically and mechanically robust optical Raman spectroscopy probe assembly that can be incorporated in a cone penetrometer (CPT) for subsurface deployment. This assembly consists of an optical Raman probe and a penetrometer compatible optical probe housing. The probe is intended for in-situ chemical analysis of chemical constituents in the surrounding environment. The probe is optically linked via fiber optics to the light source and the detection system at the surface. A built-in broadband light source provides a strobe method for direct measurement of sample optical density. A mechanically stable sapphire window is sealed directly into the side-wall of the housing using a metallic, chemically resistant, hermetic seal design. This window permits transmission of the interrogation light beam and the resultant signal. The spectroscopy probe assembly is capable of accepting Raman, Laser induced Fluorescence, reflectance, and other optical probes with collimated output for CPT deployment.

Raman scattering excitation spectroscopy of monolayer WS2.

PubMed

Molas, Maciej R; Nogajewski, Karol; Potemski, Marek; Babiński, Adam

2017-07-11

Resonant Raman scattering is investigated in monolayer WS 2 at low temperature with the aid of an unconventional technique, i.e., Raman scattering excitation (RSE) spectroscopy. The RSE spectrum is made up by sweeping the excitation energy, when the detection energy is fixed in resonance with excitonic transitions related to either neutral or charged excitons. We demonstrate that the shape of the RSE spectrum strongly depends on the selected detection energy. The resonance of outgoing light with the neutral exciton leads to an extremely rich RSE spectrum, which displays several Raman scattering features not reported so far, while no clear effect on the associated background photoluminescence is observed. Instead, when the outgoing photons resonate with the negatively charged exciton, a strong enhancement of the related emission occurs. Presented results show that the RSE spectroscopy can be a useful technique to study electron-phonon interactions in thin layers of transition metal dichalcogenides.

On the widths of Stokes lines in Raman scattering from molecules adsorbed at metal surfaces and in molecular conduction junctions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gao, Yi, E-mail: yig057@ucsd.edu; Galperin, Michael, E-mail: migalperin@ucsd.edu; Nitzan, Abraham, E-mail: nitzan@post.tau.ac.il

Within a generic model we analyze the Stokes linewidth in surface enhanced Raman scattering (SERS) from molecules embedded as bridges in molecular junctions. We identify four main contributions to the off-resonant Stokes signal and show that under zero voltage bias (a situation pertaining also to standard SERS experiments) and at low bias junctions only one of these contributions is pronounced. The linewidth of this component is determined by the molecular vibrational relaxation rate, which is dominated by interactions with the essentially bosonic thermal environment when the relevant molecular electronic energy is far from the metal(s) Fermi energy(ies). It increases whenmore » the molecular electronic level is close to the metal Fermi level so that an additional vibrational relaxation channel due to electron-hole (eh) exciton in the molecule opens. Other contributions to the Raman signal, of considerably broader linewidths, can become important at larger junction bias.« less

Dual-broadband rotational CARS modelling of nitrogen at pressures up to 9 MPa. II. Rotational Raman line widths

NASA Astrophysics Data System (ADS)

Afzelius, M.; Bengtsson, P.-E.; Bood, J.; Bonamy, J.; Chaussard, F.; Berger, H.; Dreier, T.

Rotational coherent anti-Stokes Raman spectroscopy (CARS) is a well-established spectroscopic technique for thermometry at pre-combustion temperatures and atmospheric pressure. However, at pressures of several MPa, a previous investigation revealed large discrepancies between experimental data and the theoretical model. A re-evaluation has been made of these data (at room temperature and in the range 1.5-9 MPa) with two improvements to the spectral code. The first is the inclusion of an inter-branch interference effect, which is described in detail in Paper I. The second is the use of experimental S1-branch Raman line widths measured at 295 K, with a temperature dependence extracted from semi-classical calculations following the Robert-Bonamy formalism. It is shown that these two modifications significantly improve the theoretical model, since both the spectral fits and the accuracy of the evaluated temperatures are considerably improved.

Noninvasive authentication of pharmaceutical products through packaging using spatially offset Raman spectroscopy.

PubMed

Eliasson, Charlotte; Matousek, Pavel

2007-02-15

We demonstrate the use of spatially offset Raman spectroscopy (SORS) in the identification of counterfeit pharmaceutical tablets and capsules through different types of packaging. The technique offers a substantially higher sensitivity than that available from conventional backscattering Raman spectroscopy. The 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 packaging, capsule shell, or tablet coating contaminating the much weaker subsurface Raman signals of the active pharmaceutical ingredients and excipients held in the product. It is demonstrated that such interfering signals can be effectively suppressed by SORS.

Characterization of Storage-Induced Red Blood Cell Hemolysis Using Raman Spectroscopy.

PubMed

Gautam, Rekha; Oh, Joo-Yeun; Marques, Marisa B; Dluhy, Richard A; Patel, Rakesh P

2018-06-11

The therapeutic efficacy and safety of stored red blood cells (RBCs) relies on minimal in-bag hemolysis. The accuracy of current methods of measuring hemolysis can suffer as a result of specimen collection and processing artefacts. To test whether Raman spectroscopy could be used to assess hemolysis. RBCs were stored for as long as 42 days. Raman spectra of RBCs were measured before and after washing, and hemolysis was measured in supernatant by visible spectroscopy. Raman spectra indicated increased concentrations of oxyhemoglobin (oxyHb) and methemoglobin (metHb), and decreased membrane fluidity with storage age. Changes in oxyHb and metHb were associated with the intraerythrocytic and extracellular fractions, respectively. Hemolysis increased in a storage age-dependent manner. Changes in Raman bands reflective of oxyHb, metHb, and RBC membranes correlated with hemolysis; the most statistically significant change was an increased intensity of metHb and decreased membrane fluidity. These data suggest that Raman spectroscopy may offer a new label-free modality to assess RBC hemolysis during cold storage.

Planetary surface exploration using Raman spectroscopy for minerals and organics

NASA Astrophysics Data System (ADS)

Blacksberg, J.; Alerstam, E.; Maruyama, Y.; Charbon, E.; Rossman, G. R.; Shkolyar, S.; Farmer, J. D.

2013-12-01

Raman spectroscopy has been identified as one of the primary techniques for planetary surface mineralogy. It is widely used as a laboratory technique since it can identify nearly all crystalline mineral phases. Using a small spot size on the surface (on the order of a micron), mineral phases can be mapped onto microscopic images preserving information about surface morphology. As a result, this technique has been steadily gaining support for in situ exploration of a variety of target bodies, for example Mars, the Moon, Venus, asteroids, and comets. In addition to in situ exploration, Raman spectroscopy has been identified as a feasible means for pre-selection of samples on Mars for subsequent return to Earth. This is in part due to the fact that Raman can detect many organics in addition to minerals. As a result, the most relevant rock samples containing organics (potentially fossil biosignatures) may potentially be selected for return to Earth. We present a next-generation instrument that builds on the widely used 532 nm Raman technique to provide a means for performing Raman spectroscopy without the background noise that is often generated by fluorescence of minerals and organics. We use time-resolved laser spectroscopy to eliminate this fluorescence interference that can often make it difficult or impossible to obtain Raman spectra. We will discuss significant advances leading to the feasibility of a compact time-resolved spectrometer, including the development of a new solid-state detector capable of sub-ns temporal resolution. We will address the challenges of analyzing surface materials, often organics, that exhibit short-lifetime fluorescence. We will present result on planetary analog samples to demonstrate the instrument performance including fluorescence rejection.

Raman spectroscopy and Raman imaging for early detection of cancer

NASA Astrophysics Data System (ADS)

Joshi, Narahari V.; Ortega, Angel; Estrela, Jose Maria

2004-06-01

Raman spectroscopy is a powerful technique as it provides fundamental information about vibrational modes of a system. Eigenvalues of these modes are very sensitive to the strength of the chemical bonds and perturbations caused by the environment, particularly charge distribution and alterations in the dipole strength of the system. All these parameters are profoundly modified during the tumor formation process nad hence Raman technique could be a unique and also a direct approach for evaluating tumor genesis at early stages. for this pupose the present investigation was carried out. We used cultured wild type and c-ras transformed NIH 3T3 fibroblast. The samples were treated with methyl alcohol solution ina conventional manner and then Raman spectra nad images were obtained by a specially developed confocal Raman microscope. The present results reveal differences between both cell types in the spectral details as well as in the morphology. Raman images are able to detect the exact site where cancer-related changes have taken place. These results clearly indicate the superiority of the present technique over conventional methods such as images obtained by X-rays or Nuclear Magnetic Resonance (NMR). Moreover, unlike other approaches, Raman images detect alterations at the submicron level rather than in the centimeter or millimeter range. Being an optical method it can be applied in vivo as a non-invasive technique potentially useful to early detection of cancer (particularly easy accessible cancers such as those of the skin and the digestive tract). The obtained resulsts suggest the great potential of Raman imaging in premature clinical diagnostic approaches.

Citrus fruits freshness assessment using Raman spectroscopy.

PubMed

Nekvapil, Fran; Brezestean, Ioana; Barchewitz, Daniel; Glamuzina, Branko; Chiş, Vasile; Cintă Pinzaru, Simona

2018-03-01

The freshness of citrus fruits commonly available in the market was non-destructively assessed by Raman spectroscopy. Intact clementine, mandarin and tangerine species were characterised concerning their carotenoids skin Raman signalling in a time course from the moment they were acquired as fresh stock, supplying the market, to the physical degradation, when they were no longer attractive to consumers. The freshness was found to strongly correlate to the peel Raman signal collected from the same area of the intact fruits in a time course of a maximum of 20days. We have shown that the intensity of the carotenoid Raman signal is indeed a good indicator of fruit freshness and introduced a Raman coefficient of freshness (C Fresh ), whose time course is linearly decreasing, with different slope for different citrus groups. Additionally, we demonstrated that the freshness assessment could be achieved using a portable Raman instrument. The results could have a strong impact for consumer satisfaction and the food industry. Copyright © 2017 Elsevier Ltd. All rights reserved.

Raman spectroscopy as a PAT for pharmaceutical blending: Advantages and disadvantages.

PubMed

Riolo, Daniela; Piazza, Alessandro; Cottini, Ciro; Serafini, Margherita; Lutero, Emilio; Cuoghi, Erika; Gasparini, Lorena; Botturi, Debora; Marino, Iari Gabriel; Aliatis, Irene; Bersani, Danilo; Lottici, Pier Paolo

2018-02-05

Raman spectroscopy has been positively evaluated as a tool for the in-line and real-time monitoring of powder blending processes and it has been proved to be effective in the determination of the endpoint of the mixing, showing its potential role as process analytical technology (PAT). The aim of this study is to show advantages and disadvantages of Raman spectroscopy with respect to the most traditional HPLC analysis. The spectroscopic results, obtained directly on raw powders, sampled from a two-axis blender in real case conditions, were compared with the chromatographic data obtained on the same samples. The formulation blend used for the experiment consists of active pharmaceutical ingredient (API, concentrations 6.0% and 0.5%), lactose and magnesium stearate (as excipients). The first step of the monitoring process was selecting the appropriate wavenumber region where the Raman signal of API is maximal and interference from the spectral features of excipients is minimal. Blend profiles were created by plotting the area ratios of the Raman peak of API (A API ) at 1598cm -1 and the Raman bands of excipients (A EXC ), in the spectral range between 1560 and 1630cm -1 , as a function of mixing time: the API content can be considered homogeneous when the time-dependent dispersion of the area ratio is minimized. In order to achieve a representative sampling with Raman spectroscopy, each sample was mapped in a motorized XY stage by a defocused laser beam of a micro-Raman apparatus. Good correlation between the two techniques has been found only for the composition at 6.0% (w/w). However, standard deviation analysis, applied to both HPLC and Raman data, showed that Raman results are more substantial than HPLC ones, since Raman spectroscopy enables generating data rich blend profiles. In addition, the relative standard deviation calculated from a single map (30 points) turned out to be representative of the degree of homogeneity for that blend time. Copyright © 2017

The 14th Annual James L. Waters Symposium at Pittcon: Raman Spectroscopy

ERIC Educational Resources Information Center

Gardner, Charles W.

2007-01-01

Raman Spectroscopy was the main topic of the 14th Annual James L. Waters Symposium, which was held in March 2003 at Pittcon. The development of the enabling technologies that have made Raman spectroscopy a routine analysis tool in many laboratories worldwide is discussed.

Localized surface plasmon resonances in nanostructures to enhance nonlinear vibrational spectroscopies: towards an astonishing molecular sensitivity

PubMed Central

2014-01-01

Summary Vibrational transitions contain some of the richest fingerprints of molecules and materials, providing considerable physicochemical information. Vibrational transitions can be characterized by different spectroscopies, and alternatively by several imaging techniques enabling to reach sub-microscopic spatial resolution. In a quest to always push forward the detection limit and to lower the number of needed vibrational oscillators to get a reliable signal or imaging contrast, surface plasmon resonances (SPR) are extensively used to increase the local field close to the oscillators. Another approach is based on maximizing the collective response of the excited vibrational oscillators through molecular coherence. Both features are often naturally combined in vibrational nonlinear optical techniques. In this frame, this paper reviews the main achievements of the two most common vibrational nonlinear optical spectroscopies, namely surface-enhanced sum-frequency generation (SE-SFG) and surface-enhanced coherent anti-Stokes Raman scattering (SE-CARS). They can be considered as the nonlinear counterpart and/or combination of the linear surface-enhanced infrared absorption (SEIRA) and surface-enhanced Raman scattering (SERS) techniques, respectively, which are themselves a branching of the conventional IR and spontaneous Raman spectroscopies. Compared to their linear equivalent, those nonlinear vibrational spectroscopies have proved to reach higher sensitivity down to the single molecule level, opening the way to astonishing perspectives for molecular analysis. PMID:25551056

Multiplex coherent raman spectroscopy detector and method

NASA Technical Reports Server (NTRS)

Joyner, Candace C. (Inventor); Patrick, Sheena T. (Inventor); Chen, Peter (Inventor); Guyer, Dean R. (Inventor)

2004-01-01

A multiplex coherent Raman spectrometer (10) and spectroscopy method rapidly detects and identifies individual components of a chemical mixture separated by a separation technique, such as gas chromatography. The spectrometer (10) and method accurately identify a variety of compounds because they produce the entire gas phase vibrational Raman spectrum of the unknown gas. This is accomplished by tilting a Raman cell (20) to produce a high-intensity, backward-stimulated, coherent Raman beam of 683 nm, which drives a degenerate optical parametric oscillator (28) to produce a broadband beam of 1100-1700 nm covering a range of more than 3000 wavenumber. This broadband beam is combined with a narrowband beam of 532 nm having a bandwidth of 0.003 wavenumbers and focused into a heated windowless cell (38) that receives gases separated by a gas chromatograph (40). The Raman radiation scattered from these gases is filtered and sent to a monochromator (50) with multichannel detection.

Multiplex coherent raman spectroscopy detector and method

DOEpatents

Chen, Peter; Joyner, Candace C.; Patrick, Sheena T.; Guyer, Dean R.

2004-06-08

A multiplex coherent Raman spectrometer (10) and spectroscopy method rapidly detects and identifies individual components of a chemical mixture separated by a separation technique, such as gas chromatography. The spectrometer (10) and method accurately identify a variety of compounds because they produce the entire gas phase vibrational Raman spectrum of the unknown gas. This is accomplished by tilting a Raman cell (20) to produce a high-intensity, backward-stimulated, coherent Raman beam of 683 nm, which drives a degenerate optical parametric oscillator (28) to produce a broadband beam of 1100-1700 nm covering a range of more than 3000 wavenumber. This broadband beam is combined with a narrowband beam of 532 nm having a bandwidth of 0.003 wavenumbers and focused into a heated windowless cell (38) that receives gases separated by a gas chromatograph (40). The Raman radiation scattered from these gases is filtered and sent to a monochromator (50) with multichannel detection.

Accuracy of Raman spectroscopy in differentiating brain tumor from normal brain tissue.

PubMed

Zhang, Jing; Fan, Yimeng; He, Min; Ma, Xuelei; Song, Yanlin; Liu, Ming; Xu, Jianguo

2017-05-30

Raman spectroscopy could be applied to distinguish tumor from normal tissues. This meta-analysis was conducted to assess the accuracy of Raman spectroscopy in differentiating brain tumor from normal brain tissue. PubMed and Embase were searched to identify suitable studies prior to Jan 1st, 2016. We estimated the pooled sensitivity, specificity, positive and negative likelihood ratios (LR), diagnostic odds ratio (DOR), and constructed summary receiver operating characteristics (SROC) curves to identity the accuracy of Raman spectroscopy in differentiating brain tumor from normal brain tissue. A total of six studies with 1951 spectra were included. For glioma, the pooled sensitivity and specificity of Raman spectroscopy were 0.96 (95% CI 0.94-0.97) and 0.99 (95% CI 0.98-0.99), respectively. The area under the curve (AUC) was 0.9831. For meningioma, the pooled sensitivity and specificity were 0.98 (95% CI 0.94-1.00) and 1.00 (95% CI 0.98-1.00), respectively. The AUC was 0.9955. This meta-analysis suggested that Raman spectroscopy could be an effective and accurate tool for differentiating glioma and meningioma from normal brain tissue, which would help us both avoid removal of normal tissue and minimize the volume of residual tumor.

Quantitative polarized Raman spectroscopy in highly turbid bone tissue

NASA Astrophysics Data System (ADS)

Raghavan, Mekhala; Sahar, Nadder D.; Wilson, Robert H.; Mycek, Mary-Ann; Pleshko, Nancy; Kohn, David H.; Morris, Michael D.

2010-05-01

Polarized Raman spectroscopy allows measurement of molecular orientation and composition and is widely used in the study of polymer systems. Here, we extend the technique to the extraction of quantitative orientation information from bone tissue, which is optically thick and highly turbid. We discuss multiple scattering effects in tissue and show that repeated measurements using a series of objectives of differing numerical apertures can be employed to assess the contributions of sample turbidity and depth of field on polarized Raman measurements. A high numerical aperture objective minimizes the systematic errors introduced by multiple scattering. We test and validate the use of polarized Raman spectroscopy using wild-type and genetically modified (oim/oim model of osteogenesis imperfecta) murine bones. Mineral orientation distribution functions show that mineral crystallites are not as well aligned (p<0.05) in oim/oim bones (28+/-3 deg) compared to wild-type bones (22+/-3 deg), in agreement with small-angle X-ray scattering results. In wild-type mice, backbone carbonyl orientation is 76+/-2 deg and in oim/oim mice, it is 72+/-4 deg (p>0.05). We provide evidence that simultaneous quantitative measurements of mineral and collagen orientations on intact bone specimens are possible using polarized Raman spectroscopy.

Quantitative polarized Raman spectroscopy in highly turbid bone tissue.

PubMed

Raghavan, Mekhala; Sahar, Nadder D; Wilson, Robert H; Mycek, Mary-Ann; Pleshko, Nancy; Kohn, David H; Morris, Michael D

2010-01-01

Polarized Raman spectroscopy allows measurement of molecular orientation and composition and is widely used in the study of polymer systems. Here, we extend the technique to the extraction of quantitative orientation information from bone tissue, which is optically thick and highly turbid. We discuss multiple scattering effects in tissue and show that repeated measurements using a series of objectives of differing numerical apertures can be employed to assess the contributions of sample turbidity and depth of field on polarized Raman measurements. A high numerical aperture objective minimizes the systematic errors introduced by multiple scattering. We test and validate the use of polarized Raman spectroscopy using wild-type and genetically modified (oim/oim model of osteogenesis imperfecta) murine bones. Mineral orientation distribution functions show that mineral crystallites are not as well aligned (p<0.05) in oim/oim bones (28+/-3 deg) compared to wild-type bones (22+/-3 deg), in agreement with small-angle X-ray scattering results. In wild-type mice, backbone carbonyl orientation is 76+/-2 deg and in oim/oim mice, it is 72+/-4 deg (p>0.05). We provide evidence that simultaneous quantitative measurements of mineral and collagen orientations on intact bone specimens are possible using polarized Raman spectroscopy.

Raman spectroscopy on ice cores from Greenland and Antarctica

NASA Astrophysics Data System (ADS)

Weikusat, C.; Kipfstuhl, S.

2012-04-01

Ice cores are invaluable archives for the reconstruction of the climatic history of the earth. Besides the analysis of various climatic processes from isotopes and chemical signatures they offer the unique possibility of directly extracting the past atmosphere from gaseous inclusions in the ice. Many aspects of the formation and alterations of these inclusions, e.g. the entrapment of air at the firn-ice-transition, the formation of crystalline gas hydrates (clathrates) from the bubbles or the structural relaxation during storage of the cores, need to be better understood to enable reliable interpretations of the obtained data. Modern micro Raman spectroscopy is an excellent tool to obtain high-quality data for all of these aspects. It has been productively used for phase identification of solid inclusions [1], investigation of air clathrates [2] and high-resolution measurements of N2/O2 mixing ratios inside individual air bubbles [3,4]. Detailed examples of the various uses of Raman spectroscopy will be presented along with practical information about the techniques required to obtain high-quality spectra. Retrieval and interpretation of quantitative data from the spectra will be explained. Future possibilities for advanced uses of Raman spectroscopy for ice core research will be discussed. [1] T. Sakurai et al., 2009, Direct observation of salts as micro-inclusions in the Greenland GRIP ice core. Journal of Glaciology, 55, 777-783. [2] F. Pauer et al., 1995, Raman spectroscopic study of nitrogen/oxygen ratio in natural ice clathrates in the GRIP ice core. Geophysical Research Letters, 22, 969-971. [3] T. Ikeda-Fukazawa et al., 2001, Variation in N2/O2 ratio of occluded air in Dome Fuji antarctic ice. Journal of Geophysical Research, 106, 17799-17810. [4] C. Weikusat et al., Raman spectroscopy of gaseous inclusions in EDML ice core: First results - microbubbles. Journal of Glaciology, accepted.

Time-Gated Raman Spectroscopy for Quantitative Determination of Solid-State Forms of Fluorescent Pharmaceuticals.

PubMed

Lipiäinen, Tiina; Pessi, Jenni; Movahedi, Parisa; Koivistoinen, Juha; Kurki, Lauri; Tenhunen, Mari; Yliruusi, Jouko; Juppo, Anne M; Heikkonen, Jukka; Pahikkala, Tapio; Strachan, Clare J

2018-04-03

Raman spectroscopy is widely used for quantitative pharmaceutical analysis, but a common obstacle to its use is sample fluorescence masking the Raman signal. Time-gating provides an instrument-based method for rejecting fluorescence through temporal resolution of the spectral signal and allows Raman spectra of fluorescent materials to be obtained. An additional practical advantage is that analysis is possible in ambient lighting. This study assesses the efficacy of time-gated Raman spectroscopy for the quantitative measurement of fluorescent pharmaceuticals. Time-gated Raman spectroscopy with a 128 × (2) × 4 CMOS SPAD detector was applied for quantitative analysis of ternary mixtures of solid-state forms of the model drug, piroxicam (PRX). Partial least-squares (PLS) regression allowed quantification, with Raman-active time domain selection (based on visual inspection) improving performance. Model performance was further improved by using kernel-based regularized least-squares (RLS) regression with greedy feature selection in which the data use in both the Raman shift and time dimensions was statistically optimized. Overall, time-gated Raman spectroscopy, especially with optimized data analysis in both the spectral and time dimensions, shows potential for sensitive and relatively routine quantitative analysis of photoluminescent pharmaceuticals during drug development and manufacturing.

Detection of Leukemia with Blood Samples Using Raman Spectroscopy and Multivariate Analysis

NASA Astrophysics Data System (ADS)

Martínez-Espinosa, J. C.; González-Solís, J. L.; Frausto-Reyes, C.; Miranda-Beltrán, M. L.; Soria-Fregoso, C.; Medina-Valtierra, J.

2009-06-01

The use of Raman spectroscopy to analyze blood biochemistry and hence distinguish between normal and abnormal blood was investigated. Blood samples were obtained from 6 patients who were clinically diagnosed with leukemia and 6 healthy volunteers. The imprint was put under the microscope and several points were chosen for Raman measurement. All the spectra were collected by a confocal Raman micro-spectroscopy (Renishaw) with a NIR 830 nm laser. It is shown that the serum samples from patients with leukemia and from the control group can be discriminated when the multivariate statistical methods of principal component analysis (PCA) and linear discriminated analysis (LDA) are applied to their Raman spectra. The ratios of some band intensities were analyzed and some band ratios were significant and corresponded to proteins, phospholipids, and polysaccharides. The preliminary results suggest that Raman Spectroscopy could be a new technique to study the degree of damage to the bone marrow using just blood samples instead of biopsies, treatment very painful for patients.

Characterization of Kevlar Using Raman Spectroscopy

NASA Technical Reports Server (NTRS)

Washer, Glenn; Brooks, Thomas; Saulsberry, Regor

2007-01-01

This paper explores the characterization of Kevlar composite materials using Raman spectroscopy. The goal of the research is to develop and understand the Raman spectrum of Kevlar materials to provide a foundation for the development of nondestructive evaluation (NDE) technologies based on the interaction of laser light with the polymer Kevlar. The paper discusses the fundamental aspects of experimental characterization of the spectrum of Kevlar, including the effects of incident wavelength, polarization and laser power. The effects of environmental exposure of Kevlar materials on certain characteristics of its Raman spectrum are explored, as well as the effects of applied stress. This data may provide a foundation for the development of NDE technologies intended to detect the in-situ deterioration of Kevlar materials used for engineering applications that can later be extended to other materials such as carbon fiber composites.

Gold-nanofève surface-enhanced Raman spectroscopy visualizes hypotaurine as a robust anti-oxidant consumed in cancer survival.

PubMed

Shiota, Megumi; Naya, Masayuki; Yamamoto, Takehiro; Hishiki, Takako; Tani, Takeharu; Takahashi, Hiroyuki; Kubo, Akiko; Koike, Daisuke; Itoh, Mai; Ohmura, Mitsuyo; Kabe, Yasuaki; Sugiura, Yuki; Hiraoka, Nobuyoshi; Morikawa, Takayuki; Takubo, Keiyo; Suina, Kentaro; Nagashima, Hideaki; Sampetrean, Oltea; Nagano, Osamu; Saya, Hideyuki; Yamazoe, Shogo; Watanabe, Hiroyuki; Suematsu, Makoto

2018-04-19

Gold deposition with diagonal angle towards boehmite-based nanostructure creates random arrays of horse-bean-shaped nanostructures named gold-nanofève (GNF). GNF generates many electromagnetic hotspots as surface-enhanced Raman spectroscopy (SERS) excitation sources, and enables large-area visualization of molecular vibration fingerprints of metabolites in human cancer xenografts in livers of immunodeficient mice with sufficient sensitivity and uniformity. Differential screening of GNF-SERS signals in tumours and those in parenchyma demarcated tumour boundaries in liver tissues. Furthermore, GNF-SERS combined with quantum chemical calculation identified cysteine-derived glutathione and hypotaurine (HT) as tumour-dominant and parenchyma-dominant metabolites, respectively. CD44 knockdown in cancer diminished glutathione, but not HT in tumours. Mechanisms whereby tumours sustained HT under CD44-knockdown conditions include upregulation of PHGDH, PSAT1 and PSPH that drove glycolysis-dependent activation of serine/glycine-cleavage systems to provide one-methyl group for HT synthesis. HT was rapidly converted into taurine in cancer cells, suggesting that HT is a robust anti-oxidant for their survival under glutathione-suppressed conditions.

Raman spectroscopy for grading of live osteosarcoma cells.

PubMed

Chiang, Yi-Hung; Wu, Stewart H; Kuo, Yi-Chun; Chen, How-Foo; Chiou, Arthur; Lee, Oscar K

2015-04-18

Osteosarcoma is the most common primary malignant bone tumor, and the grading of osteosarcoma cells relies on traditional histopathology and molecular biology methods, which require RNA extraction, protein isolation and immunohistological staining. All these methods require cell isolation, lysis or fixation, which is time-consuming and requires certain amount of tumor specimen. In this study, we report the use of Raman spectroscopy for grading of malignant osteosarcoma cells. We demonstrate that, based on the detection of differential production of mineral species, Raman spectroscopy can be used as a live cell analyzer to accurately assess the grades of osteosarcoma cells by evaluating their mineralization levels. Mineralization level was assessed by measuring amount of hydroxyapatite (HA), which is highly expressed in mature osteoblasts, but not in poorly differentiated osteosarcoma cell or mesenchymal stem cells, the putative cell-of-origin of osteosarcoma. We found that under Raman spectroscopy, the level of HA production was high in MG-63 cells, which are low-grade. Moreover, hydroxyapatite production was low in high-grade osteosarcoma cells such as 143B and SaOS2 cells (p < 0.05). Matrix metalloproteinase MMP2, MMP9 were highly expressed in SaOS2, 143B and MSCs and decreased in human fetal osteoblast (FOB) and MG-63 cells as expected (p < 0.05). These results may highlight the inverse correlation between HA level and prognosis of osteosarcoma. The use of Raman spectroscopy for the measurement of HA production by the protocol reported in this study may serve as a useful tool to rapidly and accurately assess the degree of malignancy in osteosarcoma cells in a label-free manner. Such application may shorten the period of pathological diagnosis and may benefit patients who are inflicted with osteosarcoma.

Matrix Effects in Quantitative Assessment of Pharmaceutical Tablets Using Transmission Raman and Near-Infrared (NIR) Spectroscopy.

PubMed

Sparén, Anders; Hartman, Madeleine; Fransson, Magnus; Johansson, Jonas; Svensson, Olof

2015-05-01

Raman spectroscopy can be an alternative to near-infrared spectroscopy (NIR) for nondestructive quantitative analysis of solid pharmaceutical formulations. Compared with NIR spectra, Raman spectra have much better selectivity, but subsampling was always an issue for quantitative assessment. Raman spectroscopy in transmission mode has reduced this issue, since a large volume of the sample is measured in transmission mode. The sample matrix, such as particle size of the drug substance in a tablet, may affect the Raman signal. In this work, matrix effects in transmission NIR and Raman spectroscopy were systematically investigated for a solid pharmaceutical formulation. Tablets were manufactured according to an experimental design, varying the factors particle size of the drug substance (DS), particle size of the filler, compression force, and content of drug substance. All factors were varied at two levels plus a center point, except the drug substance content, which was varied at five levels. Six tablets from each experimental point were measured with transmission NIR and Raman spectroscopy, and their concentration of DS was determined for a third of those tablets. Principal component analysis of NIR and Raman spectra showed that the drug substance content and particle size, the particle size of the filler, and the compression force affected both NIR and Raman spectra. For quantitative assessment, orthogonal partial least squares regression was applied. All factors varied in the experimental design influenced the prediction of the DS content to some extent, both for NIR and Raman spectroscopy, the particle size of the filler having the largest effect. When all matrix variations were included in the multivariate calibrations, however, good predictions of all types of tablets were obtained, both for NIR and Raman spectroscopy. The prediction error using transmission Raman spectroscopy was about 30% lower than that obtained with transmission NIR spectroscopy.

Raman spectroscopy and imaging: applications in human breast cancer diagnosis.

PubMed

Brozek-Pluska, Beata; Musial, Jacek; Kordek, Radzislaw; Bailo, Elena; Dieing, Thomas; Abramczyk, Halina

2012-08-21

The applications of spectroscopic methods in cancer detection open new possibilities in early stage diagnostics. Raman spectroscopy and Raman imaging represent novel and rapidly developing tools in cancer diagnosis. In the study described in this paper Raman spectroscopy has been employed to examine noncancerous and cancerous human breast tissues of the same patient. The most significant differences between noncancerous and cancerous tissues were found in regions characteristic for the vibrations of carotenoids, lipids and proteins. Particular attention was paid to the role played by unsaturated fatty acids in the differentiation between the noncancerous and the cancerous tissues. Comparison of Raman spectra of the noncancerous and the cancerous tissues with the spectra of oleic, linoleic, α-linolenic, γ-linolenic, docosahexaenoic and eicosapentaenoic acids has been presented. The role of sample preparation in the determination of cancer markers is also discussed in this study.

Medical applications of atomic force microscopy and Raman spectroscopy.

PubMed

Choi, Samjin; Jung, Gyeong Bok; Kim, Kyung Sook; Lee, Gi-Ja; Park, Hun-Kuk

2014-01-01

This paper reviews the recent research and application of atomic force microscopy (AFM) and Raman spectroscopy techniques, which are considered the multi-functional and powerful toolkits for probing the nanostructural, biomechanical and physicochemical properties of biomedical samples in medical science. We introduce briefly the basic principles of AFM and Raman spectroscopy, followed by diagnostic assessments of some selected diseases in biomedical applications using them, including mitochondria isolated from normal and ischemic hearts, hair fibers, individual cells, and human cortical bone. Finally, AFM and Raman spectroscopy applications to investigate the effects of pharmacotherapy, surgery, and medical device therapy in various medicines from cells to soft and hard tissues are discussed, including pharmacotherapy--paclitaxel on Ishikawa and HeLa cells, telmisartan on angiotensin II, mitomycin C on strabismus surgery and eye whitening surgery, and fluoride on primary teeth--and medical device therapy--collagen cross-linking treatment for the management of progressive keratoconus, radiofrequency treatment for skin rejuvenation, physical extracorporeal shockwave therapy for healing of Achilles tendinitis, orthodontic treatment, and toothbrushing time to minimize the loss of teeth after exposure to acidic drinks.

In situ monitoring of cocrystals in formulation development using low-frequency Raman spectroscopy.

PubMed

Otaki, Takashi; Tanabe, Yuta; Kojima, Takashi; Miura, Masaru; Ikeda, Yukihiro; Koide, Tatsuo; Fukami, Toshiro

2018-05-05

In recent years, to guarantee a quality-by-design approach to the development of pharmaceutical products, it is important to identify properties of raw materials and excipients in order to determine critical process parameters and critical quality attributes. Feedback obtained from real-time analyses using various process analytical technology (PAT) tools has been actively investigated. In this study, in situ monitoring using low-frequency (LF) Raman spectroscopy (10-200 cm -1 ), which may have higher discriminative ability among polymorphs than near-infrared spectroscopy and conventional Raman spectroscopy (200-1800 cm -1 ), was investigated as a possible application to PAT. This is because LF-Raman spectroscopy obtains information about intermolecular and/or lattice vibrations in the solid state. The monitoring results obtained from Furosemide/Nicotinamide cocrystal indicate that LF-Raman spectroscopy is applicable to in situ monitoring of suspension and fluidized bed granulation processes, and is an effective technique as a PAT tool to detect the conversion risk of cocrystals. LF-Raman spectroscopy is also used as a PAT tool to monitor reactions, crystallizations, and manufacturing processes of drug substances and products. In addition, a sequence of conversion behaviors of Furosemide/Nicotinamide cocrystals was determined by performing in situ monitoring for the first time. Copyright © 2018 Elsevier B.V. All rights reserved.

Coherent Raman spectroscopies for measuring molecular flow velocity

NASA Technical Reports Server (NTRS)

She, C. Y.

1982-01-01

Various types of coherent Raman spectroscopy are characterized and their application to molecular flow velocity and direction measurement and species concentration and temperature determination is discussed.

Raman spectroscopy for in-line water quality monitoring--instrumentation and potential.

PubMed

Li, Zhiyun; Deen, M Jamal; Kumar, Shiva; Selvaganapathy, P Ravi

2014-09-16

Worldwide, the access to safe drinking water is a huge problem. In fact, the number of persons without safe drinking water is increasing, even though it is an essential ingredient for human health and development. The enormity of the problem also makes it a critical environmental and public health issue. Therefore, there is a critical need for easy-to-use, compact and sensitive techniques for water quality monitoring. Raman spectroscopy has been a very powerful technique to characterize chemical composition and has been applied to many areas, including chemistry, food, material science or pharmaceuticals. The development of advanced Raman techniques and improvements in instrumentation, has significantly improved the performance of modern Raman spectrometers so that it can now be used for detection of low concentrations of chemicals such as in-line monitoring of chemical and pharmaceutical contaminants in water. This paper briefly introduces the fundamentals of Raman spectroscopy, reviews the development of Raman instrumentations and discusses advanced and potential Raman techniques for in-line water quality monitoring.

Surface- and Tip-Enhanced Raman Spectroscopy in Catalysis

PubMed Central

2016-01-01

Surface- and tip-enhanced Raman spectroscopy (SERS and TERS) techniques exhibit highly localized chemical sensitivity, making them ideal for studying chemical reactions, including processes at catalytic surfaces. Catalyst structures, adsorbates, and reaction intermediates can be observed in low quantities at hot spots where electromagnetic fields are the strongest, providing ample opportunities to elucidate reaction mechanisms. Moreover, under ideal measurement conditions, it can even be used to trigger chemical reactions. However, factors such as substrate instability and insufficient signal enhancement still limit the applicability of SERS and TERS in the field of catalysis. By the use of sophisticated colloidal synthesis methods and advanced techniques, such as shell-isolated nanoparticle-enhanced Raman spectroscopy, these challenges could be overcome. PMID:27075515

Coherent anti-Stokes Raman scattering for quantitative temperature and concentration measurements in a high-pressure gas turbine combustor rig

NASA Astrophysics Data System (ADS)

Thariyan, Mathew Paul

Dual-pump coherent anti-Stokes Raman scattering (DP-CARS) temperature and major species (CO2/N2) concentration measurements have been performed in an optically-accessible high-pressure gas turbine combustor facility (GTCF) and for partially-premixed and non-premixed flames in a laminar counter-flow burner. A window assembly incorporating pairs of thin and thick fused silica windows on three sides was designed, fabricated, and assembled in the GTCF for advanced laser diagnostic studies. An injection-seeded optical parametric oscillator (OPO) was used as a narrowband pump laser source in the dual-pump CARS system. Large prisms on computer-controlled translation stages were used to direct the CARS beams either into the main optics leg for measurements in the GTCF or to a reference optics leg for measurements of the nonresonant CARS spectrum and for aligning the CARS system. Combusting flows were stabilized with liquid fuel injection only for the central injector of a 9-element lean direct injection (LDI) device developed at NASA Glenn Research Center. The combustor was operated using Jet A fuel at inlet air temperatures up to 725 K and combustor pressures up to 1.03 MPa. Single-shot DP-CARS spectra were analyzed using the Sandia CARSFT code in the batch operation mode to yield instantaneous temperature and CO2/N2 concentration ratio values. Spatial maps of mean and standard deviations of temperature and CO2/N2 concentrations were obtained in the high-pressure LDI flames by translating the CARS probe volume in axial and vertical directions inside the combustor rig. The mean temperature fields demonstrate the effect of the combustor conditions on the overall flame length and the average flame structure. The temperature relative standard deviation values indicate thermal fluctuations due to the presence of recirculation zones and/or flame brush fluctuations. The correlation between the temperature and relative CO 2 concentration data has been studied at various combustor

Spatially offset Raman spectroscopy for explosives detection through difficult (opaque) containers

NASA Astrophysics Data System (ADS)

Maskall, Guy T.; Bonthron, Stuart; Crawford, David

2013-10-01

With the continuing threat to aviation security from homemade explosive devices, the restrictions on taking a volume of liquid greater than 100 ml onto an aircraft remain in place. From January 2014, these restrictions will gradually be reduced via a phased implementation of technological screening of Liquids, Aerosols and Gels (LAGs). Raman spectroscopy offers a highly sensitive, and specific, technique for the detection and identification of chemicals. Spatially Offset Raman Spectroscopy (SORS), in particular, offers significant advantages over conventional Raman spectroscopy for detecting and recognizing contents within optically challenging (Raman active) containers. Containers vary enormously in their composition; glass type, plastic type, thickness, reflectance, and pigmentation are all variable and cause an infinite range of absorbances, fluorescence backgrounds, Rayleigh backscattered laser light, and container Raman bands. In this paper we show that the data processing chain for Cobalt Light Systems' INSIGHT100 bottlescanner is robust to such variability. We discuss issues of model selection for the detection stage and demonstrate an overall detection rate across a wide range of threats and containers of 97% with an associated false alarm rate of 0.1% or lower.

In-vivo spinal nerve sensing in MISS using Raman spectroscopy

NASA Astrophysics Data System (ADS)

Chen, Hao; Xu, Weiliang; Broderick, Neil

2016-04-01

In modern Minimally Invasive Spine Surgery (MISS), lack of visualization and haptic feedback information are the main obstacles. The spinal cord is a part of the central nervous system (CNS). It is a continuation of the brain stem, carries motor and sensory messages between CNS and the rest of body, and mediates numerous spinal reflexes. Spinal cord and spinal nerves are of great importance but vulnerable, once injured it may result in severe consequences to patients, e.g. paralysis. Raman Spectroscopy has been proved to be an effective and powerful tool in biological and biomedical applications as it works in a rapid, non-invasive and label-free way. It can provide molecular vibrational features of tissue samples and reflect content and proportion of protein, nucleic acids lipids etc. Due to the distinct chemical compositions spinal nerves have, we proposed that spinal nerves can be identified from other types of tissues by using Raman spectroscopy. Ex vivo experiments were first done on samples taken from swine backbones. Comparative spectral data of swine spinal cord, spinal nerves and adjacent tissues (i.e. membrane layer of the spinal cord, muscle, bone and fatty tissue) are obtained by a Raman micro-spectroscopic system and the peak assignment is done. Then the average spectra of all categories of samples are averaged and normalized to the same scale to see the difference against each other. The results verified the feasibility of spinal cord and spinal nerves identification by using Raman spectroscopy. Besides, a fiber-optic Raman sensing system including a miniature Raman sensor for future study is also introduced. This Raman sensor can be embedded into surgical tools for MISS.

Raman spectroscopy applied to identify metabolites in urine of physically active subjects.

PubMed

Moreira, Letícia Parada; Silveira, Landulfo; da Silva, Alexandre Galvão; Fernandes, Adriana Barrinha; Pacheco, Marcos Tadeu Tavares; Rocco, Débora Dias Ferraretto Moura

2017-11-01

Raman spectroscopy is a rapid and non-destructive technique suitable for biological fluids analysis. In this work, dispersive Raman spectroscopy has been employed as a rapid and nondestructive technique to detect the metabolites in urine of physically active subjects before and after vigorous 30min pedaling or running compared to sedentary subjects. For so, urine samples from 9 subjects were obtained before and immediately after physical activities and submitted to Raman spectroscopy (830nm excitation, 250mW laser power, 20s integration time) and compared to urine from 5 sedentary subjects. The Raman spectra of urine from sedentary showed peaks related to urea, creatinine, ketone bodies, phosphate and other nitrogenous compounds. These metabolic biomarkers presented peaks with different intensities in the urine of physically active individuals after exercises compared to before, measured by the intensity of selected peaks the Raman spectra, which means different concentrations after training. These peaks presented different intensity values for each subject before physical activity, also behaving differently compared to the post-training: some subjects presented increase while others decrease the intensity. Raman spectroscopy may allow the development of a rapid and non-destructive test for metabolic evaluation of the physical training in active and trained subjects using urine samples, allowing nutrition adjustment with the sport's performance. Copyright © 2017 Elsevier B.V. All rights reserved.

Multi-fiber strains measured by micro-Raman spectroscopy: Principles and experiments

NASA Astrophysics Data System (ADS)

Lei, Zhenkun; Wang, Yunfeng; Qin, Fuyong; Qiu, Wei; Bai, Ruixiang; Chen, Xiaogang

2016-02-01

Based on widely used axial strain measurement method of Kevlar single fiber, an original theoretical model and measurement principle of application of micro-Raman spectroscopy to multi-fiber strains in a fiber bundle were established. The relationship between the nominal Raman shift of fiber bundle and the multi-fiber strains was deduced. The proposed principle for multi-fiber strains measurement is consistent with two special cases: single fiber deformation and multi-fiber deformation under equal strain. It is found experimentally that the distribution of Raman scattering intensity of a Kevlar 49 fiber as a function of distance between a fiber and the laser spot center follows a Gaussian function. Combining the Raman-shift/strain relationship of the Kevlar 49 single fiber and the uniaxial tension measured by micro-Raman spectroscopy, the Raman shift as a function of strain was obtained. Then the Raman peak at 1610 cm-1 for the Kevlar 49 fiber was fitted to a Lorentzian function and the FWHM showed a quadratic increase with the fiber strain. Finally, a dual-fiber tensile experiment was performed to verify the adequacy of the Raman technique for the measurement of multi-fiber strains.

Blood proteins analysis by Raman spectroscopy method

NASA Astrophysics Data System (ADS)

Artemyev, D. N.; Bratchenko, I. A.; Khristoforova, Yu. A.; Lykina, A. A.; Myakinin, O. O.; Kuzmina, T. P.; Davydkin, I. L.; Zakharov, V. P.

2016-04-01

This work is devoted to study the possibility of plasma proteins (albumin, globulins) concentration measurement using Raman spectroscopy setup. The blood plasma and whole blood were studied in this research. The obtained Raman spectra showed significant variation of intensities of certain spectral bands 940, 1005, 1330, 1450 and 1650 cm-1 for different protein fractions. Partial least squares regression analysis was used for determination of correlation coefficients. We have shown that the proposed method represents the structure and biochemical composition of major blood proteins.

Candida parapsilosis biofilm identification by Raman spectroscopy.

PubMed

Samek, Ota; Mlynariková, Katarina; Bernatová, Silvie; Ježek, Jan; Krzyžánek, Vladislav; Šiler, Martin; Zemánek, Pavel; Růžička, Filip; Holá, Veronika; Mahelová, Martina

2014-12-22

Colonies of Candida parapsilosis on culture plates were probed directly in situ using Raman spectroscopy for rapid identification of specific strains separated by a given time intervals (up to months apart). To classify the Raman spectra, data analysis was performed using the approach of principal component analysis (PCA). The analysis of the data sets generated during the scans of individual colonies reveals that despite the inhomogeneity of the biological samples unambiguous associations to individual strains (two biofilm-positive and two biofilm-negative) could be made.

Candida parapsilosis Biofilm Identification by Raman Spectroscopy

PubMed Central

Samek, Ota; Mlynariková, Katarina; Bernatová, Silvie; Ježek, Jan; Krzyžánek, Vladislav; Šiler, Martin; Zemánek, Pavel; Růžička, Filip; Holá, Veronika; Mahelová, Martina

2014-01-01

Colonies of Candida parapsilosis on culture plates were probed directly in situ using Raman spectroscopy for rapid identification of specific strains separated by a given time intervals (up to months apart). To classify the Raman spectra, data analysis was performed using the approach of principal component analysis (PCA). The analysis of the data sets generated during the scans of individual colonies reveals that despite the inhomogeneity of the biological samples unambiguous associations to individual strains (two biofilm-positive and two biofilm-negative) could be made. PMID:25535081

Real time near-infrared Raman spectroscopy for the diagnosis of nasopharyngeal cancer.

PubMed

Ming, Lim Chwee; Gangodu, Nagaraja Rao; Loh, Thomas; Zheng, Wei; Wang, Jianfeng; Lin, Kan; Zhiwei, Huang

2017-07-25

Near-infrared (NIR) Raman spectroscopy has been investigated as a tool to differentiate nasopharyngeal cancer (NPC) from normal nasopharyngeal tissue in an ex-vivo setting. Recently, we have miniaturized the fiber-optic Raman probe to investigate its utility in real time in-vivo surveillance of NPC patients. A posterior probability model using partial linear square (PLS) mathematical technique was constructed to verify the sensitivity and specificity of Raman spectroscopy in diagnosing NPC from post-irradiated and normal tissue using a diagnostic algorithm from three significant latent variables. NIR-Raman signals of 135 sites were measured from 79 patients with either newly diagnosed NPC (N = 12), post irradiated nasopharynx (N = 37) and normal nasopharynx (N = 30). The mean Raman spectra peaks identified differences at several Raman peaks at 853 cm-1, 940 cm-1, 1078 cm-1, 1335 cm-1, 1554 cm-1, 2885 cm-1 and 2940 cm-1 in the three different nasopharyngeal conditions. The sensitivity and specificity of distinguishing Raman signatures among normal nasopharynx versus NPC and post-irradiated nasopharynx versus NPC were 91% and 95%; and 77% and 96% respectively. Real time near-infrared Raman spectroscopy has a high specificity in distinguishing malignant from normal nasopharyngeal tissue in vivo, and may be investigated as a novel non-invasive surveillance tool in patients with nasopharyngeal cancer.

Micro-Raman spectroscopy of natural and synthetic indigo samples.

PubMed

Vandenabeele, Peter; Moens, Luc

2003-02-01

In this work indigo samples from three different sources are studied by using Raman spectroscopy: the synthetic pigment and pigments from the woad (Isatis tinctoria) and the indigo plant (Indigofera tinctoria). 21 samples were obtained from 8 suppliers; for each sample 5 Raman spectra were recorded and used for further chemometrical analysis. Principal components analysis (PCA) was performed as data reduction method before applying hierarchical cluster analysis. Linear discriminant analysis (LDA) was implemented as a non-hierarchical supervised pattern recognition method to build a classification model. In order to avoid broad-shaped interferences from the fluorescence background, the influence of 1st and 2nd derivatives on the classification was studied by using cross-validation. Although chemically identical, it is shown that Raman spectroscopy in combination with suitable chemometric methods has the potential to discriminate between synthetic and natural indigo samples.

Non-invasive sex assessment in bovine semen by Raman spectroscopy

NASA Astrophysics Data System (ADS)

De Luca, A. C.; Managó, S.; Ferrara, M. A.; Rendina, I.; Sirleto, L.; Puglisi, R.; Balduzzi, D.; Galli, A.; Ferraro, P.; Coppola, G.

2014-05-01

X- and Y-chromosome-bearing sperm cell sorting is of great interest, especially for animal production management systems and genetic improvement programs. Here, we demonstrate an optical method based on Raman spectroscopy to separate X- and Y-chromosome-bearing sperm cells, overcoming many of the limitations associated with current sex-sorting protocols. A priori Raman imaging of bull spermatozoa was utilized to select the sampling points (head-neck region), which were then used to discriminate cells based on a spectral classification model. Main variations of Raman peaks associated with the DNA content were observed together with a variation due to the sex membrane proteins. Next, we used principal component analysis to determine the efficiency of our device as a cell sorting method. The results (>90% accuracy) demonstrated that Raman spectroscopy is a powerful candidate for the development of a highly efficient, non-invasive, and non-destructive tool for sperm sexing.

Analysis of 2-ethylhexyl-p-methoxycinnamate in sunscreen products by HPLC and Raman spectroscopy.

PubMed

Cheng, J; Li, Y S; L Roberts, R; Walker, G

1997-10-01

The analyses of 2-ethylhexyl-p-methoxycinnamate (EHMC) using HPLC and Raman spectroscopy have been undertaken and compared. EHMC, which is one of the most widely used sunscreen agents in suncare products in the US, exhibits a strong Raman signal. This signal clearly appears in both ethanol solutions of EHMC as well as in commercial sunscreen lotions containing this sun screen agent. A method for the direct detection and analysis of EHMC has been developed using Raman spectroscopy. This was accomplished by correlating the Raman intensities with the HPLC assays for a series of prototype suncare formulations. Based upon this information, it would be possible to employ Raman spectroscopy as an in-process control method in the commercial production of suncare products containing EHMC. The possibility of applying surface-enhanced Raman scattering for trace analysis was discussed.

Characterization of uranium tetrafluoride (UF 4) with Raman spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Villa-Aleman, Eliel; Wellons, Matthew S.

The Raman spectrum of uranium tetrafluoride (UF 4) is unambiguously characterized with multiple Raman excitation laser sources for the first time. Across different laser excitation wavelengths, UF 4 demonstrates 16 distinct Raman bands within the 50-400 cm -1 region. The observed Raman bands are representative of various F-F vibrational modes. UF 4 also shows intense fluorescent bands in the 325 – 750 nm spectral region. Comparison of the UF 4 spectrum with the ZrF 4 spectrum, its crystalline analog, demonstrates a similar Raman band structure consistent with group theory predictions for expected Raman bands. Additionally, a demonstration of combined scanningmore » electron microscopy (SEM) and in situ Raman spectroscopy microanalytical measurements of UF 4 particulates shows that despite the inherent weak intensity of Raman bands, identification and characterization are possible for micron-sized particulates with modern instrumentation. The published well characterized UF 4 spectrum is extremely relevant to nuclear materials and nuclear safeguard applications.« less

Characterization of uranium tetrafluoride (UF 4) with Raman spectroscopy

DOE PAGES

Villa-Aleman, Eliel; Wellons, Matthew S.

2016-03-22

The Raman spectrum of uranium tetrafluoride (UF 4) is unambiguously characterized with multiple Raman excitation laser sources for the first time. Across different laser excitation wavelengths, UF 4 demonstrates 16 distinct Raman bands within the 50-400 cm -1 region. The observed Raman bands are representative of various F-F vibrational modes. UF 4 also shows intense fluorescent bands in the 325 – 750 nm spectral region. Comparison of the UF 4 spectrum with the ZrF 4 spectrum, its crystalline analog, demonstrates a similar Raman band structure consistent with group theory predictions for expected Raman bands. Additionally, a demonstration of combined scanningmore » electron microscopy (SEM) and in situ Raman spectroscopy microanalytical measurements of UF 4 particulates shows that despite the inherent weak intensity of Raman bands, identification and characterization are possible for micron-sized particulates with modern instrumentation. The published well characterized UF 4 spectrum is extremely relevant to nuclear materials and nuclear safeguard applications.« less

Raman spectroscopy for medical diagnostics--From in-vitro biofluid assays to in-vivo cancer detection.

PubMed

Kong, Kenny; Kendall, Catherine; Stone, Nicholas; Notingher, Ioan

2015-07-15

Raman spectroscopy is an optical technique based on inelastic scattering of light by vibrating molecules and can provide chemical fingerprints of cells, tissues or biofluids. The high chemical specificity, minimal or lack of sample preparation and the ability to use advanced optical technologies in the visible or near-infrared spectral range (lasers, microscopes, fibre-optics) have recently led to an increase in medical diagnostic applications of Raman spectroscopy. The key hypothesis underpinning this field is that molecular changes in cells, tissues or biofluids, that are either the cause or the effect of diseases, can be detected and quantified by Raman spectroscopy. Furthermore, multivariate calibration and classification models based on Raman spectra can be developed on large "training" datasets and used subsequently on samples from new patients to obtain quantitative and objective diagnosis. Historically, spontaneous Raman spectroscopy has been known as a low signal technique requiring relatively long acquisition times. Nevertheless, new strategies have been developed recently to overcome these issues: non-linear optical effects and metallic nanoparticles can be used to enhance the Raman signals, optimised fibre-optic Raman probes can be used for real-time in-vivo single-point measurements, while multimodal integration with other optical techniques can guide the Raman measurements to increase the acquisition speed and spatial accuracy of diagnosis. These recent efforts have advanced Raman spectroscopy to the point where the diagnostic accuracy and speed are compatible with clinical use. This paper reviews the main Raman spectroscopy techniques used in medical diagnostics and provides an overview of various applications. Copyright © 2015 The Authors. Published by Elsevier B.V. All rights reserved.

THE ROLE OF RAMAN SPECTROSCOPY IN THE ANALYTICAL CHEMISTRY OF POTABLE WATER

EPA Science Inventory

Advances in instrumentation are making Raman spectroscopy the tool of choice for an increasing number of chemical applications. For example, many recalcitrant industrial-process monitoring problems have been solved in recent years with in-line Raman spectrometers. Raman is attr...

THE ROLE OF RAMAN SPECTROSCOPY IN THE ANALYTICAL CHEMISTRY OF POTABLE WATER

EPA Science Inventory

Advances in instrumentation are making Raman spectroscopy the tool of choice for an increasing number of chemical applications. For example, many recalcitrant industrial process monitoring problems have been solved in recent years with in-line Raman spectrometers. Raman is attr...

Analytical Raman spectroscopic study for discriminant analysis of different animal-derived feedstuff: Understanding the high correlation between Raman spectroscopy and lipid characteristics.

PubMed

Gao, Fei; Xu, Lingzhi; Zhang, Yuejing; Yang, Zengling; Han, Lujia; Liu, Xian

2018-02-01

The objectives of the current study were to explore the correlation between Raman spectroscopy and lipid characteristics and to assess the potential of Raman spectroscopic methods for distinguishing the different sources of animal-originated feed based on lipid characteristics. A total of 105 lipid samples derived from five animal species have been analyzed by gas chromatography (GC) and FT-Raman spectroscopy. High correlations (r 2 >0.94) were found between the characteristic peak ratio of the Raman spectra (1654/1748 and 1654/1445) and the degree of unsaturation of the animal lipids. The results of FT-Raman data combined with chemometrics showed that the fishmeal, poultry, porcine and ruminant (bovine and ovine) MBMs could be well separated based on their lipid spectral characteristics. This study demonstrated that FT-Raman spectroscopy can mostly exhibit the lipid structure specificity of different species of animal-originated feed and can be used to discriminate different animal-originated feed samples. Copyright © 2017. Published by Elsevier Ltd.

Determination of the concentration of a Bryonia Dioica tincture by Raman spectroscopy

NASA Astrophysics Data System (ADS)

Milea, Irimie; Culea, E.; Iliescu, T.; Milea, Janetta

1995-03-01

It was established a method based on Raman spectroscopy in order to control the content and concentration of homeopathic dilutions. Dilutions of a tincture of Bryonia Dioica in ethanol were prepared and investigated by Raman spectroscopy. The Raman line at 881 cm-1 was found to depend linearly versus the concentration of Bryonia Dioica. This permits to obtain a calibration curve that may be used to determine the concentration of Bryonia Dioica in ethanol. The method may be extended to determine the concentration of various homeopathic dilutions.

Using Raman Spectroscopy and Surface-Enhanced Raman Scattering to Identify Colorants in Art: An Experiment for an Upper-Division Chemistry Laboratory

ERIC Educational Resources Information Center

Mayhew, Hannah E.; Frano, Kristen A.; Svoboda, Shelley A.; Wustholz, Kristin L.

2015-01-01

Surface-enhanced Raman scattering (SERS) studies of art represent an attractive way to introduce undergraduate students to concepts in nanoscience, vibrational spectroscopy, and instrumental analysis. Here, we present an undergraduate analytical or physical chemistry laboratory wherein a combination of normal Raman and SERS spectroscopy is used to…

Using Deep UV Raman Spectroscopy to Identify In Situ Microbial Activity

NASA Astrophysics Data System (ADS)

Sapers, H. M.; Wanger, G.; Amend, J.; Orphan, V. J.; Bhartia, R.

2017-12-01

Microbial communities living in close association with lithic substrates play a critical role in biogeochemical cycles. Understanding the interactions between microorganisms and their abiotic substrates requires knowledge of microbial activity. Identifying active cells adhered to complex environmental substrates, especially in low biomass systems, remains a challenge. Stable isotope probing (SIP) provides a means to trace microbial activity in environmental systems. Active members of the community take up labeled substrates and incorporate the labels into biomolecules that can be detected through downstream analyses. Here we show for the first time that Deep UV (248 nm) Raman spectroscopy can differentiate microbial cells labeled with stable isotopes. Previous studies have used Raman spectroscopy with a 532 nm source to identify active bacterial cells by measuring a Raman shift between peaks corresponding to amino acids incorporating 13C compared to controls. However, excitation at 532 nm precludes detection on complex substrates due to high autofluorescence of native minerals. Excitation in the DUV range offers non-destructive imaging on mineral surfaces - retaining critical contextual information. We prepared cultures of E. coli grown in 50 atom% 13C glucose spotted onto Al wafers to test the ability of DUV Raman spectroscopy to differentiate labeled and unlabeled cells. For the first time, we are able to demonstrate a distinct and repeatable shift between cells grown in labeled media and unlabeled media when imaged on Al wafers with DUV Raman spectroscopy. The Raman spectra are dominated by the characteristic Raman bands of guanine. The dominant marker peak for guanine attributed to N7-C8 and C8-N9 ring stretching and C8-H in-plane bending, is visible at 1480 cm-1 in the unlabeled cells and is blue-shifted by 20 wavenumbers to 1461 cm-1 in the labeled cells. The ability of DUV Raman to effectively identify regions containing cells that have incorporated isotopic

Understanding the application of Raman spectroscopy to the detection of traces of life.

PubMed

Marshall, Craig P; Edwards, Howell G M; Jehlicka, Jan

2010-03-01

Investigating carbonaceous microstructures and material in Earth's oldest sedimentary rocks is an essential part of tracing the origins of life on our planet; furthermore, it is important for developing techniques to search for traces of life on other planets, for example, Mars. NASA and ESA are considering the adoption of miniaturized Raman spectrometers for inclusion in suites of analytical instrumentation to be placed on robotic landers on Mars in the near future to search for fossil or extant biomolecules. Recently, Raman spectroscopy has been used to infer a biological origin of putative carbonaceous microfossils in Early Archean rocks. However, it has been demonstrated that the spectral signature obtained from kerogen (of known biological origin) is similar to spectra obtained from many poorly ordered carbonaceous materials that arise through abiotic processes. Yet there is still confusion in the literature as to whether the Raman spectroscopy of carbonaceous materials can indeed delineate a signature of ancient life. Despite the similar nature in spectra, rigorous structural interrogation between the thermal alteration products of biological and nonbiological organic materials has not been undertaken. Therefore, we propose a new way forward by investigating the second derivative, deconvolution, and chemometrics of the carbon first-order spectra to build a database of structural parameters that may yield distinguishable characteristics between biogenic and abiogenic carbonaceous material. To place Raman spectroscopy as a technique to delineate a biological origin for samples in context, we will discuss what is currently accepted as a spectral signature for life; review Raman spectroscopy of carbonaceous material; and provide a historical overview of Raman spectroscopy applied to Archean carbonaceous materials, interpretations of the origin of the ancient carbonaceous material, and a future way forward for Raman spectroscopy.

Spectroscopic characterization of sixteenth century panel painting references using Raman, surface-enhanced Raman spectroscopy and helium-Raman system for in situ analysis of Ibero-American Colonial paintings

NASA Astrophysics Data System (ADS)

García-Bucio, María Angélica; Casanova-González, Edgar; Ruvalcaba-Sil, José Luis; Arroyo-Lemus, Elsa; Mitrani-Viggiano, Alejandro

2016-12-01

Colonial panel paintings constitute an essential part of Latin-American cultural heritage. Their study is vital for understanding the manufacturing process, including its evolution in history, as well as its authorship, dating and other information significant to art history and conservation purposes. Raman spectroscopy supplies a non-destructive characterization tool, which can be implemented for in situ analysis, via portable equipment. Specific methodologies must be developed, comprising the elaboration of reference panel paintings using techniques and materials similar to those of the analysed period, as well as the determination of the best analysis conditions for different pigments and ground preparations. In order to do so, Raman spectroscopy at 532, 785 and 1064 nm, surface-enhanced Raman spectroscopy (SERS) and a helium-Raman system were applied to a panel painting reference, in combination with X-ray fluorescence analysis. We were able to establish the analysis conditions for a number of sixteenth century pigments and dyes, and other relevant components of panel paintings from this period, 1064 nm Raman and SERS being the most successful. The acquired spectra contain valuable specific information for their identification and they conform a very useful database that can be applied to the analysis of Ibero-American Colonial paintings. This article is part of the themed issue "Raman spectroscopy in art and archaeology".

Spectroscopic characterization of sixteenth century panel painting references using Raman, surface-enhanced Raman spectroscopy and helium-Raman system for in situ analysis of Ibero-American Colonial paintings

PubMed Central

2016-01-01

Colonial panel paintings constitute an essential part of Latin-American cultural heritage. Their study is vital for understanding the manufacturing process, including its evolution in history, as well as its authorship, dating and other information significant to art history and conservation purposes. Raman spectroscopy supplies a non-destructive characterization tool, which can be implemented for in situ analysis, via portable equipment. Specific methodologies must be developed, comprising the elaboration of reference panel paintings using techniques and materials similar to those of the analysed period, as well as the determination of the best analysis conditions for different pigments and ground preparations. In order to do so, Raman spectroscopy at 532, 785 and 1064 nm, surface-enhanced Raman spectroscopy (SERS) and a helium-Raman system were applied to a panel painting reference, in combination with X-ray fluorescence analysis. We were able to establish the analysis conditions for a number of sixteenth century pigments and dyes, and other relevant components of panel paintings from this period, 1064 nm Raman and SERS being the most successful. The acquired spectra contain valuable specific information for their identification and they conform a very useful database that can be applied to the analysis of Ibero-American Colonial paintings. This article is part of the themed issue ‘Raman spectroscopy in art and archaeology’. PMID:27799434

[Application of in situ cryogenic Raman spectroscopy to analysis of fluid inclusions in reservoirs].

PubMed

Chen, Yong; Lin, Cheng-yan; Yu, Wen-quan; Zheng, Jie; Wang, Ai-guo

2010-01-01

Identification of salts is a principal problem for analysis of fluid inclusions in reservoirs. The fluid inclusions from deep natural gas reservoirs in Minfeng sub-sag were analyzed by in situ cryogenic Raman spectroscopy. The type of fluid inclusions was identified by Raman spectroscopy at room temperature. The Raman spectra show that the inclusions contain methane-bearing brine aqueous liquids. The fluid inclusions were analyzed at -180 degrees C by in situ cryogenic Raman spectroscopy. The spectra show that inclusions contain three salts, namely NaCl2, CaCl2 and MgCl2. Sodium chloride is most salt component, coexisting with small calcium chloride and little magnesium chloride. The origin of fluids in inclusions was explained by analysis of the process of sedimentation and diagenesis. The mechanism of diagenesis in reservoirs was also given in this paper. The results of this study indicate that in situ cryogenic Raman spectroscopy is an available method to get the composition of fluid inclusions in reservoirs. Based on the analysis of fluid inclusions in reservoirs by in situ cryogenic Raman spectroscopy with combination of the history of sedimentation and diagenesis, the authors can give important evidence for the type and mechanism of diagenesis in reservoirs.

Optimizing laser crater enhanced Raman scattering spectroscopy

NASA Astrophysics Data System (ADS)

Lednev, V. N.; Sdvizhenskii, P. A.; Grishin, M. Ya.; Fedorov, A. N.; Khokhlova, O. V.; Oshurko, V. B.; Pershin, S. M.

2018-05-01

The laser crater enhanced Raman scattering (LCERS) spectroscopy technique has been systematically studied for chosen sampling strategy and influence of powder material properties on spectra intensity enhancement. The same nanosecond pulsed solid state Nd:YAG laser (532 nm, 10 ns, 0.1-1.5 mJ/pulse) was used for laser crater production and Raman scattering experiments for L-aspartic acid powder. Increased sampling area inside crater cavity is the key factor for Raman signal improvement for the LCERS technique, thus Raman signal enhancement was studied as a function of numerous experimental parameters including lens-to-sample distance, wavelength (532 and 1064 nm) and laser pulse energy utilized for crater production. Combining laser pulses of 1064 and 532 nm wavelengths for crater ablation was shown to be an effective way for additional LCERS signal improvement. Powder material properties (particle size distribution, powder compactness) were demonstrated to affect LCERS measurements with better results achieved for smaller particles and lower compactness.

Discrimination of serum Raman spectroscopy between normal and colorectal cancer

NASA Astrophysics Data System (ADS)

Li, Xiaozhou; Yang, Tianyue; Yu, Ting; Li, Siqi

2011-07-01

Raman spectroscopy of tissues has been widely studied for the diagnosis of various cancers, but biofluids were seldom used as the analyte because of the low concentration. Herein, serum of 30 normal people, 46 colon cancer, and 44 rectum cancer patients were measured Raman spectra and analyzed. The information of Raman peaks (intensity and width) and that of the fluorescence background (baseline function coefficients) were selected as parameters for statistical analysis. Principal component regression (PCR) and partial least square regression (PLSR) were used on the selected parameters separately to see the performance of the parameters. PCR performed better than PLSR in our spectral data. Then linear discriminant analysis (LDA) was used on the principal components (PCs) of the two regression method on the selected parameters, and a diagnostic accuracy of 88% and 83% were obtained. The conclusion is that the selected features can maintain the information of original spectra well and Raman spectroscopy of serum has the potential for the diagnosis of colorectal cancer.

Raman spectroscopy of synovial fluid as a tool for diagnosing osteoarthritis

NASA Astrophysics Data System (ADS)

Esmonde-White, Karen A.; Mandair, Gurjit S.; Raaii, Farhang; Jacobson, Jon A.; Miller, Bruce S.; Urquhart, Andrew G.; Roessler, Blake J.; Morris, Michael D.

2009-05-01

For many years, viscosity has been the primary method used by researchers in rheumatology to assess the physiochemical properties of synovial fluid in both normal and osteoarthritic patients. However, progress has been limited by the lack of methods that provide multiple layers of information, use small sample volumes, and are rapid. Raman spectroscopy was used to assess the biochemical composition of synovial fluid collected from 40 patients with clinical evidence of knee osteoarthritis (OA) at the time of elective surgical treatment. Severity of knee osteoarthritis was assessed by a radiologist using Kellgren/Lawrence (K/L) scores from knee joint x rays, while light microscopy and Raman spectroscopy were used to examine synovial fluid (SF) aspirates (2 to 10 μL), deposited on fused silica slides. We show that Raman bands used to describe protein secondary structure and content can be used to detect changes in synovial fluid from osteoarthritic patients. Several Raman band intensity ratios increased significantly in spectra collected from synovial fluid in patients with radiological evidence of moderate-to-severe osteoarthritis damage. These ratios can be used to provide a ``yes/no'' damage assessment. These studies provide evidence that Raman spectroscopy would be a suitable candidate in the evaluation of joint damage in knee osteoarthritis patients.

Drug Stability Analysis by Raman Spectroscopy

PubMed Central

Shende, Chetan; Smith, Wayne; Brouillette, Carl; Farquharson, Stuart

2014-01-01

Pharmaceutical drugs are available to astronauts to help them overcome the deleterious effects of weightlessness, sickness and injuries. Unfortunately, recent studies have shown that some of the drugs currently used may degrade more rapidly in space, losing their potency before their expiration dates. To complicate matters, the degradation products of some drugs can be toxic. Here, we present a preliminary investigation of the ability of Raman spectroscopy to quantify mixtures of four drugs; acetaminophen, azithromycin, epinephrine, and lidocaine, with their primary degradation products. The Raman spectra for the mixtures were replicated by adding the pure spectra of the drug and its degradant to determine the relative percent contributions using classical least squares. This multivariate approach allowed determining concentrations in ~10 min with a limit of detection of ~4% of the degradant. These results suggest that a Raman analyzer could be used to assess drug potency, nondestructively, at the time of use to ensure crewmember safety. PMID:25533308

Remote adjustable focus Raman spectroscopy probe

DOEpatents

Schmucker, John E.; Blasi, Raymond J.; Archer, William B.

1999-01-01

A remote adjustable focus Raman spectroscopy probe allows for analyzing Raman scattered light from a point of interest external probe. An environmental barrier including at least one window separates the probe from the point of interest. An optical tube is disposed adjacent to the environmental barrier and includes a long working length compound lens objective next to the window. A beam splitter and a mirror are at the other end. A mechanical means is used to translated the prove body in the X, Y, and Z directions resulting in a variable focus optical apparatus. Laser light is reflected by the beam splitter and directed toward the compound lens objective, then through the window and focused on the point of interest. Raman scattered light is then collected by the compound lens objective and directed through the beam splitter to a mirror. A device for analyzing the light, such as a monochrometer, is coupled to the mirror.

Raman spectroscopy as a tool to understand Kerogen production potential

NASA Astrophysics Data System (ADS)

Khatibi, S.; Ostadhassan, M.; Mohammed, R. A.; Alexeyev, A.

2017-12-01

A lot attention has given to unconventional reservoirs specifically oil shale in North America during the last decades. Understanding Kerogen properties in terms of maturity and production potential are crucial for unconventional reservoir. Since, the amount of hydrocarbon generation is a function of kerogen type and content in the formation, and the magnitude and duration in which heat and pressure were applied. This study presents a non-destructive and fast method to determine Kerogen properties in terms of Rock-Eval parameters by means of Raman Spectroscopy. Samples were gathered from upper and lower Bakken formation, with different maturities at different depth. Raman spectroscopy as a powerful nondestructive analytical tool for molecular reconstruction was employed to find Raman spectra of different samples. In the next step, Rock-Eval was performed for each sample and different measurements were made. Then in an original approach, correlation between Rock-Eval parameters with Raman Spectroscopy results was established to fully understand how kerogen productivity potentials can be reflected on the Raman response. Results showed, maturity related parameters (RO, Tmax), S1 (already generated oil in the rock), S2 (potential hydrocarbon) and OSI (oil saturation index as indication of potential oil flow zones) can be correlated to band separation, D band intensity, G band intensity and G/D intensity, respectively. Proposed method provide a fast nondestructive method to evaluate Kerogen quality even at field without any special sample preparation.

Vibrational characterization of pheomelanin and trichochrome F by Raman spectroscopy

NASA Astrophysics Data System (ADS)

Galván, Ismael; Jorge, Alberto; Solano, Francisco; Wakamatsu, Kazumasa

2013-06-01

We characterize for the first time the vibrational state of natural pheomelanin using Raman spectroscopy and model pigment synthesized from 5-S-cysteinyldopa. The shape of the Raman spectrum was very different from that of eumelanin. Four Raman bands were visible in the 500-2000 cm-1 wavenumber region about 500, 1150, 1490 and 2000 cm-1, which we assigned to the out-of-plane deformation and the stretching vibration of the phenyl rings, to the stretching vibration of C-N bonds or the stretching and wagging vibration of CH2, and to overtone or combination bands. Interestingly, we also show that the Raman spectrum of synthetic trichochrome F, a pigment that may be produced along with pheomelanin during pheomelanogenesis, is different from that of pheomelanin and similar to the spectrum of eumelanin. We could detect Raman signal of both eumelanin and pheomelanin in feathers and hairs where both pigments simultaneously occur without the need of isolating the pigment. This indicates that Raman spectroscopy represents a non-invasive method to detect pheomelanin and distinguish it from other pigments. This may be especially relevant to detect pheomelanin in animal skin including humans, where it has been associated with animal appearance and classification, human phototypes, prevention of skin diseases and cancer risk.

Raman spectroscopy on simple molecular systems at very high density

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schiferl, D.; LeSar, R.S.; Moore, D.S.

1988-01-01

We present an overview of how Raman spectroscopy is done on simple molecular substances at high pressures. Raman spectroscopy is one of the most powerful tools for studying these substances. It is often the quickest means to explore changes in crystal and molecular structures, changes in bond strength, and the formation of new chemical species. Raman measurements have been made at pressures up to 200 GPa (2 Mbar). Even more astonishing is the range of temperatures (4-5200/degree/K) achieved in various static and dynamic (shock-wave) pressure experiments. One point we particularly wish to emphasize is the need for a good theoreticalmore » understanding to properly interpret and use experimental results. This is particularly true at ultra-high pressures, where strong crystal field effects can be misinterpreted as incipient insulator-metal transitions. We have tried to point out apparatus, techniques, and results that we feel are particularly noteworthy. We have also included some of the /open quotes/oral tradition/close quotes/ of high pressure Raman spectroscopy -- useful little things that rarely or never appear in print. Because this field is rapidly expanding, we discuss a number of exciting new techniques that have been informally communicated to us, especially those that seem to open new possibilities. 58 refs., 18 figs.« less

Dramatic Raman Gain Suppression in the Vicinity of the Zero Dispersion Point in a Gas-Filled Hollow-Core Photonic Crystal Fiber.

PubMed

Bauerschmidt, S T; Novoa, D; Russell, P St J

2015-12-11

In 1964 Bloembergen and Shen predicted that Raman gain could be suppressed if the rates of phonon creation and annihilation (by inelastic scattering) exactly balance. This is only possible if the momentum required for each process is identical, i.e., phonon coherence waves created by pump-to-Stokes scattering are identical to those annihilated in pump-to-anti-Stokes scattering. In bulk gas cells, this can only be achieved over limited interaction lengths at an oblique angle to the pump axis. Here we report a simple system that provides dramatic Raman gain suppression over long collinear path lengths in hydrogen. It consists of a gas-filled hollow-core photonic crystal fiber whose zero dispersion point is pressure adjusted to lie close to the pump laser wavelength. At a certain precise pressure, stimulated generation of Stokes light in the fundamental mode is completely suppressed, allowing other much weaker phenomena such as spontaneous Raman scattering to be explored at high pump powers.

Identification and discrimination of polycyclic aromatic hydrocarbons using Raman spectroscopy

NASA Astrophysics Data System (ADS)

Cloutis, Edward; Szymanski, Paul; Applin, Daniel; Goltz, Douglas

2016-08-01

Polycyclic aromatic hydrocarbons (PAHs) are widely present throughout the Solar System and beyond. They have been implicated as a contributor to unidentified infrared emission bands in the interstellar medium, comprise a substantial portion of the insoluble organic matter in carbonaceous chondrites, are expected stable components of organic matter on Mars, and are present in a wide range of terrestrial hydrocarbons and as components of biomolecules. However, PAH structures can be very complicated, making their identification challenging. Raman spectroscopy is known to be especially sensitive to the highly polarizable C-C and C=C bonds found in PAHs, and therefore, can be a powerful tool for PAH structural and compositional elucidation. This study examined Raman spectra of 48 different PAHs to determine the degree to which Raman spectroscopy could be used to uniquely identify different species, factors that control the positions of major Raman peaks, the degree to which induced fluorescence affects the intensity of Raman peaks, its usefulness for PAH discrimination, and the effects of varying excitation wavelength on some PAH Raman spectra. It was found that the arrangement and composition of phenyl (benzene) rings, and the type and position of functional groups can greatly affect fluorescence, positions and intensities of Raman peaks associated with the PAH backbone, and the introduction of new Raman peaks. Among the functional groups found on many of the PAHs that were analyzed, only a few Raman peaks corresponding to the molecular vibrations of these groups could be clearly distinguished. Comparison of the PAH Raman spectra that were acquired with both 532 and 785 nm excitation found that the longer wavelength resulted in reduced fluorescence, consistent with previous studies.

Raman spectroscopy for diagnosis of glioblastoma multiforme

NASA Astrophysics Data System (ADS)

Clary, Candace Elise

Glioblastoma multiforme (GBM), the most common and most fatal malignant brain tumor, is highly infiltrative and incurable. Although improved prognosis has been demonstrated by surgically resecting the bulk tumor, a lack of clear borders at the tumor margins complicates the selection decision during surgery. This dissertation investigates the potential of Raman spectroscopy for distinguishing between normal and malignant brain tissue and sets the groundwork for a surgical diagnostic guide for resection of gross malignant gliomas. These studies revealed that Raman spectroscopy was capable of discriminating between normal scid mouse brain tissue and human xenograft tumors induced in those mice. The spectra of normal and malignant tissue were normalized by dividing by the respective magnitudes of the peaks near 1440 cm -1. Spectral differences include the shape of the broad peaks near 1440 cm-1 and 1660 cm-1 and the relative magnitudes of the peaks at 1264 cm-1, 1287 cm-1, 1297 cm-1, 1556 cm -1, 1586 cm-1, 1614 cm-1, and 1683 cm-1. From these studies emerged questions regarding how to objectively normalize and compare spectra for future automation. Some differences in the Raman spectra were shown to be inherent in the disease states of the cells themselves via differences in the Raman spectra of normal human astrocytes in culture and cultured cells derived from GBM tumors. The spectra of astrocytes and glioma cells were normalized by dividing by the respective magnitudes of the peaks near 1450 cm-1. The differences between the Raman spectra of normal and transformed cells include the ratio of the 1450 cm-1/1650 cm-1 peaks and the relative magnitudes of the peaks at 1181 cm-1, 1191 cm-1, 1225 cm-1, 1263 cm -1, 1300 cm-1, 1336 cm-1, 1477 cm-1, 1494 cm-1, and 1695 cm -1. Previous Raman spectroscopic studies of biological cells have shown that the magnitude of the Raman signal decreases over time, indicating sample damage. Cells exposed to laser excitation at similar power

Development and biological applications of optical tweezers and Raman spectroscopy

NASA Astrophysics Data System (ADS)

Xie, Chang'an

Optical tweezers is a three-dimensional manipulation tool that employs a gradient force that originates from the single highly focused laser beam. Raman spectroscopy is a molecular analytical tool that can give a highly unique "fingerprint" for each substance by measuring the unique vibrations of its molecules. The combination of these two optical techniques offers a new tool for the manipulation and identification of single biological cells and microscopic particles. In this thesis, we designed and implemented a Laser-Tweezers-Raman-Spectroscopy (LTRS) system, also called the Raman-tweezers, for the simultaneous capture and analysis of both biological particles and non-biological particles. We show that microparticles can be conveniently captured at the focus of a laser beam and the Raman spectra of trapped particles can be acquired with high quality. The LTRS system overcomes the intrinsic Brownian motion and cell motility of microparticles in solution and provides a promising tool for in situ identifying suspicious agents. In order to increase the signal to noise ratio, several schemes were employed in LTRS system to reduce the blank noise and the fluorescence signal coming from analytes and the surrounding background. These techniques include near-infrared excitation, optical levitation, confocal microscopy, and frequency-shifted Raman difference. The LTRS system has been applied for the study in cell biology at the single cell level. With the built Raman-tweezers system, we studied the dynamic physiological processes of single living cells, including cell cycle, the transcription and translation of recombinant protein in transgenic yeast cells and the T cell activation. We also studied cell damage and associated biochemical processes in optical traps, UV radiations, and evaluated heating by near-infrared Raman spectroscopy. These studies show that the Raman-tweezers system is feasible to provide rapid and reliable diagnosis of cellular disorders and can be

Investigation for the differentiation process of mouse ES cells by Raman spectroscopy

NASA Astrophysics Data System (ADS)

Yamaguchi, Yoshinori; El-Hagrasy, Maha A.; Shimizu, Eiichi; Saito, Masato; Tamiya, Eiichi

2012-03-01

The arrangement of differentiated pluripotent embryonic stem cells into three-dimensional aggregates, which are known as embryonic bodies, is a main step for progressing the embryonic stem cells differentiation. In this work, embryonic stem cells that were directly produced from the hanging drop step as a three-dimensional structure with no further twodimensional differentiation were diagnosed with Raman spectroscopy as a non-invasive and label-free technique. Raman spectroscopy was employed to discriminate between mouse embryonic bodies of different degrees of maturation. EBs were prepared applying the hanging drop method. The Raman scattering measurements were obtained in vitro with a Nanophoton RAMAN-11 micro-spectrometer (Japan: URL: www.nanophoton.jp equipped with an Olympus XLUM Plan FLN 20X/NA= 1.0 objective lens. Spectral data were smoothed, baseline corrected and normalized to the a welldefined intense 1003 cm-1 band (phenylalanine) which is insensitive to changes in conformation or environment. The differentiation process of embryonic stem cells is initiated by the removal of LIF from culture medium. 1, 7 and 17-dayold embryonic stem cells were collected and investigated by Raman spectroscopy. The main differences involve bands which decreased with maturation such as: 784 cm-1 (U, T, C ring br DNA/RNA, O-P-O str); 1177 cm-1 (cytosine, guanine) and 1578 cm-1 (G, A). It was found that with the progress of differentiation the protein content was amplified. The increase of protein to nucleic acid ratio was also previously observed with the progress of the differentiation process. Raman spectroscopy has the potential to distinguish between the Raman signatures of live embryonic stem cells with different degrees of maturation.

Charge Transfer Effect on Raman and Surface Enhanced Raman Spectroscopy of Furfural Molecules.

PubMed

Wan, Fu; Shi, Haiyang; Chen, Weigen; Gu, Zhaoliang; Du, Lingling; Wang, Pinyi; Wang, Jianxin; Huang, Yingzhou

2017-08-02

The detection of furfural in transformer oil through surface enhanced Raman spectroscopy (SERS) is one of the most promising online monitoring techniques in the process of transformer aging. In this work, the Raman of individual furfural molecules and SERS of furfural-M x (M = Ag, Au, Cu) complexes are investigated through density functional theory (DFT). In the Raman spectrum of individual furfural molecules, the vibration mode of each Raman peak is figured out, and the deviation from experimental data is analyzed by surface charge distribution. In the SERS of furfural-M x complexes, the influence of atom number and species on SERS chemical enhancement factors (EFs) are studied, and are further analyzed by charge transfer effect. Our studies strengthen the understanding of charge transfer effect in the SERS of furfural molecules, which is important in the online monitoring of the transformer aging process through SERS.

Charge Transfer Effect on Raman and Surface Enhanced Raman Spectroscopy of Furfural Molecules