Plasmon enhanced Raman scattering effect for an atom near a carbon nanotube

DOE PAGES

Bondarev, I. V.

2015-01-01

Quantum electrodynamics theory of the resonance Raman scattering is developed for an atom in a close proximity to a carbon nanotube. The theory predicts a dramatic enhancement of the Raman intensity in the strong atomic coupling regime to nanotube plasmon near-fields. This resonance scattering is a manifestation of the general electromagnetic surface enhanced Raman scattering effect, and can be used in designing efficient nanotube based optical sensing substrates for single atom detection, precision spontaneous emission control, and manipulation.

Effect on the partial least-squares prediction of yarn properties combining raman and infrared measurements and applying wavelength selection.

PubMed

de Groot, P J; Swierenga, H; Postma, G J; Melssen, W J; Buydens, L M C

2003-06-01

The combination of Raman and infrared spectroscopy on the one hand and wavelength selection on the other hand is used to improve the partial least-squares (PLS) prediction of seven selected yarn properties. These properties are important for on-line quality control during production. From 71 yarn samples, the Raman and infrared spectra are measured and reference methods are used to determine the selected properties. Making separate PLS models for all yarn properties using the Raman and infrared spectra, prior to wavelength selection, reveals that Raman spectroscopy outperforms infrared spectroscopy. If wavelength selection is applied, the PLS prediction error decreases and the correlation coefficient increases for all properties. However, a substantial wavelength selection effect is present for the infrared spectra compared to the Raman spectra. For the infrared spectra, wavelength selection results in PLS prediction errors comparable with the prediction performance of the Raman spectra prior to wavelength selection. Concatenating the Raman and infrared spectra does not enhance the PLS prediction performance, not even after wavelength selection. It is concluded that an infrared spectrometer, combined with a wavelength selection procedure, can be used if no (suitable) Raman instrument is available.

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.

Optimization of advanced Wiener estimation methods for Raman reconstruction from narrow-band measurements in the presence of fluorescence background

PubMed Central

Chen, Shuo; Ong, Yi Hong; Lin, Xiaoqian; Liu, Quan

2015-01-01

Raman spectroscopy has shown great potential in biomedical applications. However, intrinsically weak Raman signals cause slow data acquisition especially in Raman imaging. This problem can be overcome by narrow-band Raman imaging followed by spectral reconstruction. Our previous study has shown that Raman spectra free of fluorescence background can be reconstructed from narrow-band Raman measurements using traditional Wiener estimation. However, fluorescence-free Raman spectra are only available from those sophisticated Raman setups capable of fluorescence suppression. The reconstruction of Raman spectra with fluorescence background from narrow-band measurements is much more challenging due to the significant variation in fluorescence background. In this study, two advanced Wiener estimation methods, i.e. modified Wiener estimation and sequential weighted Wiener estimation, were optimized to achieve this goal. Both spontaneous Raman spectra and surface enhanced Raman spectra were evaluated. Compared with traditional Wiener estimation, two advanced methods showed significant improvement in the reconstruction of spontaneous Raman spectra. However, traditional Wiener estimation can work as effectively as the advanced methods for SERS spectra but much faster. The wise selection of these methods would enable accurate Raman reconstruction in a simple Raman setup without the function of fluorescence suppression for fast Raman imaging. PMID:26203387

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.

Self-referenced directional enhanced Raman scattering using plasmon waveguide resonance for surface and bulk sensing

NASA Astrophysics Data System (ADS)

Wan, Xiu-mei; Gao, Ran; Lu, Dan-feng; Qi, Zhi-mei

2018-01-01

Surface plasmon-coupled emission has been widely used in fluorescence imaging, biochemical sensing, and enhanced Raman spectroscopy. A self-referenced directional enhanced Raman scattering for simultaneous detection of surface and bulk effects by using plasmon waveguide resonance (PWR) based surface plasmon-coupled emission has been proposed and experimentally demonstrated. Raman scattering was captured on the prism side in Kretschmann-surface plasmon-coupled emission. The distinct penetration depths (δ) of the evanescent field for the transverse electric (TE) and transverse magnetic (TM) modes result in different detected distances of the Raman signal. The experimental results demonstrate that the self-referenced directional enhanced Raman scattering of the TE and TM modes based on the PWR can detect and distinguish the surface and bulk effects simultaneously, which appears to have potential applications in researches of chemistry, medicine, and biology.

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.

Preliminary identification of unicellular algal genus by using combined confocal resonance Raman spectroscopy with PCA and DPLS analysis

NASA Astrophysics Data System (ADS)

He, Shixuan; Xie, Wanyi; Zhang, Ping; Fang, Shaoxi; Li, Zhe; Tang, Peng; Gao, Xia; Guo, Jinsong; Tlili, Chaker; Wang, Deqiang

2018-02-01

The analysis of algae and dominant alga plays important roles in ecological and environmental fields since it can be used to forecast water bloom and control its potential deleterious effects. Herein, we combine in vivo confocal resonance Raman spectroscopy with multivariate analysis methods to preliminary identify the three algal genera in water blooms at unicellular scale. Statistical analysis of characteristic Raman peaks demonstrates that certain shifts and different normalized intensities, resulting from composition of different carotenoids, exist in Raman spectra of three algal cells. Principal component analysis (PCA) scores and corresponding loading weights show some differences from Raman spectral characteristics which are caused by vibrations of carotenoids in unicellular algae. Then, discriminant partial least squares (DPLS) classification method is used to verify the effectiveness of algal identification with confocal resonance Raman spectroscopy. Our results show that confocal resonance Raman spectroscopy combined with PCA and DPLS could handle the preliminary identification of dominant alga for forecasting and controlling of water blooms.

Biomedical Applications of Micro-Raman and Surface-Enhanced Raman Scattering (SERS) Technology

DTIC Science & Technology

2012-10-01

to be an effective media for PSA capture. For SERS-based immunoassays, nitrocellulose offers comparable results to those obtained using gold-coated...glass substrates while offering a more cost- effective and time-saving method of detecting minute amounts of PSA; (ii) Micro-Raman imaging...technology was found to be effective in chemical mapping of arteries in the tissues of a post mortem individual whose cause of death was a cardiac event

Saturation mechanisms of backward stimulated Raman scattering in a one-dimensional geometry

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

Friou, A.; Bénisti, D.; Gremillet, L.

2013-10-15

In this paper, we investigate the saturation mechanisms of backward stimulated Raman scattering (BSRS) induced by nonlinear kinetic effects. In particular, we stress the importance of accounting for both the nonlinear frequency shift of the electron plasma wave and the growth of sidebands, in order to understand what stops the coherent growth of Raman scattering. Using a Bernstein-Greene-Kruskal approach, we provide an estimate for the maximum amplitude reached by a BSRS-driven plasma wave after the phase of monotonic growth. This estimate is in very good agreement with the results from kinetic simulations of stimulated Raman scattering using both a Vlasovmore » and a Particle in Cell code. Our analysis, which may be generalized to a multidimensional geometry, should provide a means to estimate the limits of backward Raman amplification or the effectiveness of strategies that aim at strongly reducing Raman reflectivity in a fusion plasma.« less

Investigation of Skin Cancers Using MicroRaman Spectroscopy

NASA Astrophysics Data System (ADS)

Short, M. A.; Chen, X. K.; Zeng, H.; Ajlan, A. A.; McLean, D. I.; Hui, H.

2004-03-01

We have measured the Raman spectra of skin cancers, including melanoma and basal cell carcinoma, using a confocal microRaman spectrograph. In an attempt to identify the origin of the observed Raman modes, we investigated the spectra obtained from different locations of the samples, compared the observed spectra with those measured from normal human skin and pig skin, and studied the polarization dependence of the spectra. In addition, we will discuss the effects of fluorescence in the measurement of Raman spectra of skin samples.

Faraday effect on stimulated Raman scattering in the linear region

NASA Astrophysics Data System (ADS)

Liu, Z. J.; Li, B.; Xiang, J.; Cao, L. H.; Zheng, C. Y.; Hao, L.

2018-04-01

The paper presents the effect of Faraday rotation on stimulated Raman scattering (SRS). When light propagates along the magnetic field upon plasma, Faraday rotation occurs. The rotation angle can be expressed as {{d}}θ /{{d}}{s}=2.93× {10}-4B\\tfrac{{n}e/{n}c}{\\sqrt{1-{n}e/{n}c}} {cm}}-1 approximately, where θ is the rotation angle and s is distance, n e is the electron density, n c is the critical density and B is magnetic field in unit of Gauss. Both the incident light and Raman light have Faraday effects. The angle between the polarization directions of incident light and Raman light changes with position. The driven force of electron plasma wave also reduces, and then SRS scattering level is reduced. Faraday rotation effect can increase the laser intensity threshold of Raman scattering, even if the magnetic field strength is small. The circularly polarized light incident case is also compared with that of the linearly polarized light incident. The Raman scattering level of linearly polarized light is much smaller than that of circularly polarized light in the magnetized plasma. The difference between linearly and circularly polarized lights is also discussed.

Wide-Field Raman Imaging of Dental Lesions

PubMed Central

Yang, Shan; Li, Bolan; Akkus, Anna; Akkus, Ozan; Lang, Lisa

2014-01-01

Detection of dental caries at the onset remains as a great challenge in dentistry. Raman spectroscopy could be successfully applied towards detecting caries since it is sensitive to the amount of the Raman active mineral crystals, the most abundant component of enamel. Effective diagnosis requires full examination of a tooth surface via a Raman mapping. Point-scan Raman mapping is not clinically relevant (feasible) due to lengthy data acquisition time. In this work, a wide-field Raman imaging system was assembled based on a high-sensitivity 2D CCD camera for imaging the mineralization status of teeth with lesions. Wide-field images indicated some lesions to be hypomineralized and others to be hypermineralized. The observations of wide-field Raman imaging were in agreement with point-scan Raman mapping. Therefore, sound enamel and lesions can be discriminated by Raman imaging of the mineral content. In conclusion, wide-field Raman imaging is a potentially useful tool for visualization of dental lesions in the clinic. PMID:24781363

Experimental artifacts influencing polarization sensitive magneto-Raman spectroscopy

NASA Astrophysics Data System (ADS)

Thirunavukkuarasu, K.; Lu, Z.; Su, L.; Yu, Y.; Cao, L.; Ballotin, M. V.; Christianen, P. C. M.; Zhang, Y.; Smirnov, D.

Since the discovery of graphene, there has been an explosion of research on 2D layered materials such as transition metal dichalcogenides (TMDs). Among several experimental techniques utilized for studying these materials, Raman spectroscopy has proven to be a very powerful tool due to it's sensitivity to layer numbers, interlayer coupling etc. Layered MoS2, member of TMD family, is a typical example with promising applications in nano-optoelectronics. A recent magneto-Raman investigations on MoS2 published by J. Ji etal reported an observation of giant magneto-optical effect. In this work, the intensity of Raman modes exhibited dramatic change in intensities and was attributed to field-induced broken symmetry on Raman scattering cross-section. Due to the ambiguous nature of the interpretation presented in this publication, we performed further Raman studies on MoS2 at high magnetic fields to illustrate the experimental factors overlooked by the previous study. It is highly important to consider the magnetic field-induced rotation of the polarization of the light and its effect on the Raman active phonon modes in anisotropic materials. A detailed report of our magneto-Raman experiments and their outcomes will be presented.

Laser light triggers increased Raman amplification in the regime of nonlinear Landau damping

PubMed Central

Depierreux, S.; Yahia, V.; Goyon, C.; Loisel, G.; Masson-Laborde, P. -E.; Borisenko, N.; Orekhov, A.; Rosmej, O.; Rienecker, T.; Labaune, C.

2014-01-01

Stimulated Raman backscattering (SRS) has many unwanted effects in megajoule-scale inertially confined fusion (ICF) plasmas. Moreover, attempts to harness SRS to amplify short laser pulses through backward Raman amplification have achieved limited success. In high-temperature fusion plasmas, SRS usually occurs in a kinetic regime where the nonlinear response of the Langmuir wave to the laser drive and its host of complicating factors make it difficult to predict the degree of amplification that can be achieved under given experimental conditions. Here we present experimental evidence of reduced Landau damping with increasing Langmuir wave amplitude and determine its effects on Raman amplification. The threshold for trapping effects to influence the amplification is shown to be very low. Above threshold, the complex SRS dynamics results in increased amplification factors, which partly explains previous ICF experiments. These insights could aid the development of more efficient backward Raman amplification schemes in this regime. PMID:24938756

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.

Raman technology for future planetary missions

NASA Astrophysics Data System (ADS)

Thiele, Hans; Hofer, Stefan; Stuffler, Timo; Glier, Markus; Popp, Jürgen; Sqalli, Omar; Wuttig, Andreas; Riesenberg, Rainer

2017-11-01

Scientific experiments on mineral and biological samples with Raman excitation below 300nm show a wealth of scientific information. The fluorescence, which typically decreases signal quality in the visual or near infrared wavelength regime can be avoided with deep ultraviolet excitation. This wavelength regime is therefore regarded as highly attractive for a compact high performance Raman spectrometer for in-situ planetary research. Main objective of the MIRAS II breadboard activity presented here (MIRAS: Mineral Investigation with Raman Spectroscopy) is to evaluate, design and build a compact fiber coupled deep-UV Raman system breadboard. Additionally, the Raman system is combined with an innovative scanning microscope system to allow effective auto-focusing and autonomous orientation on the sample surface for high precise positioning or high resolution Raman mapping.

[Raman spectroscopy fluorescence background correction and its application in clustering analysis of medicines].

PubMed

Chen, Shan; Li, Xiao-ning; Liang, Yi-zeng; Zhang, Zhi-min; Liu, Zhao-xia; Zhang, Qi-ming; Ding, Li-xia; Ye, Fei

2010-08-01

During Raman spectroscopy analysis, the organic molecules and contaminations will obscure or swamp Raman signals. The present study starts from Raman spectra of prednisone acetate tablets and glibenclamide tables, which are acquired from the BWTek i-Raman spectrometer. The background is corrected by R package baselineWavelet. Then principle component analysis and random forests are used to perform clustering analysis. Through analyzing the Raman spectra of two medicines, the accurate and validity of this background-correction algorithm is checked and the influences of fluorescence background on Raman spectra clustering analysis is discussed. Thus, it is concluded that it is important to correct fluorescence background for further analysis, and an effective background correction solution is provided for clustering or other analysis.

The use of a handheld Raman system for virus detection

NASA Astrophysics Data System (ADS)

Song, Chunyuan; Driskell, Jeremy D.; Tripp, Ralph A.; Cui, Yiping; Zhao, Yiping

2012-06-01

The combination of surface enhanced Raman spectroscopy (SERS) with a handheld Raman system would lead to a powerful portable device for defense and security applications. The Thermo Scientific FirstDefender RM instrument is a 785-nm handheld Raman spectrometer intended for rapid field identification of unknown solid and liquid samples. Its sensitivity and effectiveness for SERS-based detection was initially confirmed by evaluating detection of 1,2-di(4- pyridyl)ethylene as a reporter molecule on a silver nanorod (AgNR) substrate, and the results are comparable to those from a confocal Bruker Raman system. As avian influenza A viruses (AIV) are recognized as an important emerging threat to public health, this portable handheld Raman spectrometer is used, for the first time, to detect and identify avian influenza A viruses using a multi-well AgNR SERS chip. The SERS spectra obtained had rich peaks which demonstrated that the instrument can be effectively used for SERS-based influenza virus detection. According to the SERS spectra, these different influenza viruses were distinguished from the negative control via the principal component analysis and by partial least squares-discriminate analysis. Together, these results show that the combination effective SERS substrates when combined with a portable Raman spectrometer provides a powerful field device for chemical and biological sensing.

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.

Raman Spectroscopic Measurements of Co2 Dissolved in Seawater for Laser Remote Sensing in Water

NASA Astrophysics Data System (ADS)

Somekawa, Toshihiro; Fujita, Masayuki

2016-06-01

We examined the applicability of Raman lidar technique as a laser remote sensing tool in water. The Raman technique has already been used successfully for measurements of CO2 gas dissolved in water and bubbles. Here, the effect of seawater on CO2 Raman spectra has been evaluated. A frequency doubled Q-switched Nd:YAG laser (532 nm) was irradiated to CO2 gas dissolved in a standard seawater. In seawater, the Raman signals at 984 and 1060-1180 cm-1 from SO42- were detected, which shows no spectral interference caused by Raman signals derived from CO2.

A Study of Scientific Reasoning in a Peripheral Context: The Discovery of the Raman Effect

ERIC Educational Resources Information Center

Dasgupta, Deepanwita

2015-01-01

This paper is an attempt to reconstruct how C.V. Raman, a peripheral scientist in the early 20th century colonial India, managed to develop a research programme in physical optics from his remote colonial location. His attempts at self-training and self-education eventually led him to the discovery of the Raman Effect and to the Nobel Prize in…

Low-Frequency Shear and Layer-Breathing Modes in Raman Scattering of Two-Dimensional Materials.

PubMed

Liang, Liangbo; Zhang, Jun; Sumpter, Bobby G; Tan, Qing-Hai; Tan, Ping-Heng; Meunier, Vincent

2017-12-26

Ever since the isolation of single-layer graphene in 2004, two-dimensional layered structures have been among the most extensively studied classes of materials. To date, the pool of two-dimensional materials (2DMs) continues to grow at an accelerated pace and already covers an extensive range of fascinating and technologically relevant properties. An array of experimental techniques have been developed and used to characterize and understand these properties. In particular, Raman spectroscopy has proven to be a key experimental technique, thanks to its capability to identify minute structural and electronic effects in nondestructive measurements. While high-frequency (HF) intralayer Raman modes have been extensively employed for 2DMs, recent experimental and theoretical progress has demonstrated that low-frequency (LF) interlayer Raman modes are more effective at determining layer numbers and stacking configurations and provide a unique opportunity to study interlayer coupling. These advantages are due to 2DMs' unique interlayer vibration patterns where each layer behaves as an almost rigidly moving object with restoring forces corresponding to weak interlayer interactions. Compared to HF Raman modes, the relatively small attention originally devoted to LF Raman modes is largely due to their weaker signal and their proximity to the strong Rayleigh line background, which previously made their detection challenging. Recent progress in Raman spectroscopy with technical and hardware upgrades now makes it possible to probe LF modes with a standard single-stage Raman system and has proven crucial to characterize and understand properties of 2DMs. Here, we present a comprehensive and forward-looking review on the current status of exploiting LF Raman modes of 2DMs from both experimental and theoretical perspectives, revealing the fundamental physics and technological significance of LF Raman modes in advancing the field of 2DMs. We review a broad array of materials, with varying thickness and stacking configurations, discuss the effect of in-plane anisotropy, and present a generalized linear chain model and interlayer bond polarizability model to rationalize the experimental findings. We also discuss the instrumental improvements of Raman spectroscopy to enhance and separate LF Raman signals from the Rayleigh line. Finally, we highlight the opportunities and challenges ahead in this fast-developing field.

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 Texas Instruments Incorporated) for analyzing dispersed light as needed in Raman and fluorescent applications.

Raman-based imaging uncovers the effects of alginate hydrogel implants in spinal cord injury

NASA Astrophysics Data System (ADS)

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

2015-07-01

The treatment of spinal cord injury by using implants that provide a permissive environment for axonal growth is in the focus of the research for regenerative therapies. Here, Raman-based label-free techniques were applied for the characterization of morphochemical properties of surgically induced spinal cord injury in the rat that received an implant of soft unfunctionalized alginate hydrogel. Raman microspectroscopy followed by chemometrics allowed mapping the different degenerative areas, while multimodal multiphoton microscopy (e.g. the combination of coherent anti-Stokes Raman scattering (CARS), endogenous two-photon fluorescence and second harmonic generation on the same platform) enabled to address the morphochemistry of the tissue at cellular level. The regions of injury, characterized by demyelination and scarring, were retrieved and the distribution of key tissue components was evaluated by Raman mapping. The alginate hydrogel was detected in the lesion up to six months after implantation and had positive effects on the nervous tissue. For instance, multimodal multiphoton microscopy complemented the results of Raman mapping, providing the micromorphology of lipid-rich tissue structures by CARS and enabling to discern lipid-rich regions that contained myelinated axons from degenerative regions characterized by myelin fragmentation and presence of foam cells. These findings demonstrate that Raman-based imaging methods provide useful information for the evaluation of alginate implant effects and have therefore the potential to contribute to new strategies for monitoring degenerative and regenerative processes induced in SCI, thereby improving the effectiveness of therapies.

Conjugated Polymer with Intrinsic Alkyne Units for Synergistically Enhanced Raman Imaging in Living Cells.

PubMed

Li, Shengliang; Chen, Tao; Wang, Yunxia; Liu, Libing; Lv, Fengting; Li, Zhiliang; Huang, Yanyi; Schanze, Kirk S; Wang, Shu

2017-10-16

Development of Raman-active materials with enhanced and distinctive Raman vibrations in the Raman-silent region (1800-2800 cm -1 ) is highly required for specific molecular imaging of living cells with high spatial resolution. Herein, water-soluble cationic conjugated polymers (CCPs), poly(phenylene ethynylene) (PPE) derivatives, are explored for use as alkyne-state-dependent Raman probes for living cell imaging due to synergetic enhancement effect of alkyne vibrations in Raman-silent region compared to alkyne-containing small molecules. The enhanced alkyne signals result from the integration of alkyne groups into the rigid backbone and the delocalized π-conjugated structure. PPE-based conjugated polymer nanoparticles (CPNs) were also prepared as Raman-responsive nanomaterials for distinct imaging application. This work opens a new way into the development of conjugated polymer materials for enhanced Raman imaging. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Raman scattering in the atmospheres of the major planets

NASA Technical Reports Server (NTRS)

Cochran, W. D.; Trafton, L. M.

1978-01-01

A technique is developed to calculate the detailed effects of Raman scattering in an inhomogeneous anisotropically scattering atmosphere. The technique is applied to evaluations of Raman scattering by H2 in the atmosphere of the major planets. It is noted that Raman scattering produces an insufficient decrease in the blue and ultraviolet regions to explain the albedos of all planets investigated. For all major planets, the filling-in of solar line cores and the generation of the Raman-shifted ghosts of the Fraunhofer spectrum are observed. With regard to Uranus and Neptune, Raman scattering is seen to exert a major influence on the formation and profile of strong red and near infrared CH4 bands, and Raman scattering by H2 explains the residual intensity in the cores of these bands. Raman scattering by H2 must also be taken into account in the scattering of photons into the cores of saturated absorption bands.

Resonance Raman scattering of β-carotene solution excited by visible laser beams into second singlet state.

PubMed

Lu, Luyao; Shi, Lingyan; Secor, Jeff; Alfano, Robert

2018-02-01

This study aimed to use self-absorption correction to determine the Raman enhancement of β-carotene. The Raman spectra of β-carotene solutions were measured using 488nm, 514nm, 532nm and 633nm laser beams, which exhibited significant resonance Raman (RR) enhancement when the laser energy approaches the electronic transition energy from S 0 to S 2 state. The Raman intensity and the actual resonance Raman gain without self-absorption from S 2 state by β-carotene were also obtained to evaluate the effect of self-absorption on RR scattering. Moreover, we observed the Raman intensity strength followed the absorption spectra. Our study found that, although 488nm and 514nm pumps seemed better for stronger RR enhancement, 532nm would be the optimum Raman pump laser with moderate RR enhancement due to reduced fluorescence and self-absorption. The 532nm excitation will be helpful for applying resonance Raman spectroscopy to investigate biological molecules in tissues. Copyright © 2017 Elsevier B.V. All rights reserved.

Non-invasive analysis of hormonal variations and effect of postmenopausal Vagifem treatment on women using in vivo high wavenumber confocal Raman spectroscopy.

PubMed

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

2013-07-21

This study aims to evaluate the feasibility of applying high wavenumber (HW) confocal Raman spectroscopy for non-invasive assessment of menopause-related hormonal changes in the cervix as well as for determining the effect of Vagifem(®) treatment on postmenopausal women with atrophic cervix. A rapid HW confocal Raman spectroscopy system coupled with a ball lens fiber-optic Raman probe was utilized for in vivo cervical tissue Raman measurements at 785 nm excitation. A total of 164 in vivo HW Raman spectra (premenopausal (n = 104), postmenopausal-prevagifem (n = 34), postmenopausal-postvagifem (n = 26)) were measured from the normal cervix of 26 patients undergoing colposcopy. We established the biochemical basis of premenopausal, postmenopausal-prevagifem and postmenopausal-postvagifem cervix using semiquantitative biomolecular modeling derived from Raman-active biochemicals (i.e., lipids, proteins and water) that play a critical role in HW Raman spectral changes associated with the menopausal process. The diagnostic algorithms developed based on partial least squares-discriminant analysis (PLS-DA) together with leave-one patient-out, cross-validation yielded the diagnostic sensitivities of 88.5%, 91.2% and 88.5%, and specificities of 91.7%, 90.8% and 99.3%, respectively, for non-invasive in vivo discrimination among premenopausal, postmenopausal-prevagifem and postmenopausal-postvagifem cervix. This work demonstrates for the first time that HW confocal Raman spectroscopy in conjunction with biomolecular modeling can be a powerful diagnostic tool for identifying hormone/menopause-related variations in the native squamous epithelium of normal cervix, as well as for assessing the effect of Vagifem treatment on postmenopausal atrophic cervix in vivo during clinical colposcopic inspections.

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.

Raman properties of gold nanoparticle-decorated individual carbon nanotubes

NASA Astrophysics Data System (ADS)

Assmus, Tilman; Balasubramanian, Kannan; Burghard, Marko; Kern, Klaus; Scolari, Matteo; Fu, Nan; Myalitsin, Anton; Mews, Alf

2007-04-01

Single-wall carbon nanotubes decorated by gold nanoparticles with sizes of a few tens of nanometers were investigated by confocal Raman microscopy. It was found that individual nanoparticles impart a sizable Raman enhancement exceeding one order of magnitude, without appreciably interfering with polarization dependent Raman measurements. By contrast, cavity effects within small nanoparticle agglomerates resulted in a 20-fold stronger enhancement and significant distortions of the polarization characteristic.

Spectroscopic diagnosis of laryngeal carcinoma using near-infrared Raman spectroscopy and random recursive partitioning ensemble techniques.

PubMed

Teh, Seng Khoon; Zheng, Wei; Lau, David P; Huang, Zhiwei

2009-06-01

In this work, we evaluated the diagnostic ability of near-infrared (NIR) Raman spectroscopy associated with the ensemble recursive partitioning algorithm based on random forests for identifying cancer from normal tissue in the larynx. A rapid-acquisition NIR Raman system was utilized for tissue Raman measurements at 785 nm excitation, and 50 human laryngeal tissue specimens (20 normal; 30 malignant tumors) were used for NIR Raman studies. The random forests method was introduced to develop effective diagnostic algorithms for classification of Raman spectra of different laryngeal tissues. High-quality Raman spectra in the range of 800-1800 cm(-1) can be acquired from laryngeal tissue within 5 seconds. Raman spectra differed significantly between normal and malignant laryngeal tissues. Classification results obtained from the random forests algorithm on tissue Raman spectra yielded a diagnostic sensitivity of 88.0% and specificity of 91.4% for laryngeal malignancy identification. The random forests technique also provided variables importance that facilitates correlation of significant Raman spectral features with cancer transformation. This study shows that NIR Raman spectroscopy in conjunction with random forests algorithm has a great potential for the rapid diagnosis and detection of malignant tumors in the larynx.

Stable optical trapping and sensitive characterization of nanostructures using standing-wave Raman tweezers

PubMed Central

Wu, Mu-ying; Ling, Dong-xiong; Ling, Lin; Li, William; Li, Yong-qing

2017-01-01

Optical manipulation and label-free characterization of nanoscale structures open up new possibilities for assembly and control of nanodevices and biomolecules. Optical tweezers integrated with Raman spectroscopy allows analyzing a single trapped particle, but is generally less effective for individual nanoparticles. 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 with confocal Raman spectroscopy. This scheme has stronger intensity gradients and balanced scattering forces, and thus 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, SERS-active metal nanoparticles, and high-refractive semiconductor nanoparticles. This would enable sorting and characterization of specific SWCNTs and other nanoparticles based on their increased Raman fingerprints. PMID:28211526

Effect of Laser Irradiation on Cell Function and Its Implications in Raman Spectroscopy.

PubMed

Yuan, Xiaofei; Song, Yanqing; Song, Yizhi; Xu, Jiabao; Wu, Yinhu; Glidle, Andrew; Cusack, Maggie; Ijaz, Umer Z; Cooper, Jonathan M; Huang, Wei E; Yin, Huabing

2018-04-15

Lasers are instrumental in advanced bioimaging and Raman spectroscopy. However, they are also well known for their destructive effects on living organisms, leading to concerns about the adverse effects of laser technologies. To implement Raman spectroscopy for cell analysis and manipulation, such as Raman-activated cell sorting, it is crucial to identify nondestructive conditions for living cells. Here, we evaluated quantitatively the effect of 532-nm laser irradiation on bacterial cell fate and growth at the single-cell level. Using a purpose-built microfluidic platform, we were able to quantify the growth characteristics, i.e., specific growth rates and lag times of individual cells, as well as the survival rate of a population in conjunction with Raman spectroscopy. Representative Gram-negative and Gram-positive species show similar trends in response to a laser irradiation dose. Laser irradiation could compromise the physiological function of cells, and the degree of destruction is both dose and strain dependent, ranging from reduced cell growth to a complete loss of cell metabolic activity and finally to physical disintegration. Gram-positive bacterial cells are more susceptible than Gram-negative bacterial strains to irradiation-induced damage. By directly correlating Raman acquisition with single-cell growth characteristics, we provide evidence of nondestructive characteristics of Raman spectroscopy on individual bacterial cells. However, while strong Raman signals can be obtained without causing cell death, the variety of responses from different strains and from individual cells justifies careful evaluation of Raman acquisition conditions if cell viability is critical. IMPORTANCE In Raman spectroscopy, the use of powerful monochromatic light in laser-based systems facilitates the detection of inherently weak signals. This allows environmentally and clinically relevant microorganisms to be measured at the single-cell level. The significance of being able to perform Raman measurement is that, unlike label-based fluorescence techniques, it provides a "fingerprint" that is specific to the identity and state of any (unlabeled) sample. Thus, it has emerged as a powerful method for studying living cells under physiological and environmental conditions. However, the laser's high power also has the potential to kill bacteria, which leads to concerns. The research presented here is a quantitative evaluation that provides a generic platform and methodology to evaluate the effects of laser irradiation on individual bacterial cells. Furthermore, it illustrates this by determining the conditions required to nondestructively measure the spectra of representative bacteria from several different groups. Copyright © 2018 Yuan et al.

Beyond spatial correlation effect in micro-Raman light scattering: An example of zinc-blende GaN/GaAs hetero-interface

NASA Astrophysics Data System (ADS)

Ning, J. Q.; Zheng, C. C.; Zheng, L. X.; Xu, S. J.

2015-08-01

Spatially resolved Raman light scattering experiments were performed on a zinc-blende GaN/GaAs heterostructure with confocal micro-Raman scattering technique under the backscattering geometric configuration. By varying the illumination spot locations across the heterostructure interface, we found that the Raman light scattering spectral features change remarkably. The interface effect on the GaAs substrate manifested as a much broader lineshape of the transverse optical (TO) phonon mode. Two kinds of broadening mechanisms, namely, spatial correlation induced wave-vector relaxation effect and lattice-mismatch strain + compositional intermixing effect, have been identified. The former leads to the broadening of the TO mode at the low-energy side, whereas the latter accounts for the broadening at the high-energy side. The diffuse light scattering from the highly defective nucleation layer of GaN was found to produce a broad scattering background of the GaN TO mode. The methodology and conclusions of the present work could be applicable to Raman spectroscopic studies on other material interfaces.

Stimulated Raman amplification, oscillation, and linewidth in barium nitrate

NASA Technical Reports Server (NTRS)

McCray, Christopher J.; Chyba, Thomas H.

1998-01-01

Measurements of Raman gain in a Ba(NO3)2 crystal are reported at 532 nm using a Raman oscillator/amplifier arrangement for differential absorption lidar measurements of ozone. The experimentally determined gain coefficient will be compared with theoretical results. The effect of single and multi-longitudinal mode pumping upon the amplification process will be discussed. Measurement of the Raman linewidth for 1st 2nd and 3d stokes shifts arc presented.

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.

Phase-locked bifrequency Raman lasing in a double-Λ system

NASA Astrophysics Data System (ADS)

Alaeian, Hadiseh; Shahriar, M. S.

2018-05-01

We show that it is possible to realize simultaneous Raman lasing at two different frequencies using a double-Λ system pumped by a bifrequency field. The bifrequency Raman lasers are phase-locked to one another and the beat-frequency matches the energy difference between the two metastable ground states. Akin to a conventional Raman laser, the bifrequency Raman lasers are expected to be subluminal. As such, these are expected to be highly stable against perturbations in cavity length and have quantum noise limited linewidths that are far below that of a conventional laser. Because of these properties, the bifrequency Raman lasers may find important applications in precision metrology, including atomic interferometry and magnetometry. The phase-locked Raman laser pair also represent a manifestation of lasing without inversion, albeit in a configuration that produces a pair of nondegenerate lasers simultaneously. This feature may enable lasing without inversion in frequency regimes not accessible using previous techniques of lasing without inversion. To elucidate the behavior of this laser pair, we develop an analytical model that describes the stimulated Raman interaction in a double-Λ system using an effective two-level transition. The approximation is valid as long as the excited states adiabatically follow the ground states, as verified by numerical simulations. The effective model is used to identify the optimal operating conditions for the bifrequency Raman lasing process. This model may also prove useful in other potential applications of the double-Λ system, including generation of squeezed light and spatial solitons.

Distribution of phthalocyanines and Raman reporters in human cancerous and noncancerous breast tissue as studied by Raman imaging.

PubMed

Brozek-Pluska, Beata; Jarota, Arkadiusz; Jablonska-Gajewicz, Joanna; Kordek, Radzislaw; Czajkowski, Wojciech; Abramczyk, Halina

2012-08-01

There is a considerable interest in the developing new diagnostic techniques allowing noninvasive tracking of the progress of therapies used to treat a cancer. Raman imaging of distribution of phthalocyanine photosensitizers may open new possibilities of Photodynamic Therapy (PDT) to treat a wide range of neoplastic lesions with improved effectiveness of treatment through precise identification of malignant areas. We have employed Raman imaging and Raman spectroscopy to analyze human breast cancer tissue that interacts with photosensitizers used in the photodynamic therapy of cancer. PCA (Principal Component Analysis) has been employed to analyze various areas of the noncancerous and cancerous breast tissues. The results show that the emission spectra combined with the Raman images are very sensitive indicators to specify the aggregation state and the distribution of phthalocyanines in the cancerous and noncancerous breast tissues. Our results provide experimental evidence on the role of aggregation of phthalocyanines as a factor of particular significance in differentiation of the normal and tumourous (cancerous or benign pathology) breast tissues. We conclude that the Raman imaging reported here has a potential to be a novel and effective photodynamic therapeutic method with improved selectivity for the treatment of breast cancer.

Influence of the nanoparticles agglomeration state in the quantum-confinement effects: Experimental evidences

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

Lorite, I., E-mail: lorite@physik.uni-leipzig.de; Division of Superconductivity and Magnetism, Faculty of Physics and Earth Sciences, Linnestrasse 5, D-04103 Leipzig; Romero, J. J.

2015-03-15

The agglomeration state facilitates particle-particle interaction which produces important effects in the phonon confinement effects at the nanoscale. A partial phonon transmission between close nanoparticles yields a lower momentum conservation relaxation than in a single isolated nanoparticle. It means a larger red shift and broadening of the Raman modes than the expected ones for Raman quantum confinement effects. This particle-particle interaction can drive to error when Raman responses are used to estimate the size of the nanoscaled materials. In this work different corrections are suggested to overtake this source of error.

Low-Frequency Shear and Layer-Breathing Modes in Raman Scattering of Two-Dimensional Materials

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

Liang, Liangbo; Zhang, Jun; Sumpter, Bobby G.

Ever since the isolation of single-layer graphene in 2004, two-dimensional layered structures have been among the most extensively studied classes of materials. To date, the pool of two-dimensional materials (2DMs) continues to grow at an accelerated pace and already covers an extensive range of fascinating and technologically relevant properties. An array of experimental techniques have been developed and used to fully characterize and understand these properties. In particular, Raman spectroscopy has proven to be a key experimental technique, thanks to its capability to identify minute structural and electronic effects in nondestructive measurements. While high-frequency (HF) intralayer Raman modes have beenmore » extensively employed for 2DMs, recent experimental and theoretical progress has demonstrated that low-frequency (LF) interlayer Raman modes are more effective at determining layer numbers and stacking configurations, and provide a unique opportunity to study interlayer coupling. These advantages are due to 2DMs’ unique interlayer vibration patterns where each layer behaves as an almost rigidly moving object with restoring forces corresponding to weak interlayer interactions. Compared to HF Raman modes, the relatively small attention originally devoted to LF Raman modes is largely due to their weaker signal and their proximity to the strong Rayleigh line background, which previously made their detection challenging. Recent progress in Raman spectroscopy with technical and hardware upgrades now makes it possible to probe LF modes with a standard single-stage Raman system and has proven crucial to characterize and understand properties of 2DMs. Here, we present a comprehensive and forward-looking review on the current status of exploiting LF Raman modes of 2DMs from both experimental and theoretical perspectives, revealing the fundamental physics and technological significance of LF Raman modes in advancing the field of 2DMs. We review a broad array of materials, with varying thickness and stacking configurations, discuss the effect of in-plane anisotropy, and present a generalized linear chain model and interlayer bond polarizability model to rationalize the experimental findings. We also discuss the instrumental improvements of Raman spectroscopy to enhance and separate LF Raman signals from the Rayleigh line. Lastly, we highlight the opportunities and challenges ahead in this fast-developing field.« less

Low-Frequency Shear and Layer-Breathing Modes in Raman Scattering of Two-Dimensional Materials

DOE PAGES

Liang, Liangbo; Zhang, Jun; Sumpter, Bobby G.; ...

2017-11-03

Ever since the isolation of single-layer graphene in 2004, two-dimensional layered structures have been among the most extensively studied classes of materials. To date, the pool of two-dimensional materials (2DMs) continues to grow at an accelerated pace and already covers an extensive range of fascinating and technologically relevant properties. An array of experimental techniques have been developed and used to fully characterize and understand these properties. In particular, Raman spectroscopy has proven to be a key experimental technique, thanks to its capability to identify minute structural and electronic effects in nondestructive measurements. While high-frequency (HF) intralayer Raman modes have beenmore » extensively employed for 2DMs, recent experimental and theoretical progress has demonstrated that low-frequency (LF) interlayer Raman modes are more effective at determining layer numbers and stacking configurations, and provide a unique opportunity to study interlayer coupling. These advantages are due to 2DMs’ unique interlayer vibration patterns where each layer behaves as an almost rigidly moving object with restoring forces corresponding to weak interlayer interactions. Compared to HF Raman modes, the relatively small attention originally devoted to LF Raman modes is largely due to their weaker signal and their proximity to the strong Rayleigh line background, which previously made their detection challenging. Recent progress in Raman spectroscopy with technical and hardware upgrades now makes it possible to probe LF modes with a standard single-stage Raman system and has proven crucial to characterize and understand properties of 2DMs. Here, we present a comprehensive and forward-looking review on the current status of exploiting LF Raman modes of 2DMs from both experimental and theoretical perspectives, revealing the fundamental physics and technological significance of LF Raman modes in advancing the field of 2DMs. We review a broad array of materials, with varying thickness and stacking configurations, discuss the effect of in-plane anisotropy, and present a generalized linear chain model and interlayer bond polarizability model to rationalize the experimental findings. We also discuss the instrumental improvements of Raman spectroscopy to enhance and separate LF Raman signals from the Rayleigh line. Lastly, we highlight the opportunities and challenges ahead in this fast-developing field.« 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.

Rapid Raman spectroscopy of musculoskeletal tissue using a visible laser and an electron-multiplying CCD (EMCCD) detector

NASA Astrophysics Data System (ADS)

Golcuk, Kurtulus; Mandair, Gurjit S.; Callender, Andrew F.; Finney, William F.; Sahar, Nadder; Kohn, David H.; Morris, Michael D.

2006-02-01

Background fluorescence can often complicate the use of Raman microspectroscopy in the study of musculoskeletal tissues. Such fluorescence interferences are undesirable as the Raman spectra of matrix and mineral phases can be used to differentiate between normal and pathological or microdamaged bone. Photobleaching with the excitation laser provides a non-invasive method for reducing background fluorescence, enabling 532 nm Raman hyperspectral imaging of bone tissue. The signal acquisition time for a 400 point Raman line image is reduced to 1-4 seconds using electronmultiplying CCD (EMCCD) detector, enabling acquisition of Raman images in less than 10 minutes. Rapid photobleaching depends upon multiple scattering effects in the tissue specimen and is applicable to some, but not all experimental situations.

Blood identification and discrimination between human and nonhuman blood using portable Raman spectroscopy.

PubMed

Fujihara, J; Fujita, Y; Yamamoto, T; Nishimoto, N; Kimura-Kataoka, K; Kurata, S; Takinami, Y; Yasuda, T; Takeshita, H

2017-03-01

Raman spectroscopy is commonly used in chemistry to identify molecular structure. This technique is a nondestructive analysis and needs no sample preparation. Recently, Raman spectroscopy has been shown to be effective as a multipurpose analytical method for forensic applications. In the present study, blood identification and discrimination between human and nonhuman blood were performed by a portable Raman spectrometer, which can be used at a crime scene. To identify the blood and to discriminate between human and nonhuman blood, Raman spectra of bloodstains from 11 species (human, rat, mouse, cow, horse, sheep, pig, rabbit, cat, dog, and chicken) were taken using a portable Raman spectrometer. Raman peaks for blood (742, 1001, 1123, 1247, 1341, 1368, 1446, 1576, and 1619 cm -1 ) could be observed by the portable Raman spectrometer in all 11 species, and the human bloodstain could be distinguished from the nonhuman ones by using a principal component analysis. This analysis can be performed on a bloodstain sample of at least 3 months old. The portable Raman spectrometer can be used at a crime scene, and this analysis is useful for forensic examination.

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.

[Laser Raman spectrum analysis of carbendazim pesticide].

PubMed

Wang, Xiao-bin; Wu, Rui-mei; Liu, Mu-hua; Zhang, Lu-ling; Lin, Lei; Yan, Lin-yuan

2014-06-01

Raman signal of solid and liquid carbendazim pesticide was collected by laser Raman spectrometer. The acquired Raman spectrum signal of solid carbendazim was preprocessed by wavelet analysis method, and the optimal combination of wavelet denoising parameter was selected through mixed orthogonal test. The results showed that the best effect was got with signal to noise ratio (SNR) being 62.483 when db2 wavelet function was used, decomposition level was 2, the threshold option scheme was 'rigisure' and reset mode was 'sln'. According to the vibration mode of different functional groups, the de-noised Raman bands could be divided into 3 areas: 1 400-2 000, 700-1 400 and 200-700 cm(-1). And the de-noised Raman bands were assigned with and analyzed. The characteristic vibrational modes were gained in different ranges of wavenumbers. Strong Raman signals were observed in the Raman spectrum at 619, 725, 964, 1 022, 1 265, 1 274 and 1 478 cm(-1), respectively. These characteristic vibrational modes are characteristic Raman peaks of solid carbendazim pesticide. Find characteristic Raman peaks at 629, 727, 1 001, 1 219, 1 258 and 1 365 cm(-1) in Raman spectrum signal of liquid carbendazim. These characteristic peaks were basically tallies with the solid carbendazim. The results can provide basis for the rapid screening of pesticide residue in food and agricultural products based on Raman spectrum.

Identification of microplastics using Raman spectroscopy: Latest developments and future prospects.

PubMed

Araujo, Catarina F; Nolasco, Mariela M; Ribeiro, Antonio M P; Ribeiro-Claro, Paulo J A

2018-06-06

Widespread microplastic pollution is raising growing concerns as to its detrimental effects upon living organisms. A realistic risk assessment must stand on representative data on the abundance, size distribution and chemical composition of microplastics. Raman microscopy is an indispensable tool for the analysis of very small microplastics (<20 μm). Still, its use is far from widespread, in part due to drawbacks such as long measurement time and proneness to spectral distortion induced by fluorescence. This review discusses each drawback followed by a showcase of interesting and easily available solutions that contribute to faster and better identification of microplastics using Raman spectroscopy. Among discussed topics are: enhanced signal quality with better detectors and spectrum processing; automated particle selection for faster Raman mapping; comprehensive reference libraries for successful spectral matching. A last section introduces non-conventional Raman techniques (non-linear Raman, hyperspectral imaging, standoff Raman) which permit more advanced applications such as real-time Raman detection and imaging of microplastics. Copyright © 2018 Elsevier Ltd. All rights reserved.

Analytic calculations of hyper-Raman spectra from density functional theory hyperpolarizability gradients

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

Ringholm, Magnus; Ruud, Kenneth; Bast, Radovan

We present the first analytic calculations of the geometrical gradients of the first hyperpolarizability tensors at the density-functional theory (DFT) level. We use the analytically calculated hyperpolarizability gradients to explore the importance of electron correlation effects, as described by DFT, on hyper-Raman spectra. In particular, we calculate the hyper-Raman spectra of the all-trans and 11-cis isomers of retinal at the Hartree-Fock (HF) and density-functional levels of theory, also allowing us to explore the sensitivity of the hyper-Raman spectra on the geometrical characteristics of these structurally related molecules. We show that the HF results, using B3LYP-calculated vibrational frequencies and force fields,more » reproduce the experimental data for all-trans-retinal well, and that electron correlation effects are of minor importance for the hyper-Raman intensities.« less

Normal mode and experimental analysis of TNT Raman spectrum

NASA Astrophysics Data System (ADS)

Liu, Yuemin; Perkins, Richard; Liu, Yucheng; Tzeng, Nianfeng

2017-04-01

In this study, a Raman spectrum of TNT was characterized through experiments and simulated using 22 hybrid density functional theory (DFT) methods. Among the different hybrid DFT methods, it was found that the most accurate simulation results of the Raman shift frequency were calculated by the O3LYP method. However, the deviations of the calculated Raman frequencies from the experimental value showed no dependency on the abilities of the DFT methods in recovering the correlation energy. The accuracies of the DFT methods in predicting the Raman bands are probably determined by the numerical grid and convergence criteria for optimizations of each DFT method. It was also decided that the prominent Raman shift 1362 cm-1 is mainly caused by symmetric stretching of the 4-nitro groups. Findings of this study can facilitate futuristic development of more effective surface enhanced Raman spectroscopy/scattering (SERS) substrates for explosive characterization and detection.

Enhancement of Raman scattering in dielectric nanostructures with electric and magnetic Mie resonances

NASA Astrophysics Data System (ADS)

Frizyuk, Kristina; Hasan, Mehedi; Krasnok, Alex; Alú, Andrea; Petrov, Mihail

2018-02-01

Resonantly enhanced Raman scattering in dielectric nanostructures has been recently proven to be an efficient tool for nanothermometry and for the experimental determination of their mode composition. In this paper we develop a rigorous analytical theory based on the Green's function approach to calculate the Raman emission from crystalline high-index dielectric nanoparticles. As an example, we consider silicon nanoparticles which have a strong Raman response due to active optical phonon modes. We relate enhancement of Raman signal emission to the Purcell effect due to the excitation of Mie modes inside the nanoparticles. We also employ our numerical approach to calculate inelastic Raman emission in more sophisticated geometries, which do not allow a straightforward analytical form of the Green's function. The Raman response from a silicon nanodisk has been analyzed with the proposed method, and the contribution of various Mie modes has been revealed.

Cavity-enhanced Raman microscopy of individual carbon nanotubes

PubMed Central

Hümmer, Thomas; Noe, Jonathan; Hofmann, Matthias S.; Hänsch, Theodor W.; Högele, Alexander; Hunger, David

2016-01-01

Raman spectroscopy reveals chemically specific information and provides label-free insight into the molecular world. However, the signals are intrinsically weak and call for enhancement techniques. Here, we demonstrate Purcell enhancement of Raman scattering in a tunable high-finesse microcavity, and utilize it for molecular diagnostics by combined Raman and absorption imaging. Studying individual single-wall carbon nanotubes, we identify crucial structural parameters such as nanotube radius, electronic structure and extinction cross-section. We observe a 320-times enhanced Raman scattering spectral density and an effective Purcell factor of 6.2, together with a collection efficiency of 60%. Potential for significantly higher enhancement, quantitative signals, inherent spectral filtering and absence of intrinsic background in cavity-vacuum stimulated Raman scattering render the technique a promising tool for molecular imaging. Furthermore, cavity-enhanced Raman transitions involving localized excitons could potentially be used for gaining quantum control over nanomechanical motion and open a route for molecular cavity optomechanics. PMID:27402165

A 1064 nm dispersive Raman spectral imaging system for food safety and quality evaluation

USDA-ARS?s Scientific Manuscript database

Raman spectral imaging is an effective method to analyze and evaluate chemical composition and structure of a sample, and has many applications for food safety and quality research. This study developed a 1064 nm Raman spectral imaging system for surface and subsurface analysis of food samples. A 10...

Using water raman intensity to determine the effective excitation and emission path lengths of fluorophotometers for correcting fluorescence inner filter effect

USDA-ARS?s Scientific Manuscript database

Fluorescence and Raman inner filter effects (IFE) cause spectral distortion and nonlinearity between spectral signal intensity with increasing analyte concentration. Convenient and effective correction of fluorescence IFE has been an active research goal for decades. Presented herein is the finding ...

THE FATE AND TOXICITY OF RAMAN ACTIVE SILICA-GOLD NANOPARTICLES IN MICE

PubMed Central

THAKOR, AVNESH S; LUONG, RICHARD; PAULMURUGAN, RAMASAMY; LIN, FRANK I; KEMPEN, PAUL; ZAVALETA, CRISTINA; CHU, PAULINE; MASSOUD, TARIK F; SINCLAIR, ROBERT; GAMBHIR, SANJIV S

2013-01-01

Raman spectroscopy is an optical imaging modality which analyses the Raman effect in which energy is exchanged between light and matter. Although Raman spectroscopy has been widely used for chemical and molecular analysis, its use in clinical applications has been hindered by the inherently weak nature of the Raman effect. Raman-silica-gold-nanoparticles (R-Si-Au-NPs) overcome this limitation by producing high Raman signals via Surface Enhanced Raman Scattering. Targeted polyethylene glycol (PEG)-ylated R-Si-Au-NPs (e.g. PEG-R-Si-Au-NPs labeled with an affibody which binds specifically to the epidermal growth factor receptor) are currently being designed to detect colorectal cancer after administration into the bowel lumen. With this approach, PEG-R-Si-Au-NPs are not expected to enter the systemic circulation and would be removed from the body via defecation. We examined the acute toxicity and biodistribution of core PEG-R-Si-Au-NPs after different routes of administration in mice. After intravenous administration, PEG-R-Si-Au-NPs were removed from the circulation by marcophages in the liver and spleen (i.e. the reticuloendothelial system). At 24 hours, PEG-R-Si-Au-NPs elicited a mild inflammatory response and an increase in oxidative stress in the liver, which subsided by 2 weeks. No evidence of significant toxicity was observed by measuring clinical, histological, biochemical or cardiovascular parameters for 2 weeks. Notably, after administration per rectum, we observed no significant bowel or systemic toxicity and no PEG-R-Si-Au-NPs were detected systemically. Although additional studies are required to investigate the long-term effects of PEG-R-Si-Au-NPs, these initial results support the idea that they can be safely used in living subjects, especially when administered rectally. PMID:21508310

Two-Dimensional Heterostructure as a Platform for Surface-Enhanced Raman Scattering.

PubMed

Tan, Yang; Ma, Linan; Gao, Zhibin; Chen, Ming; Chen, Feng

2017-04-12

Raman enhancement on a flat nonmetallic surface has attracted increasing attention, ever since the discovery of graphene enhanced Raman scattering. Recently, diverse two-dimensional layered materials have been applied as a flat surface for the Raman enhancement, attributed to different mechanisms. Looking beyond these isolated materials, atomic layers can be reassembled to design a heterostructure stacked layer by layer with an arbitrary chosen sequence, which allows the flow of charge carriers between neighboring layers and offers novel functionalities. Here, we demonstrate the heterostructure as a novel Raman enhancement platform. The WSe 2 (W) monolayer and graphene (G) were stacked together to form a heterostructure with an area of 10 mm × 10 mm. Heterostructures with different stacked structuress are used as platforms for the enhanced Raman scattering, including G/W, W/G, G/W/G/W, and W/G/G/W. On the surface of the heterostructure, the intensity of the Raman scattering is much stronger compared with isolated layers, using the copper phthalocyanine (CuPc) molecule as a probe. It is found that the Raman enhancement effect on heterostructures depends on stacked methods. Phonon modes of CuPc have the strongest enhancement on G/W. W/G and W/G/G/W have a stronger enhancement than that on the isolated WSe 2 monolayer, while lower than the graphene monolayer. The G/W/G/W/substrate demonstrated a comparable Raman enhancement effect than the G/W/substrate. These differences are due to the different interlayer couplings in heterostructures related to electron transition probability rates, which are further proved by first-principle calculations and probe-pump measurements.

Micro-Raman Spectroscopy of Silver Nanoparticle Induced Stress on Optically-Trapped Stem Cells

PubMed Central

Bankapur, Aseefhali; Krishnamurthy, R. Sagar; Zachariah, Elsa; Santhosh, Chidangil; Chougule, Basavaraj; Praveen, Bhavishna; Valiathan, Manna; Mathur, Deepak

2012-01-01

We report here results of a single-cell Raman spectroscopy study of stress effects induced by silver nanoparticles in human mesenchymal stem cells (hMSCs). A high-sensitivity, high-resolution Raman Tweezers set-up has been used to monitor nanoparticle-induced biochemical changes in optically-trapped single cells. Our micro-Raman spectroscopic study reveals that hMSCs treated with silver nanoparticles undergo oxidative stress at doping levels in excess of 2 µg/ml, with results of a statistical analysis of Raman spectra suggesting that the induced stress becomes more dominant at nanoparticle concentration levels above 3 µg/ml. PMID:22514708

Rayleigh rejection filters for 193-nm ArF laser Raman spectroscopy

NASA Technical Reports Server (NTRS)

Mckenzie, Robert L.

1993-01-01

Selected organic absorbers and their solvents are evaluated as spectral filters for the rejection of 193-nm Rayleigh light associated with the use of an ArF excimer laser for Raman spectroscopy. A simply constructed filter cell filled with 0.5 percent acetone in water and an optical path of 7 mm is shown effectively to eliminate stray Rayleigh light underlying the Raman spectrum from air while transmitting 60 percent of the Raman light scattered by O2.

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.

Effect of a Nitrogen Impurity on the Fundamental Raman Band of Diamond Single Crystals

NASA Astrophysics Data System (ADS)

Gusakov, G. A.; Samtsov, M. P.; Voropay, E. S.

2018-05-01

The effect of nitrogen defects in natural and synthetic diamond single crystals on the position and half-width of the fundamental Raman band was investigated. Samples containing the main types of nitrogen lattice defects at impurity contents of 1-1500 ppm were studied. The parameters of the Stokes and anti-Stokes components in Raman spectra of crystals situated in a cell with distilled water to minimize the influence of heating by the exciting laser radiation were analyzed to determine the effect of a nitrogen impurity in the diamond crystal lattice. It was shown that an increase of impurity atoms in the crystals in the studied concentration range resulted in broadening of the Raman band from 1.61 to 2.85 cm-1 and shifting of the maximum to lower frequency from 1332.65 to 1332.3 cm-1. The observed effect was directly proportional to the impurity concentration and depended on the form of the impurity incorporated into the diamond lattice. It was found that the changes in the position and half-width of the fundamental Raman band for diamond were consistent with the magnitude of crystal lattice distortions due to the presence of impurity defects and obeyed the Gruneisen law.

Raman microscopy of bladder cancer cells expressing green fluorescent protein

NASA Astrophysics Data System (ADS)

Mandair, Gurjit S.; Han, Amy L.; Keller, Evan T.; Morris, Michael D.

2016-11-01

Gene engineering is a commonly used tool in cellular biology to determine changes in function or expression of downstream targets. However, the impact of genetic modulation on biochemical effects is less frequently evaluated. The aim of this study is to use Raman microscopy to assess the biochemical effects of gene silencing on T24 and UMUC-13 bladder cancer cell lines. Cellular biochemical information related to nucleic acid and lipogenic components was obtained from deconvolved Raman spectra. We show that the green fluorescence protein (GFP), the chromophore that served as a fluorescent reporter for gene silencing, could also be detected by Raman microscopy. Only the gene-silenced UMUC-13 cell lines exhibited low-to-moderate GFP fluorescence as determined by fluorescence imaging and Raman spectroscopic studies. Moreover, we show that gene silencing and cell phenotype had a greater effect on nucleic acid and lipogenic components with minimal interference from GFP expression. Gene silencing was also found to perturb cellular protein secondary structure in which the amount of disorderd protein increased at the expense of more ordered protein. Overall, our study identified the spectral signature for cellular GFP expression and elucidated the effects of gene silencing on cancer cell biochemistry and protein secondary structure.

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.

Contributions of Raman spectroscopy to the understanding of bone strength.

PubMed

Mandair, Gurjit S; Morris, Michael D

2015-01-01

Raman spectroscopy is increasingly commonly used to understand how changes in bone composition and structure influence tissue-level bone mechanical properties. The spectroscopic technique provides information on bone mineral and matrix collagen components and on the effects of various matrix proteins on bone material properties as well. The Raman spectrum of bone not only contains information on bone mineral crystallinity that is related to bone hardness but also provides information on the orientation of mineral crystallites with respect to the collagen fibril axis. Indirect information on collagen cross-links is also available and will be discussed. After a short introduction to bone Raman spectroscopic parameters and collection methodologies, advances in in vivo Raman spectroscopic measurements for animal and human subject studies will be reviewed. A discussion on the effects of aging, osteogenesis imperfecta, osteoporosis and therapeutic agents on bone composition and mechanical properties will be highlighted, including genetic mouse models in which structure-function and exercise effects are explored. Similarly, extracellular matrix proteins, proteases and transcriptional proteins implicated in the regulation of bone material properties will be reviewed.

[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.

Raman microspectroscopy, surface-enhanced Raman scattering microspectroscopy, and stable-isotope Raman microspectroscopy for biofilm characterization.

PubMed

Ivleva, Natalia P; Kubryk, Patrick; Niessner, Reinhard

2017-07-01

Biofilms represent the predominant form of microbial life on our planet. These aggregates of microorganisms, which are embedded in a matrix formed by extracellular polymeric substances, may colonize nearly all interfaces. Detailed knowledge of microorganisms enclosed in biofilms as well as of the chemical composition, structure, and functions of the complex biofilm matrix and their changes at different stages of the biofilm formation and under various physical and chemical conditions is relevant in different fields. Important research topics include the development and improvement of antibiotics and medical devices and the optimization of biocides, antifouling strategies, and biological wastewater treatment. Raman microspectroscopy is a capable and nondestructive tool that can provide detailed two-dimensional and three-dimensional chemical information about biofilm constituents with the spatial resolution of an optical microscope and without interference from water. However, the sensitivity of Raman microspectroscopy is rather limited, which hampers the applicability of Raman microspectroscopy especially at low biomass concentrations. Fortunately, the resonance Raman effect as well as surface-enhanced Raman scattering can help to overcome this drawback. Furthermore, the combination of Raman microspectroscopy with other microscopic techniques, mass spectrometry techniques, or particularly with stable-isotope techniques can provide comprehensive information on monospecies and multispecies biofilms. Here, an overview of different Raman microspectroscopic techniques, including resonance Raman microspectroscopy and surface-enhanced Raman scattering microspectroscopy, for in situ detection, visualization, identification, and chemical characterization of biofilms is given, and the main feasibilities and limitations of these techniques in biofilm research are presented. Future possibilities of and challenges for Raman microspectroscopy alone and in combination with other analytical techniques for characterization of complex biofilm matrices are discussed in a critical review. Graphical Abstract Applicability of Raman microspectroscopy for biofilm analysis.

The focusing effect in backward Raman amplification in plasma

NASA Astrophysics Data System (ADS)

Li, Zhaoli; Peng, Hao; Zuo, Yanlei; Su, Jingxin; Yang, Suhui

2018-04-01

In this paper, the focusing effect on backward Raman amplification in plasma is investigated. A fluid model, used to simulate the backward Raman amplification and including the relativistic, ponderomotive, and thermal self-focusing and the mutual-focusing effect simultaneously, is proposed and investigated. The focusing effect is shown to severely distort the profile of the seed when the seed intensity was as high as 10 17 W/cm2. Reducing the plasma density can relax the focusing effect, but at the cost of decreasing the amplification efficiency. Changing the profile of the seed has a limited effect on mitigating the focusing effect. A Gaussian profile of the pump and a defocusing shape of the plasma density seem to be an effective way to mitigate the focusing effect without decreasing the amplification efficiency.

Strongly enhanced Raman scattering of Cu-phthalocyanine sandwiched between graphene and Au(111).

PubMed

Lin, Wan-Ing; Gholami, Mohammad Fardin; Beyer, Paul; Severin, Nikolai; Shao, Feng; Zenobi, Renato; Rabe, Jürgen P

2017-01-05

Graphene and flat gold have both been argued to enhance Raman scattering of molecular adsorbates through a chemical mechanism. Here we show that these two effects can add to each other. For Cu-phthalocyanine in between graphene and Au(111) on mica a Raman enhancement up to 68-fold has been observed.

Progress on Raman laser for sodium resonance fluorescence lidar

NASA Astrophysics Data System (ADS)

Li, Steven X.; Yu, Anthony W.; Krainak, Michael A.; Bai, Yingxin; Konoplev, Oleg; Fahey, Molly E.; Numata, Kenji

2018-02-01

We are developing a Q-switched narrow linewidth intra-cavity Raman laser for a space based sodium lidar application. A novel Raman laser injection seeding scheme is proposed and is experimentally verified. A Q-switched, diode pumped, c-cut Nd:YVO4 laser has been designed to emit a fundamental wavelength at 1066.6 nm. This fundamental wavelength is used as the pump in an intra-cavity Raman conversion in a Gd0.2Y0.8VO4 composite material. By tuning the temperature of the crystal, we tuned the Raman shifting to the desired sodium absorption line. A diode end pumped, T-shaped laser cavity has been built for experimental investigation. The fundamental pump laser cavity is a twisted mode cavity to eliminate the spatial hole burning for effective injection seeding. The Raman laser cavity is a linear standing wave cavity because Raman gain medium does not suffer spatial hole burning as traditional laser gain medium. The linewidth and temporal profile of the Raman laser is experimentally investigated with narrow and broadband fundamental pump emission. We have, for the first time, demonstrated an injection seeded, high peak power, narrow linewidth intra-cavity Raman laser for potential use in a sodium resonance fluorescence lidar.

Raman spectroscopic instrumentation and plasmonic methods for material characterization

NASA Astrophysics Data System (ADS)

Tanaka, Kazuki

The advent of nanotechnology has led to incredible growth in how we consume, make and approach advanced materials. By exploiting nanoscale material properties, unique control of optical, thermal, mechanical, and electrical characteristics becomes possible. This thesis describes the development of a novel localized surface plasmon resonant (LSPR) color sensitive photosensor, based on functionalization of gold nanoparticles onto tianium dioxide nanowires and sensing by a metal-semiconducting nanowire-metal photodiode structure. This LSPR photosensor has been integrated into a system that incorporates Raman spectroscopy, microfluidics, optical trapping, and sorting flow cytometry into a unique material characterization system called the microfluidic optical fiber trapping Raman sorting flow cytometer (MOFTRSFC). Raman spectroscopy is utilized as a powerful molecular characterization technique used to analyze biological, mineralogical and nanomaterial samples. To combat the inherently weak Raman signal, plasmonic methods have been applied to exploit surface enhanced Raman scattering (SERS) and localized surface plasmon resonance (LSPR), increasing Raman intensity by up to 5 orders of magnitude. The resultant MOFTRSFC system is a prototype instrument that can effectively trap, analyze, and sort micron-sized dielectric particles and biological cells. Raman spectroscopy has been presented in several modalities, including the development of a portable near-infrared Raman spectrometer and other emerging technologies.

Raman mapping probing of tip-induced anomalous polarization behavior in V2O5 waveguiding nanoribbons

NASA Astrophysics Data System (ADS)

Yan, Bin; Du, Chaoling; Liao, Lei; You, Yumeng; Cheng, Hao; Shen, Zexiang; Yu, Ting

2010-02-01

Spatially resolved and polarized micro-Raman spectroscopy has been performed on individual V2O5 waveguiding nanoribbons. The experimental results establish that the Raman-antenna patterns are strongly correlated with the local positions of the sample, which gives rise to a pronounced intensity contrast in the polarized mapping for certain phonon modes. The suppressed phonon signals at the body of a ribbon can be enhanced at the end facets, resulting from the effective waveguiding propagation along the nanoribbon and strong local electric field intensity at the ends. The phenomena reported here, in addition to providing insight into the tip effects on optoelectronic nanodevices, will facilitate the rational design of Raman detection in nanostructures.

Non-destructive NIR-FT-Raman spectroscopy of plant and animal tissues, of food and works of art.

PubMed

Schrader, B; Schulz, H; Andreev, G N; Klump, H H; Sawatzki, J

2000-10-02

Just after the discovery of Raman spectroscopy in 1928, it became evident that fluorescence with a quantum yield of several orders of magnitude higher than that of the Raman effect was a great and apparently unbeatable competitor. Raman spectroscopy could therefore, in spite of many exciting advantages during the last 60 years, not be applied as an analytical routine method: for nearly every sample, fluorescing impurities had to be removed by distillation or crystallisation. Purification, however, is not possible for cells and tissues, since the removal of the fluorescing enzymes and coenzymes would destroy the cells. There is fortunately one alternative solution. When excited with the radiation of the Nd:YAG laser at 1064 nm Raman spectra are practically free of fluorescence. Raman spectra can now be recorded with minimal sample preparation. In order to facilitate non-destructive Raman spectroscopy of any sample, cells and tissues, food, textiles and works of art, a new entrance optics for Raman spectrometers is used. Typical results from several fields are demonstrated.

Quick detection of traditional Chinese medicine ‘Atractylodis Macrocephalae Rhizoma’ pieces by surface-enhanced Raman spectroscopy

NASA Astrophysics Data System (ADS)

Huang, Hao; Shi, Hong; Feng, Shangyuan; Lin, Juqiang; Chen, Weiwei; Yu, Yun; Lin, Duo; Xu, Qian; Chen, Rong

2013-01-01

A surface-enhanced Raman spectroscopy (SERS) method was developed for the analysis of traditional Chinese medicine ‘Atractylodis Macrocephalae Rhizoma’ pieces (AMRP) for the first time with the aim to develop a quick method for traditional Chinese medicine detection. Both Raman spectra and SERS spectra were obtained from AMRP, and tentative assignments of the Raman bands in the measured spectra suggested that only a few weak Raman peaks could be observed in the regular Raman spectra, while primary Raman peaks at around 536, 555, 619, 648, 691, 733, 790, 958, 1004, 1031, 1112, 1244, 1324, 1395, 1469, 1574 and 1632 cm-1 could be observed in the SERS spectra, with the strongest signals at 619, 733, 958, 1324, 1395 and 1469 cm-1. This was due to a strong interaction between the silver colloids and the AMRP, which led to an extraordinary enhancement in the intensity of the Raman scattering in AMRP. This exploratory study suggests the SERS technique has great potential for providing a novel non-destructive method for effectively and accurately detecting traditional Chinese medicine without complicated separation and extraction.

Raman and AFM study of gamma irradiated plastic bottle sheets

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

Ali, Yasir; Kumar, Vijay; Dhaliwal, A. S.

2013-02-05

In this investigation, the effects of gamma irradiation on the structural properties of plastic bottle sheet are studied. The Plastic sheets were exposed with 1.25MeV {sup 60}Co gamma rays source at various dose levels within the range from 0-670 kGy. The induced modifications were followed by micro-Raman and atomic force microscopy (AFM). The Raman spectrum shows the decrease in Raman intensity and formation of unsaturated bonds with an increase in the gamma dose. AFM image displays rough surface morphology after irradiation. The detailed Raman analysis of plastic bottle sheets is presented here, and the results are correlated with the AFMmore » observations.« less

Destruction of Raman biosignatures by ionising radiation and the implications for life detection on Mars.

PubMed

Dartnell, Lewis R; Page, Kristian; Jorge-Villar, Susana E; Wright, Gary; Munshi, Tasnim; Scowen, Ian J; Ward, John M; Edwards, Howell G M

2012-04-01

Raman spectroscopy has proven to be a very effective approach for the detection of microorganisms colonising hostile environments on Earth. The ExoMars rover, due for launch in 2018, will carry a Raman laser spectrometer to analyse samples of the martian subsurface collected by the probe's 2-m drill in a search for similar biosignatures. The martian surface is unprotected from the flux of cosmic rays, an ionising radiation field that will degrade organic molecules and so diminish and distort the detectable Raman signature of potential martian microbial life. This study employs Raman spectroscopy to analyse samples of two model organisms, the cyanobacterium Synechocystis sp. PCC 6803 and the extremely radiation resistant polyextremophile Deinococcus radiodurans, that have been exposed to increasing doses of ionising radiation. The three most prominent peaks in the Raman spectra are from cellular carotenoids: deinoxanthin in D. radiodurans and β-carotene in Synechocystis. The degradative effect of ionising radiation is clearly seen, with significant diminishment of carotenoid spectral peak heights after 15 kGy and complete erasure of Raman biosignatures by 150 kGy of ionising radiation. The Raman signal of carotenoid in D. radiodurans diminishes more rapidly than that of Synechocystis, believed to be due to deinoxanthin acting as a superior scavenger of radiolytically produced reactive oxygen species, and so being destroyed more quickly than the less efficient antioxidant β-carotene. This study highlights the necessity for further experimental work on the manner and rate of degradation of Raman biosignatures by ionising radiation, as this is of prime importance for the successful detection of microbial life in the martian near subsurface.

Finite-size effects in surface-enhanced Raman scattering in noble-metal nanoparticles: a semiclassical approach.

PubMed

Pustovit, Vitaliy N; Shahbazyan, Tigran V

2006-06-01

We study finite-size effects in surface-enhanced Raman scattering (SERS) from molecules adsorbed on small metal particles. Within an electromagnetic description of SERS, the enhancement of the Raman signal originates from the local field of the surface plasmon resonance in a nanoparticle. With decreasing particle sizes, this enhancement is reduced due to the size-dependent Landau damping of the surface plasmon. We show that, in small noble-metal particles, the reduction of interband screening in the surface layer leads to an additional increase in the local field acting on a molecule close to the metal surface. The overall size dependence of Raman signal enhancement is determined by the interplay between Landau damping and underscreening effects. Our calculations, based on a two-region model, show that the role of the surface layer increases for smaller nanoparticle sizes due to a larger volume fraction of the underscreened region.

Giant magneto-optical Raman effect in a layered transition metal compound

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

Ji, Jianting; Zhang, Anmin; Fan, Jiahe

2016-02-16

Here, we report a dramatic change in the intensity of a Raman mode with applied magnetic field, displaying a gigantic magneto-optical effect. Using the nonmagnetic layered material MoS 2 as a prototype system, we demonstrate that the application of a magnetic field perpendicular to the layers produces a dramatic change in intensity for the out-of-plane vibrations of S atoms, but no change for the in-plane breathing mode. The distinct intensity variation between these two modes results from the effect of field-induced broken symmetry on Raman scattering cross-section. A quantitative analysis on the field-dependent integrated Raman intensity provides a unique methodmore » to precisely determine optical mobility. Our analysis is symmetry-based and material-independent, and thus the observations should be general and inspire a new branch of inelastic light scattering and magneto-optical applications.« less

Remote measurements of the atmosphere using Raman scattering.

NASA Technical Reports Server (NTRS)

Melfi, S. H.

1972-01-01

Raman optical radar measurements of the atmosphere demonstrate that the technique may be used to obtain quantitative measurements of the spatial distribution of individual atmospheric molecular trace constituents (in particular water vapor) and of the major constituents. It is shown that monitoring Raman signals from atmospheric nitrogen aids in interpreting elastic scattering measurements by eliminating attenuation effects. In general, the experimental results show good agreement with independent meteorological measurements. Finally, experimental data are utilized to estimate the Raman backscatter cross section for water vapor excited at 3471.5 A.

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.

Raman vibrational spectra of bulk to monolayer Re S 2 with lower symmetry

DOE PAGES

Feng, Yanqing; Zhou, Wei; Wang, Yaojia; ...

2015-08-26

Lattice structure and symmetry of two-dimensional (2D) layered materials are of key importance to their fundamental mechanical, thermal, electronic and optical properties. Raman spectroscopy, as a convenient and nondestructive tool, however has its limitations on identifying all symmetry allowing Raman modes and determining the corresponding crystal structure of 2D layered materials with high symmetry like graphene and MoS 2. Due to lower structural symmetry and extraordinary weak interlayer coupling of ReS 2, we successfully identified all 18 first-order Raman active modes for bulk and monolayer ReS 2. Without van der Waals (vdW) correction, our local density approximation (LDA) calculations successfullymore » reproduce all the Raman modes. Our calculations also suggest no surface reconstruction effect and the absence of low frequency rigid-layer Raman modes below 100 cm -1. As a result, combining with Raman and LDA thus provides a general approach for studying the vibrational and structural properties of 2D layered materials with lower symmetry.« less

Raman spectroscopy for the evaluation of the effects of different concentrations of Copper on the chemical composition and biological activity of basil essential oil

NASA Astrophysics Data System (ADS)

Nawaz, Haq; Hanif, Muhammad Asif; Ayub, Muhammad Adnan; Ishtiaq, Faiqa; Kanwal, Nazish; Rashid, Nosheen; Saleem, Muhammad; Ahmad, Mushtaq

2017-10-01

The present study is performed to evaluate the effect of different concentrations of Cu as fertilizer on the chemical composition of basil essential oil and its biological activity including antioxidant and antifungal activities by employing Raman spectroscopy. Moreover, the effect of Cu is also determined on the vegetative growth and essential oil yield. Both, antifungal and antioxidant activities were found to be maximum with essential oils obtained at 0.04 mg/l concentration of Cu fertilizer. The results of the GC-MS and Raman spectroscopy have revealed that the linalool and estragole are found to be as a major chemical compound in basil essential oil. The Raman spectral changes associated with these biological components lead to the conclusion that estragole seems to have dominating effect in the biological activities of the basil essential oil as compared to linalool although the latter is observed in greater concentration.

Wave-mixing-induced transparency with zero phase shift in atomic vapors

NASA Astrophysics Data System (ADS)

Zhou, F.; Zhu, C. J.; Li, Y.

2017-12-01

We present a wave-mixing induced transparency that can lead to a hyper-Raman gain-clamping effect. This new type of transparency is originated from a dynamic gain cancellation effect in a multiphoton process where a highly efficient light field of new frequency is generated and amplified. We further show that this novel dynamic gain cancellation effect not only makes the medium transparent to a probe light field at appropriate frequency but also eliminates the probe field propagation phase shift. This gain-cancellation-based induced transparency holds for many potential applications on optical communication and may lead to effective suppression of parasitic Raman/hyper-Raman noise field generated in high intensity optical fiber transmissions.

Estimation of Cellulose Crystallinity of Lignocelluloses Using Near-IR FT-Raman Spectroscopy and Comparison of the Raman and Segal-WAXS Methods

Treesearch

Umesh P. Agarwal; Richard R. Reiner; Sally A. Ralph

2013-01-01

Of the recently developed univariate and multivariate near-IR FT-Raman methods for estimating cellulose crystallinity, the former method was applied to a variety of lignocelluloses: softwoods, hardwoods, wood pulps, and agricultural residues/fibers. The effect of autofluorescence on the crystallinity estimation was minimized by solvent extraction or chemical treatment...

Principal component analysis and analysis of variance on the effects of Entellan New on the Raman spectra of fibers.

PubMed

Yu, Marcia M L; Sandercock, P Mark L

2012-01-01

During the forensic examination of textile fibers, fibers are usually mounted on glass slides for visual inspection and identification under the microscope. One method that has the capability to accurately identify single textile fibers without subsequent demounting is Raman microspectroscopy. The effect of the mountant Entellan New on the Raman spectra of fibers was investigated to determine if it is suitable for fiber analysis. Raman spectra of synthetic fibers mounted in three different ways were collected and subjected to multivariate analysis. Principal component analysis score plots revealed that while spectra from different fiber classes formed distinct groups, fibers of the same class formed a single group regardless of the mounting method. The spectra of bare fibers and those mounted in Entellan New were found to be statistically indistinguishable by analysis of variance calculations. These results demonstrate that fibers mounted in Entellan New may be identified directly by Raman microspectroscopy without further sample preparation. © 2011 American Academy of Forensic Sciences.

Si/Ge elatform for lasers, amplifiers, and nonlinear optical devices based on the Raman Effect

NASA Astrophysics Data System (ADS)

Claps, Ricardo; Dimitropoulos, Dimitrios; Raghunathan, Varun; Fathpour, Sasan; Jalali, Bahram; Jusserand, Bernard

2007-02-01

The use of a silicon-germanium platform for the development of optically active devices will be discussed in this paper, from the perspective of Raman and Brillouin scattering phenomena. Silicon-Germanium is becoming a prevalent technology for the development of high speed CMOS transistors, with advances in several key parameters as high carrier mobility, low cost, and reduced manufacturing logistics. Traditionally, Si-Ge structures have been used in the optoelectronics arena as photodetectors, due to the enhanced absorption of Ge in the telecommunications band. Recent developments in Raman-based nonlinearities for devices based on a silicon-on-insulator platform have shed light on the possibility of using these effects in Si-Ge architectures. Lasing and amplification have been demonstrated using a SiGe alloy structure, and Brillouin/Raman activity from acoustic phonon modes in SiGe superlattices has been predicted. Moreover, new Raman-active branches and inhomogeneously broadened spectra result from optical phonon modes, offering new perspectives for optical device applications. The possibilities for an electrically-pumped Raman laser will be outlined, and the potential for design and development of silicon-based, Tera-Hertz wave emitters and/or receivers.

Analytic calculations of anharmonic infrared and Raman vibrational spectra

PubMed Central

Louant, Orian; Ruud, Kenneth

2016-01-01

Using a recently developed recursive scheme for the calculation of high-order geometric derivatives of frequency-dependent molecular properties [Ringholm et al., J. Comp. Chem., 2014, 35, 622], we present the first analytic calculations of anharmonic infrared (IR) and Raman spectra including anharmonicity both in the vibrational frequencies and in the IR and Raman intensities. In the case of anharmonic corrections to the Raman intensities, this involves the calculation of fifth-order energy derivatives—that is, the third-order geometric derivatives of the frequency-dependent polarizability. The approach is applicable to both Hartree–Fock and Kohn–Sham density functional theory. Using generalized vibrational perturbation theory to second order, we have calculated the anharmonic infrared and Raman spectra of the non- and partially deuterated isotopomers of nitromethane, where the inclusion of anharmonic effects introduces combination and overtone bands that are observed in the experimental spectra. For the major features of the spectra, the inclusion of anharmonicities in the calculation of the vibrational frequencies is more important than anharmonic effects in the calculated infrared and Raman intensities. Using methanimine as a trial system, we demonstrate that the analytic approach avoids errors in the calculated spectra that may arise if numerical differentiation schemes are used. PMID:26784673

New Examination of the Raman Lidar Technique for Water Vapor and Aerosols. Paper 1; Evaluating the Temperature Dependent Lidar Equations

NASA Technical Reports Server (NTRS)

Whiteman, David N.

2003-01-01

The intent of this paper and its companion is to compile together the essential information required for the analysis of Raman lidar water vapor and aerosol data acquired using a single laser wavelength. In this first paper several details concerning the evaluation of the lidar equation when measuring Raman scattering are considered. These details include the influence of the temperature dependence of both pure rotational and vibrational-rotational Raman scattering on the lidar profile. These are evaluated for the first time using a new form of the lidar equation. The results indicate that, for the range of temperatures encountered in the troposphere, the magnitude of the temperature dependent effect can reach 10% or more for narrowband Raman water vapor measurements. Also the calculation of atmospheric transmission is examined carefully including the effects of depolarization. Different formulations of Rayleigh cross section determination commonly used in the lidar field are compared revealing differences up to 5% among the formulations. The influence of multiple scattering on the measurement of aerosol extinction using the Raman lidar technique is considered as are several photon pulse-pileup correction techniques.

Processing Raman Spectra of High-Pressure Hydrogen Flames

NASA Technical Reports Server (NTRS)

Nguyen, Quang-Viet; Kojima, Jun

2006-01-01

The Raman Code automates the analysis of laser-Raman-spectroscopy data for diagnosis of combustion at high pressure. On the basis of the theory of molecular spectroscopy, the software calculates the rovibrational and pure rotational Raman spectra of H2, O2, N2, and H2O in hydrogen/air flames at given temperatures and pressures. Given a set of Raman spectral data from measurements on a given flame and results from the aforementioned calculations, the software calculates the thermodynamic temperature and number densities of the aforementioned species. The software accounts for collisional spectral-line-broadening effects at pressures up to 60 bar (6 MPa). The line-broadening effects increase with pressure and thereby complicate the analysis. The software also corrects for spectral interference ("cross-talk") among the various chemical species. In the absence of such correction, the cross-talk is a significant source of error in temperatures and number densities. This is the first known comprehensive computer code that, when used in conjunction with a spectral calibration database, can process Raman-scattering spectral data from high-pressure hydrogen/air flames to obtain temperatures accurate to within 10 K and chemical-species number densities accurate to within 2 percent.

Analysis of root surface properties by fluorescence/Raman intensity ratio.

PubMed

Nakamura, Shino; Ando, Masahiro; Hamaguchi, Hiro-O; Yamamoto, Matsuo

2017-11-01

The aim of this study is to evaluate the existence of residual calculus on root surfaces by determining the fluorescence/Raman intensity ratio. Thirty-two extracted human teeth, partially covered with calculus on the root surface, were evaluated by using a portable Raman spectrophotometer, and a 785-nm, 100-mW laser was applied for fluorescence/Raman excitation. The collected spectra were normalized to the hydroxyapatite Raman band intensity at 960 cm -1 . Raman spectra were recorded from the same point after changing the focal distance of the laser and the target radiating angle. In seven teeth, the condition of calculus, cementum, and dentin were evaluated. In 25 teeth, we determined the fluorescence/Raman intensity ratio following three strokes of debridement. Raman spectra collected from the dentin, cementum, and calculus were different. After normalization, spectra values were constant. The fluorescence/Raman intensity ratio of calculus region showed significant differences compared to the cementum and dentin (p < 0.05). The fluorescence/Raman intensity ratio decreased with calculus debridement. For this analysis, the delta value was defined as the difference between the values before and after three strokes, with the final 2 delta values close to zero, indicating a gradual asymptotic curve and the change in intensity ratio approximating that of individual constants. Fluorescence/Raman intensity ratio was effectively used to cancel the angle- and distance-dependent fluctuations of fluorescence collection efficiency during measurement. Changes in the fluorescence/Raman intensity ratio near zero suggested that cementum or dentin was exposed, and calculus removed.

Quantum Interference Effects in Resonant Raman Spectroscopy of Single- and Triple-Layer MoTe2 from First-Principles

NASA Astrophysics Data System (ADS)

Miranda, Henrique P. C.; Reichardt, Sven; Froehlicher, Guillaume; Molina-Sánchez, Alejandro; Berciaud, Stéphane; Wirtz, Ludger

2017-04-01

We present a combined experimental and theoretical study of resonant Raman spectroscopy in single- and triple-layer MoTe$_2$. Raman intensities are computed entirely from first principles by calculating finite differences of the dielectric susceptibility. In our analysis, we investigate the role of quantum interference effects and the electron-phonon coupling. With this method, we explain the experimentally observed intensity inversion of the $A^\\prime_1$ vibrational modes in triple-layer MoTe2 with increasing laser photon energy. Finally, we show that a quantitative comparison with experimental data requires the proper inclusion of excitonic effects.

Effect of boron doping on first-order Raman scattering in superconducting boron doped diamond films

NASA Astrophysics Data System (ADS)

Kumar, Dinesh; Chandran, Maneesh; Ramachandra Rao, M. S.

2017-05-01

Aggregation of impurity levels into an impurity band in heavily boron doped diamond results in a background continuum and discrete zone centre phonon interference during the inelastic light scattering process. In order to understand the Raman scattering effect in granular BDD films, systematically heavily doped samples in the semiconducting and superconducting regimes have been studied using the excitation wavelengths in the UV and visible regions. A comprehensive analysis of the Fano resonance effect as a function of the impurity concentrations and the excitation frequencies is presented. Various Raman modes available in BDD including signals from the grain boundaries are discussed.

Isotope effect on superconductivity and Raman phonons of Pyrochlore Cd2Re2O7

NASA Astrophysics Data System (ADS)

Razavi, F. S.; Hajialamdari, M.; Reedyk, M.; Kremer, R. K.

2018-06-01

Cd2Re2O7 is the only α-Pyrochlore exhibiting superconductivity with a transition temperature (Tc) of ∼ 1 K. In this study, we present the effect of oxygen isotope (18O) as well as combined 18O and cadmium isotope (116Cd) substitution on the superconductivity and Raman scattering spectrum of Cd2Re2O7. The change of Tc and the energy gap Δ(T) are reported using various techniques including point contact spectroscopy. The shift in Raman phonon frequencies upon isotope substitution will be compared with measurement of the isotope effect on the superconducting transition temperature.

A portable fiber-optic raman spectrometer concept for evaluation of mineral content within enamel tissue.

PubMed

Akkus, Anna; Yang, Shan; Roperto, Renato; Mustafa, Hathem; Teich, Sorin; Akkus, Ozan

2017-02-01

Measurement of tooth enamel mineralization using a clinically viable method is essential since variation of mineralization may be used to monitor caries risk or in assessing the effectiveness of remineralization therapy. Fiber optic Raman systems are becoming more affordable and popular in context of biomedical applications. However, the applicability of fiber optic Raman systems for measurement of mineral content within enamel tissue has not been elucidated significantly in the prior literature. Human teeth with varying degrees of enamel mineralization were selected. In addition alligator, boar and buffalo teeth which have increasing amount of mineral content, respectively, were also included as another set of samples. Reference Raman measurements of mineralization were performed using a high-fidelity confocal Raman microscope. Analysis of human teeth by research grade Raman system indicated a 2-fold difference in the Raman intensities of v1 symmetric-stretch bands of mineral-related phosphate bonds and 7-fold increase in mineral related Raman intensities of animal teeth. However, fiber optic system failed to resolve the differences in the mineralization of human teeth. These results indicate that the sampling volume of fiber optic systems extends to the underlying dentin and that confocal aperture modification is essential to limit the sampling volume to within the enamel. Further research efforts will focus on putting together portable Raman systems integrated with confocal fiber probe. Key words: Enamel, mineral content, raman spectroscopy.

Strain mapping in single-layer two-dimensional crystals via Raman activity

NASA Astrophysics Data System (ADS)

Yagmurcukardes, M.; Bacaksiz, C.; Unsal, E.; Akbali, B.; Senger, R. T.; Sahin, H.

2018-03-01

By performing density functional theory-based ab initio calculations, Raman-active phonon modes of single-layer two-dimensional (2D) materials and the effect of in-plane biaxial strain on the peak frequencies and corresponding activities of the Raman-active modes are calculated. Our findings confirm the Raman spectrum of the unstrained 2D crystals and provide expected variations in the Raman-active modes of the crystals under in-plane biaxial strain. The results are summarized as follows: (i) frequencies of the phonon modes soften (harden) under applied tensile (compressive) strains; (ii) the response of the Raman activities to applied strain for the in-plane and out-of-plane vibrational modes have opposite trends, thus, the built-in strains in the materials can be monitored by tracking the relative activities of those modes; (iii) in particular, the A peak in single-layer Si and Ge disappears under a critical tensile strain; (iv) especially in mono- and diatomic single layers, the shift of the peak frequencies is a stronger indication of the strain rather than the change in Raman activities; (v) Raman-active modes of single-layer ReX2 (X =S , Se) are almost irresponsive to the applied strain. Strain-induced modifications in the Raman spectrum of 2D materials in terms of the peak positions and the relative Raman activities of the modes could be a convenient tool for characterization.

The Influence of Trace Gases Absorption on Differential Ring Cross Sections

NASA Astrophysics Data System (ADS)

Han, Dong; Zhao, Keyi

2017-04-01

The Ring effect refers to the filling in of Fraunhofer lines, which is known as solar absorption lines, caused almost entirely by rotational Raman scattering. The rotational Raman scattering by N2 and O2 in the atmosphere is the main factor that leads to Ring effect. The Ring effect is one significant limitation to the accuracy of the retrieval of trace gas constituents in atmosphere, while using satellite data with Differential Optical Absorption Spectroscopy technique. In this study, firstly the solar spectrum is convolved with rotational Raman cross sections of atmosphere, which is calculated with rotational Raman cross sections of N2 and O2, divided by the original solar spectrum, with a cubic polynomial subtracted off, to create differential Ring spectrum Ring1. Secondly, the Ring effect for pure Raman scattering of the Fraunhofer spectrum plus the contribution from interference by terrestrial absorption which always comes from a kind of trace gas (e.g., O3) are derived. To allow for more generality, the optically thin term as well as the next term in the expansion for the Beer-Lambert law are calculated.Ring1, Ring2, and Ring3are the Fraunhofer only, 1st terrestrial correction, and 2nd terrestrial correction for DOAS fitting.

Quantitative Analysis of Temperature Dependence of Raman shift of monolayer WS2

NASA Astrophysics Data System (ADS)

Huang, Xiaoting; Gao, Yang; Yang, Tianqi; Ren, Wencai; Cheng, Hui-Ming; Lai, Tianshu

2016-08-01

We report the temperature-dependent evolution of Raman spectra of monolayer WS2 directly CVD-grown on a gold foil and then transferred onto quartz substrates over a wide temperature range from 84 to 543 K. The nonlinear temperature dependence of Raman shifts for both and A1g modes has been observed. The first-order temperature coefficients of Raman shifts are obtained to be -0.0093 (cm-1/K) and -0.0122 (cm-1/K) for and A1g peaks, respectively. A physical model, including thermal expansion and three- and four-phonon anharmonic effects, is used quantitatively to analyze the observed nonlinear temperature dependence. Thermal expansion coefficient (TEC) of monolayer WS2 is extracted from the experimental data for the first time. It is found that thermal expansion coefficient of out-plane mode is larger than one of in-plane mode, and TECs of and A1g modes are temperature-dependent weakly and strongly, respectively. It is also found that the nonlinear temperature dependence of Raman shift of mode mainly originates from the anharmonic effect of three-phonon process, whereas one of A1g mode is mainly contributed by thermal expansion effect in high temperature region, revealing that thermal expansion effect cannot be ignored.

Anisotropic stress in narrow sGe fin field-effect transistor channels measured using nano-focused Raman spectroscopy

NASA Astrophysics Data System (ADS)

Nuytten, T.; Bogdanowicz, J.; Witters, L.; Eneman, G.; Hantschel, T.; Schulze, A.; Favia, P.; Bender, H.; De Wolf, I.; Vandervorst, W.

2018-05-01

The continued importance of strain engineering in semiconductor technology demands fast and reliable stress metrology that is non-destructive and process line-compatible. Raman spectroscopy meets these requirements but the diffraction limit prevents its application in current and future technology nodes. We show that nano-focused Raman scattering overcomes these limitations and can be combined with oil-immersion to obtain quantitative anisotropic stress measurements. We demonstrate accurate stress characterization in strained Ge fin field-effect transistor channels without sample preparation or advanced microscopy. The detailed analysis of the enhanced Raman response from a periodic array of 20 nm-wide Ge fins provides direct access to the stress levels inside the nanoscale channel, and the results are validated using nano-beam diffraction measurements.

Efficient 1.5-μm Raman generation in ethane-filled hollow-core fiber

NASA Astrophysics Data System (ADS)

Chen, Yubin; Gu, Bo; Wang, Zefeng; Lu, Qisheng

2016-11-01

We demonstrated for the first time a novel and effective method for obtaining both high peak-power and narrow linewidth 1.5 μm fiber sources through gas Raman effect in hollow core fibers. An Ethane-filled ice-cream antiresonance hollow-core fiber is pumped with a high peak-power pulse 1064 nm microchip laser, generating 1552.7 nm Stokes wave by pure vibrational stimulated Raman scattering of ethane molecules. A maximum peak-power of about 400 kW is achieved with 6 meter fiber length at 2 bar pressure, and the linewidth is about 6.3 GHz. The maximum Raman conversion efficiency of 1064 nm to 1552.7 nm is about 38%, and the corresponding laser slope efficiency is about 61.5%.

The effects of Raman scattering accompanied by the soliton excitation occurring in molecular crystals

NASA Astrophysics Data System (ADS)

Pang, X. F.

2001-06-01

A theoretical research is made for the effects of Raman scattering caused by the soliton excitation occurring in the organic molecular crystals, e.g., acetanilide, on the basis of vibration model of amide-I. The energy gap between the soliton state and the vibron state have been found by partial diagonalized method in second quantized representation, which is 18.1-33 cm -1. This result is approximately consistent with the red shift value obtained from the experiments, 16 cm -1. The differential cross-section of the Raman scattering, arising from the soliton excitation, has also been obtained. Finally, we derive some properties of the Raman scattering in such a case. This result establishes spectral signatures of the soliton in the molecular crystals, which may be observed in the experiment.

Differentiation of bacterial versus viral otitis media using a combined Raman scattering spectroscopy and low coherence interferometry probe (Conference Presentation)

NASA Astrophysics Data System (ADS)

Zhao, Youbo; Shelton, Ryan L.; Tu, Haohua; Nolan, Ryan M.; Monroy, Guillermo L.; Chaney, Eric J.; Boppart, Stephen A.

2016-02-01

Otitis media (OM) is a highly prevalent disease that can be caused by either a bacterial or viral infection. Because antibiotics are only effective against bacterial infections, blind use of antibiotics without definitive knowledge of the infectious agent, though commonly practiced, can lead to the problems of potential harmful side effects, wasteful misuse of medical resources, and the development of antimicrobial resistance. In this work, we investigate the feasibility of using a combined Raman scattering spectroscopy and low coherence interferometry (LCI) device to differentiate OM infections caused by viruses and bacteria and improve our diagnostic ability of OM. Raman spectroscopy, an established tool for molecular analysis of biological tissue, has been shown capable of identifying different bacterial species, although mostly based on fixed or dried sample cultures. LCI has been demonstrated recently as a promising tool for determining tympanic membrane (TM) thickness and the presence and thickness of middle-ear biofilm located behind the TM. We have developed a fiber-based ear insert that incorporates spatially-aligned Raman and LCI probes for point-of-care diagnosis of OM. As shown in human studies, the Raman probe provides molecular signatures of bacterial- and viral-infected OM and normal middle-ear cavities, and LCI helps to identify depth-resolved structural information as well as guide and monitor positioning of the Raman spectroscopy beam for relatively longer signal acquisition time. Differentiation of OM infections is determined by correlating in vivo Raman data collected from human subjects with the Raman features of different bacterial and viral species obtained from cultured samples.

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.

Defining the temperature range for cooking with extra virgin olive oil using Raman spectroscopy

NASA Astrophysics Data System (ADS)

Ahmad, Naveed; Saleem, M.; Ali, H.; Bilal, M.; Khan, Saranjam; Ullah, Rahat; Ahmed, M.; Mahmood, S.

2017-09-01

Using the potential of Raman spectroscopy, new findings regarding the effects of heating on extra virgin olive oil (EVOO) during frying/cooking are presented. A temperature range from 140 to 150 °C has been defined within which EVOO can be used for cooking/frying without much loss of its natural molecular composition. Raman spectra from the EVOO samples were recorded using an excitation laser at 785 nm in the range from 540 to 1800 cm-1. Due to heating, prominent variations in intensity are observed at Raman bands from 540 to 770 cm-1, 790 to 1170 cm-1 and 1267 and 1302 cm-1. The Raman bands at 1267 and 1302 cm-1 represent cis unsaturated fats and their ratio is used to investigate the effects of temperature on the molecular composition of EVOO. In addition, principal component analysis has been applied on all the groups of data to classify the heated EVOO samples at different temperatures and for different times. In addition, it has been found that use of EVOO for frying twice does not have any prominent effect on its molecular composition.

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.

A transform from absorption to Raman excitation profile. A time-dependent approach

NASA Astrophysics Data System (ADS)

Lee, Soo-Y.; Yeo, Robert C. K.

1994-04-01

An alternative time-frame approach, which is canonically conjugate to the energy-frame approach, for implementing the transform relations for calculating Raman excitation profiles directly from the optical absorption spectrum is presented. Practical and efficient fast Fourier transformation in the time frame replaces the widely used Chan and Page algorithm for evaluating the Hilbert transform in the energy frame. The time-frame approach is applied to: (a) a two-mode model which illustrates the missing mode effect in both absorption and Raman excitation profiles, (b) carotene, in which both the absorption spectrum and the Raman excitation profile show vibrational structure and (c) hexamethylbenzene: TCNE electron donor—acceptor complex where the same spectra are structureless and the Raman excitation profile for the 168 cm -1 mode poses a problem for the energy-frame approach. A similar time-frame approach can be used for the inverse transform from the Raman excitation profile to the optical absorption spectrum.

Sensitive Phonon-Based Probe for Structure Identification of 1T' MoTe 2

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

Zhou, Lin; Huang, Shengxi; Tatsumi, Yuki

In this work, by combining transmission electron microscopy and polarized Raman spectroscopy for the 1T' MoTe 2 flakes with different thicknesses, we found that the polarization dependence of Raman intensity is given as a function of excitation laser wavelength, phonon symmetry, and phonon frequency, but has weak dependence on the flake thickness from few-layer to multilayer. Additionally, the frequency of Raman peaks and the relative Raman intensity are sensitive to flake thickness, which manifests Raman spectroscopy as an effective probe for thickness of 1T' MoTe 2. This work demonstrates that polarized Raman spectroscopy is a powerful and nondestructive method tomore » quickly identify the crystal structure and thickness of 1T' MoTe 2 simultaneously, which opens up opportunities for the in situ probe of anisotropic properties and broad applications of this novel material.« less

Sensitive Phonon-Based Probe for Structure Identification of 1T' MoTe 2

DOE PAGES

Zhou, Lin; Huang, Shengxi; Tatsumi, Yuki; ...

2017-05-25

In this work, by combining transmission electron microscopy and polarized Raman spectroscopy for the 1T' MoTe 2 flakes with different thicknesses, we found that the polarization dependence of Raman intensity is given as a function of excitation laser wavelength, phonon symmetry, and phonon frequency, but has weak dependence on the flake thickness from few-layer to multilayer. Additionally, the frequency of Raman peaks and the relative Raman intensity are sensitive to flake thickness, which manifests Raman spectroscopy as an effective probe for thickness of 1T' MoTe 2. This work demonstrates that polarized Raman spectroscopy is a powerful and nondestructive method tomore » quickly identify the crystal structure and thickness of 1T' MoTe 2 simultaneously, which opens up opportunities for the in situ probe of anisotropic properties and broad applications of this novel material.« less

Early identification of cervical neoplasia with Raman spectroscopy and advanced methods for biomedical applications

NASA Astrophysics Data System (ADS)

Jess, Phillip R. T.; Smith, Daniel D. W.; Mazilu, Michael; Cormack, Iain; Riches, Andrew C.; Herrington, C. Simon; Dholakia, Kishan

2008-02-01

Early detection of malignant tumours, or their precursor lesions, can dramatically improve patient outcome. High risk human Papillomavirus (HPV), particularly HPV16, infection can lead to the initiation and development of uterine cervical neoplasia. Bearing this in mind the identification of the effects of HPV infection may have clinical value. In this manuscript we investigate the application of Raman microspectroscopy to detect the presence of HPV in cultured cells when compared with normal cells. We also investigate the effect of sample fixation, which is a common clinical practice, on the ability of Raman spectroscopy to detect the presence of HPV. Raman spectra were acquired from Primary Human Keratinocytes (PHK), PHK expressing the E7 gene of HPV 16 (PHK E7) and CaSki cells, an HPV16 containing cervical carcinoma derived cell line. The average Raman spectra display variations, mostly in peaks relating to DNA and proteins, consistent with HPV gene expression and the onset of neoplasia in both live and fixed samples. Principle component analysis was used to objectively discriminate between the cells types giving sensitivities up to 100% for the comparison between PHK and CaSki. These results show that Raman spectroscopy can discriminate between cell lines representing different stages of cervical neoplasia. Furthermore Raman spectroscopy was able to identify cells expressing the HPV 16 E7 gene suggesting the approach may be of value in clinical practice. Finally this technique was also able to detect the effects of the virus in fixed samples demonstrating the compatibility of this technique with current cervical screening methods. However if Raman spectroscopy is to make a significant impact in clinical practice the long acquisition times must be addressed. In this report we examine the potential for beam shaping and advanced to improve the signal to noise ration hence subsequently facilitating a reduction in acquisition time.

An Empirical Study on Raman Peak Fitting and Its Application to Raman Quantitative Research.

PubMed

Yuan, Xueyin; Mayanovic, Robert A

2017-10-01

Fitting experimentally measured Raman bands with theoretical model profiles is the basic operation for numerical determination of Raman peak parameters. In order to investigate the effects of peak modeling using various algorithms on peak fitting results, the representative Raman bands of mineral crystals, glass, fluids as well as the emission lines from a fluorescent lamp, some of which were measured under ambient light whereas others under elevated pressure and temperature conditions, were fitted using Gaussian, Lorentzian, Gaussian-Lorentzian, Voigtian, Pearson type IV, and beta profiles. From the fitting results of the Raman bands investigated in this study, the fitted peak position, intensity, area and full width at half-maximum (FWHM) values of the measured Raman bands can vary significantly depending upon which peak profile function is used in the fitting, and the most appropriate fitting profile should be selected depending upon the nature of the Raman bands. Specifically, the symmetric Raman bands of mineral crystals and non-aqueous fluids are best fit using Gaussian-Lorentzian or Voigtian profiles, whereas the asymmetric Raman bands are best fit using Pearson type IV profiles. The asymmetric O-H stretching vibrations of H 2 O and the Raman bands of soda-lime glass are best fit using several Gaussian profiles, whereas the emission lines from a florescent light are best fit using beta profiles. Multiple peaks that are not clearly separated can be fit simultaneously, provided the residuals in the fitting of one peak will not affect the fitting of the remaining peaks to a significant degree. Once the resolution of the Raman spectrometer has been properly accounted for, our findings show that the precision in peak position and intensity can be improved significantly by fitting the measured Raman peaks with appropriate profiles. Nevertheless, significant errors in peak position and intensity were still observed in the results from fitting of weak and wide Raman bands having unnormalized intensity/FWHM ratios lower than 200 counts/cm -1 .

[Detection of single-walled carbon nanotube bundles by tip-enhanced Raman spectroscopy].

PubMed

Wu, Xiao-Bin; Wang, Jia; Wang, Rui; Xu, Ji-Ying; Tian, Qian; Yu, Jian-Yuan

2009-10-01

Raman spectroscopy is a powerful technique in the characterization of carbon nanotubes (CNTs). However, this spectral method is subject to two obstacles. One is spatial resolution, namely the diffraction limits of light, and the other is its inherent small Raman cross section and weak signal. To resolve these problems, a new approach has been developed, denoted tip-enhanced Raman spectroscopy (TERS). TERS has been demonstrated to be a powerful spectroscopic and microscopic technique to characterize nanomaterial or nanostructures. Excited by a focused laser beam, an enhanced electric field is generated in the vicinity of a metallic tip because of the surface plasmon polariton (SPP) and lightening rod effect. Consequently, Raman signal from the sample area illuminated by the enhanced field nearby the tip is enhanced. At the same time, the topography is obtained in the nanometer scale. The exact corresponding relationship between the localized Raman and the topography makes the Raman identification at the nanometer scale to be feasible. In the present paper, based on an inverted microscope and a metallic AFM tip, a tip-enhanced Raman system was set up. The radius of the Au-coated metallic tip is about 30 nm. The 532 nm laser passes through a high numerical objective (NA0.95) from the bottom to illuminate the tip to excite the enhanced electric field. Corresponding with the AFM image, the tip-enhanced near-field Raman of a 100 nm diameter single-walled carbon nanotube (SWNT) bundles was obtained. The SWNTs were prepared by arc method. Furthermore, the near-field Raman of about 3 SWNTs of the bundles was received with the spatial resolution beyond the diffraction limit. Compared with the far-field Raman, the enhancement factor of the tip-enhanced Raman is more than 230. With the super-diffraction spatial resolution and the tip-enhanced Raman ability, tip-enhanced Raman spectroscopy will play an important role in the nano-material and nano-structure characterization.

Raman Imaging of Plant Cell Walls in Sections of Cucumis sativus

PubMed Central

Zeise, Ingrid; Heiner, Zsuzsanna; Holz, Sabine; Joester, Maike; Büttner, Carmen

2018-01-01

Raman microspectra combine information on chemical composition of plant tissues with spatial information. The contributions from the building blocks of the cell walls in the Raman spectra of plant tissues can vary in the microscopic sub-structures of the tissue. Here, we discuss the analysis of 55 Raman maps of root, stem, and leaf tissues of Cucumis sativus, using different spectral contributions from cellulose and lignin in both univariate and multivariate imaging methods. Imaging based on hierarchical cluster analysis (HCA) and principal component analysis (PCA) indicates different substructures in the xylem cell walls of the different tissues. Using specific signals from the cell wall spectra, analysis of the whole set of different tissue sections based on the Raman images reveals differences in xylem tissue morphology. Due to the specifics of excitation of the Raman spectra in the visible wavelength range (532 nm), which is, e.g., in resonance with carotenoid species, effects of photobleaching and the possibility of exploiting depletion difference spectra for molecular characterization in Raman imaging of plants are discussed. The reported results provide both, specific information on the molecular composition of cucumber tissue Raman spectra, and general directions for future imaging studies in plant tissues. PMID:29370089

Raman Imaging of Plant Cell Walls in Sections of Cucumis sativus.

PubMed

Zeise, Ingrid; Heiner, Zsuzsanna; Holz, Sabine; Joester, Maike; Büttner, Carmen; Kneipp, Janina

2018-01-25

Raman microspectra combine information on chemical composition of plant tissues with spatial information. The contributions from the building blocks of the cell walls in the Raman spectra of plant tissues can vary in the microscopic sub-structures of the tissue. Here, we discuss the analysis of 55 Raman maps of root, stem, and leaf tissues of Cucumis sativus , using different spectral contributions from cellulose and lignin in both univariate and multivariate imaging methods. Imaging based on hierarchical cluster analysis (HCA) and principal component analysis (PCA) indicates different substructures in the xylem cell walls of the different tissues. Using specific signals from the cell wall spectra, analysis of the whole set of different tissue sections based on the Raman images reveals differences in xylem tissue morphology. Due to the specifics of excitation of the Raman spectra in the visible wavelength range (532 nm), which is, e.g., in resonance with carotenoid species, effects of photobleaching and the possibility of exploiting depletion difference spectra for molecular characterization in Raman imaging of plants are discussed. The reported results provide both, specific information on the molecular composition of cucumber tissue Raman spectra, and general directions for future imaging studies in plant tissues.

Portable Raman instrument for rapid biological agent detection and identification

NASA Astrophysics Data System (ADS)

Lesaicherre, Marie L.; Paxon, Tracy L.; Mondello, Frank J.; Burrell, Michael C.; Linsebigler, Amy

2009-05-01

The rapid and sensitive identification of biological species is a critical need for the 1st responder and military communities. Raman spectroscopy is a powerful tool for substance identification that has gained popularity with the respective communities due to the increasing availability of portable Raman spectrometers. Attempts to use Raman spectroscopy for the direct identification of biological pathogens has been hindered by the complexity of the generated Raman spectrum. We report here the use of a sandwich immunoassay containing antibody modified magnetic beads to capture and concentrate target analytes in solution and Surface Enhanced Raman Spectroscopy (SERS) tags conjugated with these same antibodies for specific detection. Using this approach, the biological complexity of a microorganism can be translated into chemical simplicity and Raman can be used for the identification of biological pathogens. The developed assay has a low limit of detection due to the SERS effect, robust to commonly found white powders interferants, and stable at room temperature over extended period of time. This assay is being implemented into a user-friendly interface to be used in conjunction with the GE Homeland Protection StreetLab MobileTM Raman instrument for rapid, field deployable chemical and biological identification.

Unveiling the Aggregation of Lycopene in Vitro and in Vivo: UV-Vis, Resonance Raman, and Raman Imaging Studies.

PubMed

Ishigaki, Mika; Meksiarun, Phiranuphon; Kitahama, Yasutaka; Zhang, Leilei; Hashimoto, Hideki; Genkawa, Takuma; Ozaki, Yukihiro

2017-08-31

The present study investigates the structure of lycopene aggregates both in vitro and in vivo using ultraviolet-visible (UV-vis) and Raman spectroscopies. The electronic absorption bands of the J- and H-aggregates in vitro shift to lower and higher energies, respectively, compared to that of the lycopene monomer. Along with these results, the frequencies of the ν 1 Raman bands were shifted to lower and higher frequencies, respectively. By plotting the frequencies of the ν 1 Raman band against the S 0 → S 2 transition energy, a linear relationship between the data set with different aggregation conformations can be obtained. Therefore, the band positions depending on the different conformations can be explained based on the idea that the effective conjugated C═C chain lengths within lycopene molecules are different due to the environmental effect (site-shift effect) caused by the aggregation conformation. Applying this knowledge to the in vivo measurement of a tomato fruit sample, the relationship between the aggregation conformation of lycopene and the spectral patterns observed in the UV-vis as well as Raman spectra in different parts of tomato fruits was discussed in detail. The results showed that the concentration of lycopene (particularly that of the J-aggregate) specifically increased, whereas that of chlorophyll decreased, with ripening. Furthermore, Raman imaging indicated that lycopene with different aggregate conformations was distributed inhomogeneously, even within one sample. The layer formation in tomato tissues with high concentrations of J- and H-aggregates was successfully visualized. In this manner, the presence of lycopene distributions with different aggregate conformations was unveiled in vivo.

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.

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

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.

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.

Rapid acquisition of mean Raman spectra of eukaryotic cells for a robust single cell classification.

PubMed

Schie, Iwan W; Kiselev, Roman; Krafft, Christoph; Popp, Jürgen

2016-11-14

Raman spectroscopy has previously been used to identify eukaryotic and prokaryotic cells. While prokaryotic cells are small in size and can be assessed by a single Raman spectrum, the larger size of eukaryotic cells and their complex organization requires the acquisition of multiple Raman spectra to properly characterize them. A Raman spectrum from a diffraction-limited spot at an arbitrary location within a cell results in spectral variations that affect classification approaches. To probe whole cells with Raman imaging at high spatial resolution is time consuming, because a large number of Raman spectra need to be collected, resulting in low cell throughput and impairing statistical analysis due to low cell numbers. Here we propose a method to overcome the effects of cellular heterogeneity by acquiring integrated Raman spectra covering a large portion of a cell. The acquired spectrum represents the mean macromolecular composition of a cell with an exposure time that is comparable to acquisition of a single Raman spectrum. Data sets were collected from T lymphocyte Jurkat cells, and pancreatic cell lines Capan1 and MiaPaca2. Cell classification by support vector machines was compared for single spectra, spectra of images and integrated Raman spectra of cells. The integrated approach provides better and more stable prediction for individual cells, and in the current implementation, the mean macromolecular information of a cell can be acquired faster than with the acquisition of individual spectra from a comparable region. It is expected that this approach will have a major impact on the implementation of Raman based cell classification.

Effect of hormonal variation on in vivo high wavenumber Raman spectra improves cervical precancer detection

NASA Astrophysics Data System (ADS)

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

2012-03-01

Raman spectroscopy is a unique analytical probe for molecular vibration and is capable of providing specific spectroscopic fingerprints of molecular compositions and structures of biological tissues. The aim of this study is to improve the classification accuracy of cervical precancer by characterizing the variations in the normal high wavenumber (HW - 2800-3700cm-1) Raman spectra arising from the menopausal status of the cervix. A rapidacquisition near-infrared (NIR) Raman spectroscopic system was used for in vivo tissue Raman measurements at 785 nm excitation. Individual HW Raman spectrum was measured with a 5s exposure time from both normal and precancer tissue sites of 15 patients recruited. The acquired Raman spectra were stratified based on the menopausal status of the cervix before the data analysis. Significant differences were noticed in Raman intensities of prominent band at 2924 cm-1 (CH3 stretching of proteins) and the broad water Raman band (in the 3100-3700 cm-1 range) with a peak at 3390 cm-1 in normal and dysplasia cervical tissue sites. Multivariate diagnostic decision algorithm based on principal component analysis (PCA) and linear discriminant analysis (LDA) was utilized to successfully differentiate the normal and precancer cervical tissue sites. By considering the variations in the Raman spectra of normal cervix due to the hormonal or menopausal status of women, the diagnostic accuracy was improved from 71 to 91%. By incorporating these variations prior to tissue classification, we can significantly improve the accuracy of cervical precancer detection using HW Raman spectroscopy.

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

Effect of particle size and laser power on the Raman spectra of CuAlO2 delafossite nanoparticles

NASA Astrophysics Data System (ADS)

Yassin, O. A.; Alamri, S. N.; Joraid, A. A.

2013-06-01

A transparent conductive oxide CuAlO2 delafossite is studied using x-ray powder diffraction (XRD) and micro-Raman spectroscopy measurements as a function of the particle size and laser power from 2 to 20 mW. The XRD results indicate that the lattice parameters and the cell volume expand as the particle size reduces. Large red shifts (˜60 cm-1) and line broadening (˜50 cm-1) are observed as the particle size becomes of the order of 13 nm. These huge values can only be justified if collective effects on the Raman spectra created by the lattice expansion, confinement of phonons and enhanced phonon-phonon interactions are included in the interpretations of the Raman spectra of the CuAlO2 nanoparticles.

Electron Raman scattering in a double quantum well tuned by an external nonresonant intense laser field

NASA Astrophysics Data System (ADS)

Tiutiunnyk, A.; Mora-Ramos, M. E.; Morales, A. L.; Duque, C. M.; Restrepo, R. L.; Ungan, F.; Martínez-Orozco, J. C.; Kasapoglu, E.; Duque, C. A.

2017-02-01

In this work we shall present a study of inelastic light scattering involving inter-subband electron transitions in coupled GaAs-(Ga,Al)As quantum wells. Calculations include the electron related Raman differential cross section and Raman gain. The effects of an external nonresonant intense laser field are used in order to tune these output properties. The confined electron states will be described by means of a diagonalization procedure within the effective mass and parabolic band approximations. It is shown that the application of the intense laser field can produce values of the intersubband electron Raman gain above 400 cm-1. The system proposed here is an alternative choice for the development of AlxGa1-xAs semiconductor laser diodes that can be tuned via an external nonresonant intense laser field.

Strain, doping, and disorder effects in GaAs/Ge/Si heterostructures: A Raman spectroscopy investigation

NASA Astrophysics Data System (ADS)

Mlayah, A.; Carles, R.; Leycuras, A.

1992-01-01

The present work is devoted to a Raman study of GaAs/Ge/Si heterostructures grown by the vapor-phase epitaxy technique. We first show that the GaAs epilayers are submitted to a biaxial tensile strain. The strain relaxation generates misfit dislocations and thus disorder effects which we analyze in terms of translational invariance loss and Raman selection rules violation. The first-order Raman spectra of annealed samples exhibit an unexpected broadband we identify as due to scattering by a coupled LO phonon-damped plasmon mode. This is corroborated by an accurate line-shape analysis which accounts for the recorded spectra and makes evident the presence of free carriers within the GaAs layers. Their density is estimated from the deduced plasmon frequency and also using a method we have presented in a previous work.

Limitations of using Raman microscopy for the analysis of high-content-carbon-filled ethylene propylene diene monomer rubber.

PubMed

Ghanbari-Siahkali, Afshin; Almdal, Kristoffer; Kingshott, Peter

2003-12-01

The effects of laser irradiation on changes to the surface chemistry and structure of a commercially available ethylene propylene diene monomer (EPDM) rubber sample after Raman microscopy analysis was investigated. The Raman measurements were carried out with different levels of laser power on the sample, ranging from 4.55 mW to 0.09 mW. The surface of the EPDM was analyzed before and after laser exposure using X-ray photoelectron spectroscopy (XPS) and attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy. The techniques have surface probe depths of approximately < or = 10 nm and 1 microm, respectively. Both sets of analysis show that ingredients of the blended EPDM rubber "bloom" to the surface as a result of local heating that takes place due to the absorption of laser by carbon black during the Raman analysis. Scanning electron microscopy (SEM) analysis was also performed on the Raman analyzed areas to visually illustrate the effects created due to laser light exposure (i.e., burning marks). The change in surface chemistry also occurs in regions a few millimeters from the exposed sites, indicating that the effect is quite long range. However, this phenomenon has no major influence, as far as XPS or ATR-FTIR results disclose, on the backbone structure of the rubber sample. The results indicate that precautions should be taken when analyzing complex blended polymer samples using Raman spectroscopy.

Raman spectroscopic analysis for gastric and colorectal cancer in surgical treatment toward molecular-guided surgery

NASA Astrophysics Data System (ADS)

Koga, Shigehiro; Watanabe, Yuji; Oshima, Yusuke

2018-02-01

Raman spectroscopy provides a wealth of diagnostic information to the surgeon with in situ cancer detection and label-free histopathology in intraoperative conditions. Raman spectroscopy is a promising 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, and also confirmed that Raman spectra obtained from cancer cells and their environment including other cells and extracellular matrix in xenograft models and spontaneous metastasis models were distinguishable using Raman spectroscopy combined with fluorescence microscopy and photoluminescence imaging. 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, but to identify and detect cancer diagnostic biomarkers in vivo on Raman spectroscopy is still challenging. Here we investigate morphological and molecular dynamics in advanced cancer specimens obtained from patients. We are also constructing a customdesigned 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.

NONLINEAR AND FIBER OPTICS: Mutual suppression of the electron stimulated Raman scattering and four-wave parametric mixing

NASA Astrophysics Data System (ADS)

Malakyan, Yu P.

1990-04-01

A new effect is considered: self-induced suppression of electron stimulated Raman scattering involving generation of two new fields from the Stokes radiation as a result of four-wave mixing, interfering destructively with electron stimulated Raman scattering and suppressing it, which in turn suppresses the mixing process. The effect occurs in the steady-state case and not under transient conditions. The results account in a simple manner for the generation of the Stokes radiation in barium vapor as a result of different transitions, depending on the duration of the pump pulse.

Experimental optimization during SERS application

NASA Astrophysics Data System (ADS)

Laha, Ranjit; Das, Gour Mohan; Ranjan, Pranay; Dantham, Venkata Ramanaiah

2018-05-01

The well known surface enhanced Raman scattering (SERS) needs a lot of experimental optimization for its proper implementation. In this report, we demonstrate the efficient SERS using gold nanoparticles (AuNPs) on quartz plate. The AuNPs were prepared by depositing direct current sputtered Au thin film followed by suitable annealing. The parameters varied for getting best SERS effect were 1) Numerical Aperture of Raman objective lens and 2) Sputtering duration of Au film. It was found that AuNPs formed from the Au layer deposited for 40s and Raman objective lens of magnification 50X are the best combination for obtaining efficient SERS effect.

The effect of external magnetic field on the Raman peaks in manganites

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

Sahu, A. K., E-mail: ajitsahu@seemantaengg.ac.in; Rout, G. C.

2014-04-24

We report here a microscopic theoretical model study exhibiting the effect of external magnetic field on the Raman excitation peaks in the CMR manganite system. The Hamiltonian consists of Jahn-Teller (J-T) distortion in e{sub g} band, the double exchange interaction and the Heisenberg spin-spin interaction. Further the phonons are coupled to e{sub g} band electrons, J-T distorted e{sub g} band and the double exchange interaction. The Raman spectral intensity is calculated from the imaginary part of the phonon Green function. The spectra exhibits three peaks besides a very weak high energy peak. The magnetic field effect on these peaks aremore » reported.« less

Evaluation of quantum confinement effect in nanocrystal Si dot layer by Raman spectroscopy.

PubMed

Mizukami, Y; Kosemura, D; Numasawa, Y; Ohshita, Y; Ogura, A

2012-11-01

Quantum confinement effect in the nanocrystal-Si (nc-Si) was evaluated by Raman spectroscopy. The nc-Si dot layers were fabricated by the H2 plasma treatment for the nucleation site formation followed by the SiH4 irradiation for the nc-Si growth. Post-oxidation annealing was also performed to improve the crystalline quality. After post-oxidation annealing for 5 or 10 min, the asymmetric broadening on the lower frequency sides in Raman spectra were obtained, which can be attributed to the phonon confinement effect in nc-Si. Furthermore we confirmed that hydrostatic stress of approximately 500 MPa was induced in nc-Si after post-oxidation annealing.

Biological pH sensing based on the environmentally friendly Raman technique through a polyaniline probe.

PubMed

Li, Songyang; Liu, Zhiming; Su, Chengkang; Chen, Haolin; Fei, Xixi; Guo, Zhouyi

2017-02-01

The biological pH plays an important role in various cellular processes. In this work, a novel strategy is reported for biological pH sensing by using Raman spectroscopy and polyaniline nanoparticles (PANI NPs) as the pH-sensitive Raman probe. It is found that the Raman spectrum of PANI NPs is strongly dependent on the pH value. The intensities of Raman spectral bands at 1225 and 1454 cm -1 increase obviously with pH value varying from 5.5 to 8.0, which covers the range of regular biological pH variation. The pH-dependent Raman performance of PANI NPs, as well as their robust Raman signals and sensitivities to pH, was well retained after the nanoparticles incorporated into living 4T1 breast adenocarcinoma cells. The data indicate that such PANI NPs can be used as an effective biological pH sensor. Most interestingly, the PANI spherical nanostructures can be acquired by a low-cost, metal-free, and one-pot oxidative polymerization, which gives them excellent biocompatibility for further biological applications.

Raman Lidar Measurements of Pinatubo Aerosols over Southeastern Kansas During November-december 1991

NASA Technical Reports Server (NTRS)

Ferrare, R. A.; Melfi, S. H.; Whiteman, D. N.; Evans, K. D.

1992-01-01

The eruptions of the Philippine volcano Pinatubo during June 1991 produced large amounts of stratospheric aerosols that could significantly affect earth's climate as well as trigger stratospheric ozone depletion through heterogeneous chemical reactions. Information regarding the physical and optical properties of these aerosols is required to quantify those effects. By measuring both the elastically backscattered signal and the inelastic signal produced by Raman scattering from nitrogen molecules, Raman lidar can provide some of this information. In this presentation we discuss Raman lidar measurements of the scattering ratio, backscattering, extinction, extinction/backscattering ratio, and optical thickness of the Pinatubo aerosols over southeastern Kansas made on 10 nights during November and December, 1991. The Raman lidar developed at GSFC is a trailer-based system which uses an XeF excimer laser to transmit light at 351 nm. The light backscattered by molecules and aerosols at this wavelength is detected as well as Raman scattered light from water vapor, nitrogen, and oxygen molecules. Since background skylights interfere with the detection of the Raman signals the data discussed in this paper were acquired only at night.

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

Daniel S. Clark; Nathaniel J. Fisch

A critical issue in the generation of ultra-intense, ultra-short laser pulses by backward Raman scattering in plasma is the stability of the pumping pulse to premature backscatter from thermal fluctuations in the preformed plasma. Malkin et al. [V.M. Malkin, et al., Phys. Rev. Lett. 84 (6):1208-1211, 2000] demonstrated that density gradients may be used to detune the Raman resonance in such a way that backscatter of the pump from thermal noise can be stabilized while useful Raman amplification persists. Here plasma conditions for which the pump is stable to thermal Raman backscatter in a homogeneous plasma and the density gradientsmore » necessary to stabilize the pump for other plasma conditions are quantified. Other ancillary constraints on a Raman amplifier are also considered to determine a specific region in the Te-he plane where Raman amplification is feasible. By determining an operability region, the degree of uncertainty in density or temperature tolerable for an experimental Raman amplifier is thus also identified. The fluid code F3D, which includes the effects of thermal fluctuations, is used to verify these analytic estimates.« less

Raman spectral properties of squamous cell carcinoma of oral tissues and cells

NASA Astrophysics Data System (ADS)

Su, L.; Sun, Y. F.; Chen, Y.; Chen, P.; Shen, A. G.; Wang, X. H.; Jia, J.; Zhao, Y. F.; Zhou, X. D.; Hu, J. M.

2012-01-01

Early diagnosis is the key of the improved survival rates of oral cancer. Raman spectroscopy is sensitive to the early changes of molecular composition and structure that occur in benign lesion during carcinogenesis. In this study, in situ Raman analysis provided distinct spectra that can be used to discriminate between normal and malignant tissues, as well as normal and cancer cells. The biochemical variations between different groups were analyzed by the characteristic bands by comparing the normalized mean spectra. Spectral profiles of normal, malignant conditions show pronounced differences between one another, and multiple Raman markers associated with DNA and protein vibrational modes have been identified that exhibit excellent discrimination power for cancer sample identification. Statistical analyses of the Raman data and classification using principal component analysis (PCA) are shown to be effective for the Raman spectral diagnosis of oral mucosal diseases. The results indicate that the biomolecular differences between normal and malignant conditions are more obviously at the cellular level. This technique could provide a research foundation for the Raman spectral diagnosis of oral mucosal diseases.

Application of Raman spectroscopy for on-line monitoring of low dose blend uniformity.

PubMed

Hausman, Debra S; Cambron, R Thomas; Sakr, Adel

2005-07-14

On-line Raman spectroscopy was used to evaluate the effect of blending time on low dose, 1%, blend uniformity of azimilide dihydrochloride. An 8 qt blender was used for the experiments and instrumented with a Raman probe through the I-bar port. The blender was slowed to 6.75 rpm to better illustrate the blending process (normal speed is 25 rpm). Uniformity was reached after 20 min of blending at 6.75 rpm (135 revolutions or 5.4 min at 25 rpm). On-line Raman analysis of blend uniformity provided more benefits than traditional thief sampling and off-line analysis. On-line Raman spectroscopy enabled generating data rich blend profiles, due to the ability to collect a large number of samples during the blending process (sampling every 20s). In addition, the Raman blend profile was rapidly generated, compared to the lengthy time to complete a blend profile with thief sampling and off-line analysis. The on-line Raman blend uniformity results were also significantly correlated (p-value < 0.05) to the HPLC uniformity results of thief samples.

Spontaneous Raman Scattering Diagnostics for High-pressure Gaseous Flames

NASA Technical Reports Server (NTRS)

Kojima, Jun; Nguyen, Quang-Viet; Reddy, D. R. (Technical Monitor)

2002-01-01

A high-pressure (up to 60 atm) gaseous burner facility with optical access that provides steady, reproducible flames with high precision, and the ability to use multiple fuel/oxidizer combinations has been developed. In addition, a high-performance spontaneous Raman scattering system for use in the above facility has also been developed. Together, the two systems will be used to acquire and establish a comprehensive Raman scattering spectral database for use as a quantitative high-pressure calibration of single-shot Raman scattering measurements in high-pressure combustion systems. Using these facilities, the Raman spectra of H2-Air flames were successfully measured at pressures up to 20 atm. The spectra demonstrated clear rotational and ro-vibrational Raman features of H2, N2, and H2O. theoretical Raman spectra of pure rotational H2, vibrational H2, and vibrational N2 were calculated using a classical harmonic-oscillator model with pressure broadening effects and fitted to the data. At a gas temperature of 1889 K for a phi = 1.34 H2-Air flame, the model and the data showed good agreement, confirming a ro-vibrational equilibrium temperature.

Preparation of surface enhanced Raman substrate and its characterization

NASA Astrophysics Data System (ADS)

Liu, Y.; Wang, J. Y.; Wang, J. Q.

2017-10-01

Surface enhanced Raman spectroscopy (SERS) is a fast, convenient and highly sensitive detection technique, and preparing the good effect and repeatable substrate is the key to realize the trace amount and quantitative detection in the field of food safety detection. In this paper, a surface enhanced Raman substrate based on submicrometer silver particles structure was prepared by chemical deposition method, and characterized its structure and optical properties.

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

Combination of surface- and interference-enhanced Raman scattering by CuS nanocrystals on nanopatterned Au structures

PubMed Central

Yeryukov, Nikolay A; Sveshnikova, Larisa L; Duda, Tatyana A; Rodyakina, Ekaterina E; Gridchin, Victor A; Sheremet, Evgeniya S; Zahn, Dietrich R T

2015-01-01

Summary We present the results of a Raman study of optical phonons in CuS nanocrystals (NCs) with a low areal density fabricated through the Langmuir–Blodgett technology on nanopatterned Au nanocluster arrays using a combination of surface- and interference-enhanced Raman scattering (SERS and IERS, respectively). Micro-Raman spectra of one monolayer of CuS NCs deposited on a bare Si substrate reveal only features corresponding to crystalline Si. However, a new relatively strong peak occurs in the Raman spectrum of CuS NCs on Au nanocluster arrays at 474 cm−1. This feature is related to the optical phonon mode in CuS NCs and manifests the SERS effect. For CuS NCs deposited on a SiO2 layer this phonon mode is also observed due to the IERS effect. Its intensity changes periodically with increasing SiO2 layer thickness for different laser excitation lines and is enhanced by a factor of about 30. CuS NCs formed on Au nanocluster arrays fabricated on IERS substrates combine the advantages of SERS and IERS and demonstrate stronger SERS enhancement allowing for the observation of Raman signals from CuS NCs with an ultra-low areal density. PMID:25977845

Raman spectroscopic analysis of cytotoxic effect of cisplatin-treated leukemic cells

NASA Astrophysics Data System (ADS)

Lin, Juqiang; Li, Yongzeng; Feng, Shangyuan; Chen, Rong; Chen, Guannan; Chen, Qisong; Pan, Jianji; Lin, Shaojun; Yu, Yun

2009-08-01

An antitumor drug cisplatin was employed to treat the leukemic cells and induce apoptosis of the cancer cells. Confocal Raman micro-spectroscopy has been applied to investigate the effectiveness of the treatment using near-infrared laser (785nm) excitation, scanning range from 500 to 2000 cm-1. The Raman spectra of leukemic cell treated with cisplatin for 4, 6, 8, 12 and 14 h were measured separately. The major difference of the apoptotic cells from the cancer cells are the reduction in intensities of vibration bands generated by cellular lipids, proteins and nucleic acids. In particular, large intensity reduction in nucleic vibrations at 782, 1092, 1320, 1340, and 1578 cm-1 was observed upon apoptosis of the leukemic cells. Up to 45% reduction in the magnitude of the 782 cm-1 peak in Raman spectra of the apoptotic cells was observed, which suggests the breakdown of phosphodiester bonds and DNA bases. We showed that the principal components analysis (PCA), a multivariate statistical tool, can be used to distinguish single apoptotic cells and leukemic cells based on their Raman spectra. Our results indicate that the Raman spectroscopy with PCA is a novel, nondestructive mean for studying the cisplatin -treated leukemic cells, which could also provide useful data for clinical dosage optimization for cisplatin.

Parametric second Stokes Raman laser output pulse shortening to 300 ps due to depletion of pumping of intracavity Raman conversion

NASA Astrophysics Data System (ADS)

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

2016-10-01

A new effect of the pulse shortening of the parametrically generated radiation down to hundreds of picosecond via depletion of pumping of intracavity Raman conversion in the miniature passively Q-switched Nd: SrMoO4 parametric self-Raman laser with the increasing energy of the shortened pulse under pulsed pumping by a high-power laser diode bar is demonstrated. The theoretical estimation of the depletion stage duration of the convertible fundamental laser radiation via intracavity Raman conversion is in agreement with the experimentally demonstrated duration of the parametrically generated pulse. Using the mathematical modeling of the pulse shortening quality and quantity deterioration is disclosed, and the solution ways are found by the optimization of the laser parameters.

Influence of strong and weak hydrogen bonds in ices on stimulated Raman scattering.

PubMed

Li, Tianyu; Li, Fangfang; Li, Zhanlong; Sun, Chenglin; Tong, Junhong; Fang, Wenhui; Men, Zhiwei

2016-03-15

Stimulated Raman scattering (SRS) in liquid water and ice Ih using Nd:YAG laser is investigated. The spectrum of backward SRS (BSRS) in water is acquired. The spectrum shows an unexpected SRS peak at around 3453  cm(-1) besides the normal peak, which is similar to the spontaneous Raman spectrum of ice VII. The ice VII phase will be formed by laser-induced shock compression in liquid water. Simultaneously, unlike the spontaneous Raman spectrum, the pre-resonance SRS of ice Ih at around 3110 and 3210  cm(-1) is observed. The Raman peaks appeared in liquid water and ice Ih are attributed to the effect of strong and weak hydrogen bonds (H bonds), which should be ubiquitous in other ice phases.

Mapping residual stress fields from Vickers hardness indents using Raman microprobe spectroscopy

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

Sparks, R.G.; Enloe, W.S.; Paesler, M.A.

Micro-Raman spectroscopy is used to map the residual stress fields in the vicinity of Vickers hardness indents. Both 514.5 and 488.0 nm, light is used to excite the effect and the resulting shifted and broadened Raman peaks are analyzed using computer deconvolution. Half-wave plates are used to vary the orientation of the incident later light`s polarization state with respect to crystal orientation. The Raman scattered light is then analyzed for polarization dependences which are indicative of the various components of the Raman scattering tensor. Such studies can yield valuable information about the orientation of stress components in a well knownmore » stress field. The results can then be applied to the determination of stress components in machined semiconductor materials.« less

Effect of pressure on Zircon's (ZrSiO4) Raman active modes: a first-principles study

NASA Astrophysics Data System (ADS)

Sheremetyeva, Natalya; Cherniak, Daniele; Watson, Bruce; Meunier, Vincent

Zircon is a mineral commonly found in the Earth crust. Its remarkable properties have given rise to considerable attention. This includes possible inclusion of radioactive elements in natural samples, which allows for geochronological investigations. Subsequently, Zircon was proposed as possible host material for radioactive waste management. Internal radiation damage in zircon leads to the destruction of its crystal structure (an effect known as metamictization) which is subject to ongoing research. Recently, the effect of pressure and temperature on synthetic zircon has been analyzed experimentally using Raman spectroscopy which led to the calibration of zircon as a pressure sensor in diamond-anvil cell experiments. While there have been a number of theoretical studies, the effect of pressure on the Raman active modes of zircon has not been investigated theoretically. Here we present a first-principles pressure calibration of the Raman active modes in Zircon employing density-functional theory (DFT). We find excellent quantitative agreement of the slopes ∂ω / ∂P with the experimental ones and are able to rationalize the ω vs. P behavior based on the details of the vibrational modes.

Raman scattering tensors of tyrosine.

PubMed

Tsuboi, M; Ezaki, Y; Aida, M; Suzuki, M; Yimit, A; Ushizawa, K; Ueda, T

1998-01-01

Polarized Raman scattering measurements have been made of a single crystal of L-tyrosine by the use of a Raman microscope with the 488.0-nm exciting beam from an argon ion laser. The L-tyrosine crystal belongs to the space group P2(1)2(1)2(1) (orthorhombic), and Raman scattering intensities corresponding to the aa, bb, cc, ab and ac components of the crystal Raman tensor have been determined for each prominent Raman band. A similar set of measurements has been made of L-tyrosine-d4, in which four hydrogen atoms on the benzene ring are replaced by deuterium atoms. The effects of NH3-->ND3 and OH-->OD on the Raman spectrum have also been examined. In addition, depolarization ratios of some bands of L-tyrosine in aqueous solutions of pH 13 and pH 1 were examined. For comparison with these experimental results, on the other hand, ab initio molecular orbital calculations have been made of the normal modes of vibration and their associated polarizability oscillations of the L-tyrosine molecule. On the basis of these experimental data and by referring to the results of the calculations, discussions have been presented on the Raman tensors associated to some Raman bands, including those at 829 cm-1 (benzene ring breathing), 642 cm-1 (benzene ring deformation), and 432 cm-1 (C alpha-C beta-C gamma bending).

Mapping of Low-Frequency Raman Modes in CVD-Grown Transition Metal Dichalcogenides: Layer Number, Stacking Orientation and Resonant Effects

PubMed Central

O’Brien, Maria; McEvoy, Niall; Hanlon, Damien; Hallam, Toby; Coleman, Jonathan N.; Duesberg, Georg S.

2016-01-01

Layered inorganic materials, such as the transition metal dichalcogenides (TMDs), have attracted much attention due to their exceptional electronic and optical properties. Reliable synthesis and characterization of these materials must be developed if these properties are to be exploited. Herein, we present low-frequency Raman analysis of MoS2, MoSe2, WSe2 and WS2 grown by chemical vapour deposition (CVD). Raman spectra are acquired over large areas allowing changes in the position and intensity of the shear and layer-breathing modes to be visualized in maps. This allows detailed characterization of mono- and few-layered TMDs which is complementary to well-established (high-frequency) Raman and photoluminescence spectroscopy. This study presents a major stepping stone in fundamental understanding of layered materials as mapping the low-frequency modes allows the quality, symmetry, stacking configuration and layer number of 2D materials to be probed over large areas. In addition, we report on anomalous resonance effects in the low-frequency region of the WS2 Raman spectrum. PMID:26766208

Residual pesticide detection on food with particle-enhanced Raman scattering

NASA Astrophysics Data System (ADS)

Ranjan, Bikas; Huang, LiChuan; Masui, Kyoko; Saito, Yuika; Verma, Prabhat

2014-08-01

Modern farming relies highly on pesticides to protect agricultural food items from insects for high yield and better quality. Increasing use of pesticide has raised concern about its harmful effects on human health and hence it has become very important to detect even small amount of pesticide residues. Raman spectroscopy is a suitable nondestructive method for pesticide detection, however, it is not very effective for low concentration of pesticide molecules. Here, we report an approach based on plasmonic enhancement, namely, particle enhanced Raman spectroscopy (PERS), which is rapid, nondestructive and sensitive. In this technique, Raman signals are enhanced via the resonance excitation of localized plasmons in metallic nanoparticles. Gold nanostructures are promising materials that have ability to tune surface plasmon resonance frequency in visible to near-IR, which depends on shape and size of nanostructures. We synthesized gold nanorods (GNRs) with desired shape and size by seed mediated growth method, and successfully detected very tiny amount of pesticide present on food items. We also conformed that the detection of pesticide was not possible by usual Raman spectroscopy.

Raman spectroscopy and atomic force microscopy study of interfacial polytypism in GaP/Ge(111) heterostructures

NASA Astrophysics Data System (ADS)

Aggarwal, R.; Ingale, Alka A.; Dixit, V. K.

2018-01-01

Effects of lattice and polar/nonpolar mismatch between the GaP layer and Ge(111) substrate are investigated by spatially resolved Raman spectroscopy. The red shifted transverse optical (TO) and longitudinal optical (LO) phonons due to residual strain, along with asymmetry to TO phonon ∼358 cm-1 are observed in GaP/Ge(111). The peak intensity variation of mode ∼358 cm-1 with respect to TO phonon across the crystallographic morphed surface of GaP micro structures is associated with the topographical variations using atomic force microscopy mapping and Raman spectroscopy performed on both in plane and cross-sectional surface. Co-existence of GaP allotropes, i.e. wurtzite phase near heterojunction interface and dominant zinc-blende phase near surface is established using the spatially resolved polarized Raman spectroscopy from the cross sectional surface of heterostructures. This consistently explains effect of surface morphology on Raman spectroscopy from GaP(111). The study shows the way to identify crystalline phases in other advanced semiconductor heterostructures without any specific sample preparation.

Raman imaging of pharmaceutical materials: refractive index effects on contrast at buried interfaces.

PubMed

Mecker-Pogue, Laura C; Kauffman, John F

2015-02-01

Resolution targets composed of bilayer polydimethylsiloxane (PDMS) devices with buried polyethylene glycol (PEG) channels have been fabricated using traditional photolithographic and micromolding techniques to develop resolution targets that mimic pharmaceutical materials. Raman chemical images of the resulting PEG-in-PDMS devices composed of varying parallel line widths were investigated by imaging the PEG lines through a thin overlayer of PDMS. Additionally, a scattering agent, Al2O3, was introduced at varying concentrations to each layer of the device to explore the effects of scattering materials on Raman images. Features in the resulting chemical images of the PEG lines suggest that reflection at the PEG/PDMS interface contributes to the Raman signal. A model based on geometric optics was developed to simulate the observed image functions of the targets. The results emphasize the influence of refractive index discontinuities at the PEG/PDMS interface on the apparent size and shape of the PEG features. Such findings have an impact on interpretation of Raman images of nonabsorbing, opaque pharmaceutical samples. Published by Elsevier B.V.

Solid-state Raman frequency converters for CO2-DIAL systems at 1.6 μm

NASA Astrophysics Data System (ADS)

Rhee, Hanjo; Lisinetskii, Victor; Kaminskii, Alexander A.; Eichler, Hans-Joachim

2009-09-01

Measurement of the three-dimensional distribution of atmospheric trace gases, especially CO2, is an important factor to improve the accuracy of climate models and to understand the global effects of the greenhouse effect. This can be achieved by differential absorption Lidar (DIAL). The absorption spectrum of CO2 features several suitable absorption lines for a ground-based or air-borne DIAL system working at wavelengths between 1.57 μm and 1.61 μm. An appropriate laser transmitter must emit laser pulses with pulse energies of more than 10 mJ and pulse duration in the nanosecond range. For high spectral purity the bandwidth is required to be less than 60 MHz. OPOs and Er-doped solid-state lasers emit around 1.6 μm, but we describe here alternatively Nd:YAG and Nd:glass laser systems with Raman converters. The use of stimulated Raman scattering in crystalline and ceramic materials is a possibility to shift the wavelength of existing lasers depending on the size of the Raman shift. After the investigation of a large number of Raman-active materials some of them could be identified as promising candidates for the conversion of typical Nd:YAG emission wavelengths, including LiNH2C6H4SO3•H2O, Ba(NO3)2, Li2SO4•H2O, Y(HCOO)3•2H2O, β-BBO and diamond. Our experiments with Ba(NO3)2 showed that the choice of the material should not be restricted to those with an adequate first order Stokes Raman line position, but also second or third order Raman shift should be considered. Development of Raman frequency converters for high pulse energies concentrates on linear and folded resonator designs and seeded Raman amplifiers using the Raman material as a direct amplifier. With Ba(NO3)2 pulse energy up to 116 mJ and 42 % quantum efficiency at the third Stokes wavelength with 1599 nm has been demonstrated. High power operation at 5 W with compensation of thermal lensing was achieved.

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 non-coincidence effect of boroxol ring: The interplay between repulsion and attraction forces in the glassy, supercooled and liquid state

NASA Astrophysics Data System (ADS)

Kalampounias, Angelos G.; Papatheodorou, George N.

2018-06-01

Temperature dependent Raman spectra of boric oxide have been measured in a temperature range covering the glassy, supercooled and liquid state. The shift of the isotropic band assigned to boroxol rings relative to the anisotropic component upon heating the glass is measured and attributed to the Raman non-coincidence effect. The measured shift is associated with the competition between attraction and repulsion forces with increasing temperature. The relation of dephasing and orientational relaxation times to the non-coincidence effect of the condensed phases has been examined. We discuss our results in the framework of the current phenomenological status of the field in an attempt to separate the attraction and repulsion contributions corresponding to the observed non-coincidence effect.

Raman scattering in crystals

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

Edwards, D.F.

1988-09-30

A tutorial presentation is given of Raman scattering in crystals. The physical concepts are emphasized rather than the detailed mathematical formalism. Starting with an introduction to the concepts of phonons and conservation laws, the effects of photon-phonon interactions are presented. This interaction concept is shown for a simple cubic crystal and is extended to a uniaxial crystal. The correlation table method is used for determining the number and symmetry of the Raman active modes. Finally, examples are given to illustrate the relative ease of using this group theoretical method and the predictions are compared with measured Raman spectra. 37 refs.,more » 17 figs., 6 tabs.« less

Remote measurements of the atmosphere using Raman scattering.

PubMed

Melfi, S H

1972-07-01

The Raman optical radar measurements of the atmosphere presented demonstrate that the technique may be used to obtain quantitative measurements of the spatial distribution of individual atmospheric molecular trace constituents, in particular water vapor, as well as those of the major constituents. In addition, it is shown that monitoring Raman signals from atmospheric nitrogen aids in interpreting elastic scattering measurements by eliminating attenuation effects. In general, the experimental results show good agreement with independent meteorological measurements. Finally, experimental data are utilized to estimate the Raman backscatter cross section for water vapor excited at 3471.5 A as sigmaH(2)O/sigmaN(2) = 3.8 +/- 25%.

Surface enhanced Raman scattering of aged graphene: Effects of annealing in vacuum

NASA Astrophysics Data System (ADS)

Wang, Yingying; Ni, Zhenhua; Li, Aizhi; Zafar, Zainab; Zhang, Yan; Ni, Zhonghua; Qu, Shiliang; Qiu, Teng; Yu, Ting; Xiang Shen, Ze

2011-12-01

In this paper, we report a simple method to recover the surface enhanced Raman scattering activity of aged graphene. The Raman signals of Rhodamine molecules absorbed on aged graphene are dramatically increased after vacuum annealing and comparable to those on fresh graphene. Atomic force microscopy measurements indicate that residues on aged graphene surface can efficiently be removed by vacuum annealing, which makes target molecule closely contact with graphene. We also find that the hole doping in graphene will facilitate charge transfer between graphene and molecule. These results confirm the strong Raman enhancement of target molecule absorbed on graphene is due to the charge transfer mechanism.

Surface Plasmon-Coupled Directional Enhanced Raman Scattering by Means of the Reverse Kretschmann Configuration.

PubMed

Huo, Si-Xin; Liu, Qian; Cao, Shuo-Hui; Cai, Wei-Peng; Meng, Ling-Yan; Xie, Kai-Xin; Zhai, Yan-Yun; Zong, Cheng; Yang, Zhi-Lin; Ren, Bin; Li, Yao-Qun

2015-06-04

Surface-enhanced Raman scattering (SERS) is a unique analytical technique that provides fingerprint spectra, yet facing the obstacle of low collection efficiency. In this study, we demonstrated a simple approach to measure surface plasmon-coupled directional enhanced Raman scattering by means of the reverse Kretschmann configuration (RK-SPCR). Highly directional and p-polarized Raman scattering of 4-aminothiophenol (4-ATP) was observed on a nanoparticle-on-film substrate at 46° through the prism coupler with a sharp angle distribution (full width at half-maximum of ∼3.3°). Because of the improved collection efficiency, the Raman scattering signal was enhanced 30-fold over the conventional SERS mode; this was consistent with finite-difference time-domain simulations. The effect of nanoparticles on the coupling efficiency of propagated surface plasmons was investigated. Possessing straightforward implementation and directional enhancement of Raman scattering, RK-SPCR is anticipated to simplify SERS instruments and to be broadly applicable to biochemical assays.

Low vibration high numerical aperture automated variable temperature Raman microscope

DOE PAGES

Tian, Y.; Reijnders, A. A.; Osterhoudt, G. B.; ...

2016-04-05

Raman micro-spectroscopy is well suited for studying a variety of properties and has been applied to wide- ranging areas. Combined with tuneable temperature, Raman spectra can offer even more insights into the properties of materials. However, previous designs of variable temperature Raman microscopes have made it extremely challenging to measure samples with low signal levels due to thermal and positional instability as well as low collection efficiencies. Thus, contemporary Raman microscope has found limited applicability to probing the subtle physics involved in phase transitions and hysteresis. This paper describes a new design of a closed-cycle, Raman microscope with full polarizationmore » rotation. High collection efficiency, thermal and mechanical stability are ensured by both deliberate optical, cryogenic, and mechanical design. Measurements on two samples, Bi 2Se 3 and V 2O 3, which are known as challenging due to low thermal conductivities, low signal levels and/or hysteretic effects, are measured with previously undemonstrated temperature resolution.« less

Studying the distribution of deep Raman spectroscopy signals using liquid tissue phantoms with varying optical properties.

PubMed

Vardaki, Martha Z; Gardner, Benjamin; Stone, Nicholas; Matousek, Pavel

2015-08-07

In this study we employed large volume liquid tissue phantoms, consisting of a scattering agent (Intralipid), an absorption agent (Indian ink) and a synthesized calcification powder (calcium hydroxyapatite (HAP)) similar to that found in cancerous tissues (e.g. breast and prostate), to simulate human tissues. We studied experimentally the magnitude and origin of Raman signals in a transmission Raman geometry as a function of optical properties of the medium and the location of calcifications within the phantom. The goal was to inform the development of future noninvasive cancer screening applications in vivo. The results provide insight into light propagation and Raman scattering distribution in deep Raman measurements, exploring also the effect of the variation of relative absorbance of laser and Raman photons within the phantoms. Most notably when modeling breast and prostate tissues it follows that maximum signals is obtained from the front and back faces of the tissue with the central region contributing less to the measured spectrum.

Laser radar studies: A study of the feasibility of remote measurement of atmospheric density and turbidity by means of rotational Raman scattering of laser light

NASA Technical Reports Server (NTRS)

Reiss, N.; Schotland, R. M.

1973-01-01

A remote sensing technique is described which utilizes elastic scattering and rotational Raman scattering of laser light in the atmosphere to obtain soundings of turbidity, transmissivity and density. A scheme is devised whereby, through selective weighting of the rotational Raman lines, the effect of atmospheric temperature structure may be eliminated. The close spectral proximity of the elastic and Raman-scattered signals, combined with the fact that the Raman scattering is quite weak, produces special requirements for the spectroscopic and light-gathering components of a rotational Raman laser radar system. These requirements are investigated. A computation of typical signal-to-noise ratios is made. It is shown that daytime signal-to-noise ratios greater than 10 db are to be expected for observation heights of 5 km and below. For nighttime work, 10 db signal-to-noise ratios are achievable to altitudes as high as 15 km.

Confocal micro-Raman spectroscopy of single biological cells using optical trapping and shifted excitation difference techniques

NASA Astrophysics Data System (ADS)

Xie, Changan; Li, Yong-qing

2003-03-01

We report on the study of single biological cells with a confocal micro-Raman spectroscopy system that uses optical trapping and shifted excitation Raman difference technique. A tunable diode laser was used to capture a living cell in solution, confine it in the confocal excitation volume, and then excite the Raman scattering. The optical trapping allows us to lift the cell well off the cover plate so that the fluorescence interference from the plate can be effectively reduced. In order to further remove the interference of the fluorescence and stray light from the trapped cell, we employed a shifted excitation Raman difference technique with slightly tuned laser frequencies. With this system, high-quality Raman spectra were obtained from single optically trapped biological cells including E. coli bacteria, yeast cells, and red blood cells. A significant difference between control and heat-treated E. coli B cells was observed due to the denaturation of biomolecules.

Low vibration high numerical aperture automated variable temperature Raman microscope

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

Tian, Y.; Reijnders, A. A.; Osterhoudt, G. B.

Raman micro-spectroscopy is well suited for studying a variety of properties and has been applied to wide- ranging areas. Combined with tuneable temperature, Raman spectra can offer even more insights into the properties of materials. However, previous designs of variable temperature Raman microscopes have made it extremely challenging to measure samples with low signal levels due to thermal and positional instability as well as low collection efficiencies. Thus, contemporary Raman microscope has found limited applicability to probing the subtle physics involved in phase transitions and hysteresis. This paper describes a new design of a closed-cycle, Raman microscope with full polarizationmore » rotation. High collection efficiency, thermal and mechanical stability are ensured by both deliberate optical, cryogenic, and mechanical design. Measurements on two samples, Bi 2Se 3 and V 2O 3, which are known as challenging due to low thermal conductivities, low signal levels and/or hysteretic effects, are measured with previously undemonstrated temperature resolution.« less

New insight into UO 2F 2 particulate structure by micro-Raman spectroscopy

DOE PAGES

Stefaniak, Elzbieta A.; Darchuk, Larysa; Sapundjiev, Danislav; ...

2013-02-19

Uranyl fluoride particles produced via hydrolysis of uranium hexafluoride have been deposited on different substrates: polished graphite disks, silver foil, stainless steel and gold-coated silicon wafer, and measured with micro-Raman spectroscopy (MRS). All three metallic substrates enhanced the Raman signal delivered by UO 2F 2 in comparison to graphite. The fundamental stretching of the U–O band appeared at 867 cm –1 in case of the graphite substrate, while in case of the others it was shifted to lower frequencies (down to 839 cm –1). All applied metallic substrates showed the expected effect of Raman signal enhancement; however the gold layermore » appeared to be most effective. Lastly, application of new substrates provides more information on the molecular structure of uranyl fluoride precipitation, which is interesting for nuclear safeguards and nuclear environmental analysis.« less

Experimental Observation of Near-Field Deterioration Induced by Stimulated Rotational Raman Scattering in Long Air Paths

NASA Astrophysics Data System (ADS)

Wang, Jing; Zhang, Xiao-Min; Han, Wei; Li, Fu-Quan; Zhou, Li-Dan; Feng, Bin; Xiang, Yong

2011-08-01

We report the experimental investigation of a stimulated rotational Raman scattering effect in long air paths on SG-III TIL, with a 1053 nm, 20-cm-diameter, linearly polarized, 3 ns flat-topped laser pulse. An intense speckle pattern of near field with thickly dotted hot spots is observed at the end of propagation with an intensity-length product above 17TW/cm. The Stokes developing from the scattering of the laser beam by quantum fluctuations is characterized by a combination of high spatial frequency components. The observed speckle pattern with small-diameter hot spots results from the combination of the nonlinear Raman amplification and the linear diffraction propagation effect of the Stokes with a noise pattern arising from the spontaneous Raman scattering. A new promising suppression concept based on the special characteristic of the Stokes, called active and selective filtering of Stokes, is proposed.

Nanoscale deformation and friction characteristics of atomically thin WSe2 and heterostructure using nanoscratch and Raman spectroscopy

NASA Astrophysics Data System (ADS)

Manimunda, P.; Nakanishi, Y.; Jaques, Y. M.; Susarla, S.; Woellner, C. F.; Bhowmick, S.; Asif, S. A. S.; Galvão, D. S.; Tiwary, C. S.; Ajayan, P. M.

2017-12-01

2D transition metals di-selenides are attracting a lot of attention due to their interesting optical, chemical and electronics properties. Here, the deformation characteristics of monolayer, multi- layer WSe2 and its heterostructure with MoSe2 were investigated using a new technique that combines nanoscratch and Raman spectroscopy. The 2D monolayer WSe2 showed anisotropy in deformation. Effect of number of WSe2 layers on friction characteristics were explored in detail. Experimental observations were further supported by MD simulations. Raman spectra recorded from the scratched regions showed strain induced degeneracy splitting. Further nano-scale scratch tests were extended to MoSe2-WSe2 lateral heterostructures. Effect of deformation on lateral hetero junctions were further analysed using PL and Raman spectroscopy. This new technique is completely general and can be applied to study other 2D materials.

The role of ion irradiation in activating silent Raman modes via tuning in plasmonic behaviour and surface disorder of Au/ZnO/Pt NFG system

NASA Astrophysics Data System (ADS)

Singh, Udai B.; Gautam, Subodh K.; Kumar, Sunil; Ojha, Sunil; Ghosh, Santanu; Singh, Fouran

2017-09-01

The perceptible progression of Raman modes of zinc oxide (ZnO) is studied in nanostructures film gap (Au (10 nm)/ZnO (70 nm)/Pt (50 nm)) system with 1.2 MeV Xe ion irradiation. Unattainable silent Raman modes of ZnO turn out to be strongly visible after ion irradiation. The creation of ion-beam-induced lattice disorder, defects, and impurities in a ZnO layer leads to breakdown the translational crystal symmetry that results in the origin of silent modes. The formation of hot-spots in the ZnO layer of the NFG system also supports the enhancement of the intensity of Raman modes. Overall results are attributed to combined effects of lattice disorder, defects, and impurities along with plasmonic effect and explained in the framework of elastic-thermal-spike formation.

Raman Scattering by Molecular Hydrogen and Nitrogen in Exoplanetary Atmospheres

NASA Astrophysics Data System (ADS)

Oklopčić, Antonija; Hirata, Christopher M.; Heng, Kevin

2016-11-01

An important source of opacity in exoplanet atmospheres at short visible and near-UV wavelengths is Rayleigh scattering of light on molecules. It is accompanied by a related, albeit weaker process—Raman scattering. We analyze the signatures of Raman scattering imprinted in the reflected light and the geometric albedo of exoplanets, which could provide information about atmospheric properties. Raman scattering affects the geometric albedo spectra of planets in the following ways. First, it causes filling-in of strong absorption lines in the incident radiation, thus producing sharp peaks in the albedo. Second, it shifts the wavelengths of spectral features in the reflected light causing the so-called Raman ghost lines. Raman scattering can also cause a broadband reduction of the albedo due to wavelength shifting of a stellar spectrum with red spectral index. Observing the Raman peaks in the albedo could be used to measure the column density of gas, thus providing constraints on the presence of clouds in the atmosphere. Observing the Raman ghost lines could be used to spectroscopically identify the main scatterer in the atmosphere, even molecules like H2 or N2, which do not have prominent spectral signatures in the optical wavelength range. If detected, ghost lines could also provide information about the temperature of the atmosphere. In this paper, we investigate the effects of Raman scattering in hydrogen- and nitrogen-dominated atmospheres. We analyze the feasibility of detecting the signatures of Raman scattering with the existing and future observational facilities, and of using these signatures as probes of exoplanetary atmospheres.

VizieR Online Data Catalog: Raman scattering cross sections for H2 (Oklopcic+,

NASA Astrophysics Data System (ADS)

Oklopcic, A.; Hirata, C. M.; Heng, K.

2017-02-01

An important source of opacity in exoplanet atmospheres at short visible and near-UV wavelengths is Rayleigh scattering of light on molecules. It is accompanied by a related, albeit weaker process-Raman scattering. We analyze the signatures of Raman scattering imprinted in the reflected light and the geometric albedo of exoplanets, which could provide information about atmospheric properties. Raman scattering affects the geometric albedo spectra of planets in the following ways. First, it causes filling-in of strong absorption lines in the incident radiation, thus producing sharp peaks in the albedo. Second, it shifts the wavelengths of spectral features in the reflected light causing the so-called Raman ghost lines. Raman scattering can also cause a broadband reduction of the albedo due to wavelength shifting of a stellar spectrum with red spectral index. Observing the Raman peaks in the albedo could be used to measure the column density of gas, thus providing constraints on the presence of clouds in the atmosphere. Observing the Raman ghost lines could be used to spectroscopically identify the main scatterer in the atmosphere, even molecules like H2 or N2, which do not have prominent spectral signatures in the optical wavelength range. If detected, ghost lines could also provide information about the temperature of the atmosphere. In this paper, we investigate the effects of Raman scattering in hydrogen- and nitrogen-dominated atmospheres. We analyze the feasibility of detecting the signatures of Raman scattering with the existing and future observational facilities, and of using these signatures as probes of exoplanetary atmospheres. (1 data file).

RAMAN SCATTERING BY MOLECULAR HYDROGEN AND NITROGEN IN EXOPLANETARY ATMOSPHERES

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

Oklopčić, Antonija; Hirata, Christopher M.; Heng, Kevin, E-mail: oklopcic@astro.caltech.edu

2016-11-20

An important source of opacity in exoplanet atmospheres at short visible and near-UV wavelengths is Rayleigh scattering of light on molecules. It is accompanied by a related, albeit weaker process—Raman scattering. We analyze the signatures of Raman scattering imprinted in the reflected light and the geometric albedo of exoplanets, which could provide information about atmospheric properties. Raman scattering affects the geometric albedo spectra of planets in the following ways. First, it causes filling-in of strong absorption lines in the incident radiation, thus producing sharp peaks in the albedo. Second, it shifts the wavelengths of spectral features in the reflected lightmore » causing the so-called Raman ghost lines. Raman scattering can also cause a broadband reduction of the albedo due to wavelength shifting of a stellar spectrum with red spectral index. Observing the Raman peaks in the albedo could be used to measure the column density of gas, thus providing constraints on the presence of clouds in the atmosphere. Observing the Raman ghost lines could be used to spectroscopically identify the main scatterer in the atmosphere, even molecules like H{sub 2} or N{sub 2}, which do not have prominent spectral signatures in the optical wavelength range. If detected, ghost lines could also provide information about the temperature of the atmosphere. In this paper, we investigate the effects of Raman scattering in hydrogen- and nitrogen-dominated atmospheres. We analyze the feasibility of detecting the signatures of Raman scattering with the existing and future observational facilities, and of using these signatures as probes of exoplanetary atmospheres.« less

Scaling Studies of Efficient Raman Converters.

DTIC Science & Technology

1983-07-01

allowed without deleterious effects due to competing processes. These processes include amplified spontaneous emission (Raman superfluorescence...tively introducing noise injection that could potentially degrade conversion efficiency and/or beam quality. The conditions under which these competing ...good beam qual- ity. Section 5.1 discusses Stokes injection level requirements in terms of suppressing competing effects which can reduce conversion

Temperature-dependent μ-Raman investigation of struvite crystals.

PubMed

Prywer, Jolanta; Kasprowicz, D; Runka, T

2016-04-05

The effect of temperature on the vibrational properties of struvite crystals grown from silica gels was systematically studied by μ-Raman spectroscopy. The time-dependent Raman spectra recorded in the process of long time annealing of struvite crystal at 353 K do not indicate structural changes in the struvite crystal with the time of annealing. The temperature-dependent Raman spectra recorded in the range 298-423 K reveal a phase transition in struvite at about 368 K. Above this characteristic temperature, some of bands assigned to vibrations of the PO4 and NH4 tetrahedra and water molecules observed in the Raman spectra in low temperatures (orthorhombic phase) change their spectral parameters or disappear, which indicates a transition to a higher symmetry structure of struvite in the range of high temperatures. Copyright © 2016 Elsevier B.V. All rights reserved.

Effectiveness of surface enhanced Raman spectroscopy of tear fluid with soft substrate for point-of-care therapeutic drug monitoring

NASA Astrophysics Data System (ADS)

Yamada, K.; Endo, T.; Imai, H.; Kido, M.; Jeong, H.; Ohno, Y.

2016-03-01

We have developed the point-of-care therapeutic drug monitoring kit based on Raman Spectroscopy of tear fluid. In this study, we were examined a soft substrate for an optimal lattice based on nanoimprint lithography using cyclo-olefin polymer to improve the sensitivity for measuring drug concentration in tear fluid. This is photonics crystal which is one of the nano-photonics based device was fabricated. Target is Sodium Phenobarbital which is an anticonvulsant agent. We show the effectiveness of Surface Enhanced Raman Spectroscopy of tear fluid with soft substrate for point-of-care therapeutic drug monitoring.

Stress Characterization of 4H-SiC Metal-Oxide-Semiconductor Field-Effect Transistor (MOSFET) using Raman Spectroscopy and the Finite Element Method.

PubMed

Yoshikawa, Masanobu; Kosaka, Kenichi; Seki, Hirohumi; Kimoto, Tsunenobu

2016-07-01

We measured the depolarized and polarized Raman spectra of a 4H-SiC metal-oxide-semiconductor field-effect transistor (MOSFET) and found that compressive stress of approximately 20 MPa occurs under the source and gate electrodes and tensile stress of approximately 10 MPa occurs between the source and gate electrodes. The experimental result was in close agreement with the result obtained by calculation using the finite element method (FEM). A combination of Raman spectroscopy and FEM provides much data on the stresses in 4H-SiC MOSFET. © The Author(s) 2016.

Ultrasensitive molecular sensor using N-doped graphene through enhanced Raman scattering

PubMed Central

Feng, Simin; dos Santos, Maria Cristina; Carvalho, Bruno R.; Lv, Ruitao; Li, Qing; Fujisawa, Kazunori; Elías, Ana Laura; Lei, Yu; Perea-López, Nestor; Endo, Morinobu; Pan, Minghu; Pimenta, Marcos A.; Terrones, Mauricio

2016-01-01

As a novel and efficient surface analysis technique, graphene-enhanced Raman scattering (GERS) has attracted increasing research attention in recent years. In particular, chemically doped graphene exhibits improved GERS effects when compared with pristine graphene for certain dyes, and it can be used to efficiently detect trace amounts of molecules. However, the GERS mechanism remains an open question. We present a comprehensive study on the GERS effect of pristine graphene and nitrogen-doped graphene. By controlling nitrogen doping, the Fermi level (EF) of graphene shifts, and if this shift aligns with the lowest unoccupied molecular orbital (LUMO) of a molecule, charge transfer is enhanced, thus significantly amplifying the molecule’s vibrational Raman modes. We confirmed these findings using different organic fluorescent molecules: rhodamine B, crystal violet, and methylene blue. The Raman signals from these dye molecules can be detected even for concentrations as low as 10−11 M, thus providing outstanding molecular sensing capabilities. To explain our results, these nitrogen-doped graphene-molecule systems were modeled using dispersion-corrected density functional theory. Furthermore, we demonstrated that it is possible to determine the gaps between the highest occupied and the lowest unoccupied molecular orbitals (HOMO-LUMO) of different molecules when different laser excitations are used. Our simulated Raman spectra of the molecules also suggest that the measured Raman shifts come from the dyes that have an extra electron. This work demonstrates that nitrogen-doped graphene has enormous potential as a substrate when detecting low concentrations of molecules and could also allow for an effective identification of their HOMO-LUMO gaps. PMID:27532043

Digital micromirror devices in Raman trace detection of explosives

NASA Astrophysics Data System (ADS)

Glimtoft, Martin; Svanqvist, Mattias; Ågren, Matilda; Nordberg, Markus; Östmark, Henric

2016-05-01

Imaging Raman spectroscopy based on tunable filters is an established technique for detecting single explosives particles at stand-off distances. However, large light losses are inherent in the design due to sequential imaging at different wavelengths, leading to effective transmission often well below 1 %. The use of digital micromirror devices (DMD) and compressive sensing (CS) in imaging Raman explosives trace detection can improve light throughput and add significant flexibility compared to existing systems. DMDs are based on mature microelectronics technology, and are compact, scalable, and can be customized for specific tasks, including new functions not available with current technologies. This paper has been focusing on investigating how a DMD can be used when applying CS-based imaging Raman spectroscopy on stand-off explosives trace detection, and evaluating the performance in terms of light throughput, image reconstruction ability and potential detection limits. This type of setup also gives the possibility to combine imaging Raman with non-spatially resolved fluorescence suppression techniques, such as Kerr gating. The system used consists of a 2nd harmonics Nd:YAG laser for sample excitation, collection optics, DMD, CMOScamera and a spectrometer with ICCD camera for signal gating and detection. Initial results for compressive sensing imaging Raman shows a stable reconstruction procedure even at low signals and in presence of interfering background signal. It is also shown to give increased effective light transmission without sacrificing molecular specificity or area coverage compared to filter based imaging Raman. At the same time it adds flexibility so the setup can be customized for new functionality.

Raman spectral markers of collagen denaturation and hydration in human cortical bone tissue are affected by radiation sterilization and high cycle fatigue damage.

PubMed

Flanagan, Christopher D; Unal, Mustafa; Akkus, Ozan; Rimnac, Clare M

2017-11-01

Thermal denaturation and monotonic mechanical damage alter the organic and water-related compartments of cortical bone. These changes can be detected using Raman spectroscopy. However, less is known regarding Raman sensitivity to detect the effects of cyclic fatigue damage and allograft sterilization doses of gamma radiation. To determine if Raman spectroscopic biomarkers of collagen denaturation and hydration are sensitive to the effects of (a) high cycle fatigue damage and (b) 25kGy irradiation. Unirradiated and gamma-radiation sterilized human cortical bone specimens previously tested in vitro under high-cycle (> 100,000 cycles) fatigue conditions at 15MPa, 25MPa, 35MPa, 45MPa, and 55MPa cyclic stress levels were studied. Cortical bone Raman spectral profiles from wavenumber ranges of 800-1750cm -1 and 2700-3800cm -1 were obtained and compared from: a) non-fatigue vs fatigue fracture sites and b) radiated vs. unirradiated states. Raman biomarker ratios 1670/1640 and 3220/2949, which reflect collagen denaturation and organic matrix (mainly collagen)-bound water, respectively, were assessed. One- and two-way ANOVA analyses were utilized to identify differences between groups along with interaction effects between cyclic fatigue and radiation-induced damage. Cyclic fatigue damage resulted in increases in collagen denaturation (1670/1640: 1.517 ± 0.043 vs 1.579 ± 0.021, p < 0.001) and organic matrix-bound water (3220/2949: 0.109 ± 0.012 vs 0.131 ± 0.008, p < 0.001). Organic matrix-bound water increased secondary to 25kGy irradiation (3220/2949: 0.105 ± 0.010 vs 0.1161 ± 0.009, p = 0.003). Organic matrix-bound water was correlated positively with collagen denaturation (r = 0.514, p < 0.001). Raman spectroscopy can detect the effects of cyclic fatigue damage and 25kGy irradiation via increases in organic matrix (mainly collagen)-bound water. A Raman measure of collagen denaturation was sensitive to cyclic fatigue damage but not 25kGy irradiation. Collagen denaturation was correlated with organic matrix-bound water, suggesting that denaturation of collagen to gelatinous form may expose more binding sites to water by unwinding the triple alpha chains. This research may eventually be useful to help identify allograft quality and more appropriately match donors to recipients. Copyright © 2017 Elsevier Ltd. All rights reserved.

Raman spectroscopic features of Al- Fe3+- poor magnesiochromite and Fe2+- Fe3+- rich ferrian chromite solid solutions

NASA Astrophysics Data System (ADS)

Kharbish, Sherif

2018-04-01

Naturally occurring Al- Fe3 +- poor magnesiochromite and Fe2+- Fe3 +- rich ferrian chromite solid solutions have been analyzed by micro-Raman spectroscopy. The results reflect a strong positive correlation between the Fe3 + # [Fe3+/(Fe3 ++Cr + Al)] and the positions of all Raman bands. A positive correlation of the Raman band positions with Mg# [Mg/(Mg + Fe2 +)] is less stringent. Raman spectra of magnesiochromite and ferrian chromite show seven and six bands, respectively, in the spectral region of 800 - 100 cm- 1. The most intense band in both minerals is identified as symmetric stretching vibrational mode, ν 1( A 1 g ). In the intermediate Raman-shift region (400-600 cm- 1), the significant bands are attributed to the ν 3( F 2 g ) > ν 4( F 2 g ) > ν 2( E g ) modes. The bands with the lowest Raman shifts (< 200 cm- 1) are assigned to F 2 g ( trans) translatory lattice modes. Extra bands in magnesiochromite (two bands) and in ferrian chromite (one weak band) are attributed to lowering in local symmetry and order/disorder effects.

Near-infrared confocal micro-Raman spectroscopy combined with PCA-LDA multivariate analysis for detection of esophageal cancer

NASA Astrophysics Data System (ADS)

Chen, Long; Wang, Yue; Liu, Nenrong; Lin, Duo; Weng, Cuncheng; Zhang, Jixue; Zhu, Lihuan; Chen, Weisheng; Chen, Rong; Feng, Shangyuan

2013-06-01

The diagnostic capability of using tissue intrinsic micro-Raman signals to obtain biochemical information from human esophageal tissue is presented in this paper. Near-infrared micro-Raman spectroscopy combined with multivariate analysis was applied for discrimination of esophageal cancer tissue from normal tissue samples. Micro-Raman spectroscopy measurements were performed on 54 esophageal cancer tissues and 55 normal tissues in the 400-1750 cm-1 range. The mean Raman spectra showed significant differences between the two groups. Tentative assignments of the Raman bands in the measured tissue spectra suggested some changes in protein structure, a decrease in the relative amount of lactose, and increases in the percentages of tryptophan, collagen and phenylalanine content in esophageal cancer tissue as compared to those of a normal subject. The diagnostic algorithms based on principal component analysis (PCA) and linear discriminate analysis (LDA) achieved a diagnostic sensitivity of 87.0% and specificity of 70.9% for separating cancer from normal esophageal tissue samples. The result demonstrated that near-infrared micro-Raman spectroscopy combined with PCA-LDA analysis could be an effective and sensitive tool for identification of esophageal cancer.

Characterization method for relative Raman enhancement for surface-enhanced Raman spectroscopy using gold nanoparticle dimer array

NASA Astrophysics Data System (ADS)

Sugano, Koji; Ikegami, Kohei; Isono, Yoshitada

2017-06-01

In this paper, a characterization method for Raman enhancement for highly sensitive and quantitative surface-enhanced Raman spectroscopy (SERS) is reported. A particle dimer shows a marked electromagnetic enhancement when the particle connection direction is matched to the polarization direction of incident light. In this study, dimers were arrayed by nanotrench-guided self-assembly for a marked total Raman enhancement. By measuring acetonedicarboxylic acid, the fabricated structures were characterized for SERS depending on the polarization angle against the particle connection direction. This indicates that the fabricated structures cause an effective SERS enhancement, which is dominated by the electromagnetic enhancement. Then, we measured 4,4‧-bipyridine, which is a pesticide material, for quantitative analysis. In advance, we evaluated the enhancement of the particle structure by the Raman measurement of acetonedicarboxylic acid. Finally, we compared the Raman intensities of acetonedicarboxylic acid and 4,4‧-bipyridine. Their intensities showed good correlation. The advantage of this method for previously evaluating the enhancement of the substrate was demonstrated. This developed SERS characterization method is expected to be applied to various quantitative trace analyses of molecules with high sensitivity.

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.

FT-Raman spectra of cellulose and lignocellulose materials : “self-absorption” phenomenon and its implications for quantitative work

Treesearch

Umesh Agarwal; Nancy Kawai

2003-01-01

The phenomenon of “self-absorption” was found to exist in the FT-Raman spectra of cellulose and thermomechanical pulp (TMP), but not in the spectrum of milled wood lignin. For cellulose and TMP, the effect was responsible for reducing the intensity of the Raman bands in the C-H stretch region. Several factors including sampling position, sample thickness, and moisture...

Surface-enhanced hyper-Raman spectroscopy with a picosecond laser: gold and copper colloids

NASA Astrophysics Data System (ADS)

Lipscomb, Leigh Ann; Nie, Shuming; Feng, Sibo; Yu, Nai-Teng

1990-07-01

We have obtained surface-enhanced hyper-Raman scattering (SEHRS) spectra of crystal violet, rhodamine 6G and Ru(trpy) (BPE) 32+ adsorbed on gold and copper colloidal surfaces (where trpy=2,2',2″-terpyridine, BPE=trans-bis(4-pyridyl)ethylene). Our results demonstrate that the SEHRS effect is not intrinsically restricted to a Ag substrate and that surface enhancements at the emitted hyper-Raman photon frequencies are not required for observing SEHRS signals.

Vibrational fingerprinting of bacterial pathogens by surface enhanced Raman scattering (SERS)

NASA Astrophysics Data System (ADS)

Premasiri, W. Ranjith; Moir, D. T.; Ziegler, Lawrence D.

2005-05-01

The surface enhanced Raman scattering (SERS) spectra of vegetative whole-cell bacteria were obtained using in-situ grown gold nanoparticle cluster-covered silicon dioxide substrates excited at 785 nm. SERS spectra of Gram-negative bacteria; E. coli and S. typhimurium, and Gram-positive bacteria; B. subtilis, B. cereus, B. thuringeinsis and B. anthracis Sterne, have been observed. Raman enhancement factors of ~104-105 per cell are found for both Gram positive and Gram negative bacteria on this novel SERS substrate. The bacterial SERS spectra are species specific and exhibit greater species differentiation and reduced spectral congestion than their corresponding non-SERS (bulk) Raman spectra. Fluorescence observed in the 785 nm excited bulk Raman emission of Bacillus species is not apparent in the corresponding SERS spectra. The surface enhancement effect allows the observation of Raman spectra at the single cell level excited by low incident laser powers (< 3 mW) and short data acquisition times (~20 sec.). Comparison with previous SERS studies suggests that these SERS vibrational signatures are sensitively dependent on the specific morphology and nature of the SERS active substrate. Exposure to biological environments, such as human blood serum, has an observable effect on the bacterial SERS spectra. However, reproducible, species specific SERS vibrational fingerprints are still obtained. The potential of SERS for detection and identification of bacteria with species specificity on these gold nanoparticle coated substrates is demonstrated by these results.

Tunable SERS signals of Rhodamine B molecules on Fe3O4@Au nanocomposite substrates controlled by magnetic field

NASA Astrophysics Data System (ADS)

Song, Hao; Fang, Rui Yang; Li, Ling

2018-02-01

In this work, we experimentally synthesized the Fe3O4@Au nanocomposites and used them as surface-enhanced Raman scattering (SERS) substrates. The Fe3O4@Au nanocomposites retained the metallic plasmon resonant effect and possessed the magnetic field controllable characteristics. The Raman spectra of Rhodamine B (RhB) probe molecules were studied under different external magnetic field. The magnitude of external magnetic field varied from 0 Gs to 700 Gs (1 Gs = 10-4 T) with intervals of 100 Gs. When the magnetic field magnitude increased, the Raman intensity of RhB probe molecules at 1356 cm-1 increased linearly. The slope of the linear fitting curves for the Raman intensity and area were 0.118/Gs and 3.700/Gs. The Raman enhancement could raise up to 7 times for RhB probe molecules when the magnetic field magnitude increased to 700 Gs. After removing the external magnetic field, the Raman peaks returned to its original intensity in several minutes. Under the external magnetic field, the Fe3O4@Au nanocomposites were concentrated, leading to the increase number of SERS "hot spots" and the surface Au density. The results show that the magnetic field controlled Fe3O4@Au nanocomposites can realize the enhanced and controllable SERS effect, which can be used in the reversible optical sensing and bio-medical applications.

Effect of pH value of probe molecule on the graphene oxide-based surface enhanced Raman scattering

NASA Astrophysics Data System (ADS)

Cui, Shao-li; Du, Xiao-qing; Zeng, Chao; Li, Lu; Bao, Jun

2017-06-01

The dependence of graphene oxide (GO)-based surface enhanced Raman scattering (SERS) on the pH value of probe molecule was investigated. Water-soluble copper phthalocyanine (TSCuPc) was used as probe molecule and its pH value was adjusted with HCl and NaOH solution. The Raman spectra of TSCuPc with pH equaling 3, 8, and 11 on GO base were tested, respectively. The results show that both Raman enhanced intensity and full width at half maximum (FWHM) of characteristic peaks vary with the pH value of TSCuPc. It is shown that there is no obvious spectral widening of TSCuPc characteristic peaks when TSCuPc is neutral or acidic, and the chemical enhancement intensity of neutral TSCuPc on GO is biggest. In contrast, when TSCuPc is alkaline, the characteristic Raman peaks between 1350 and 1600 cm-1 of TSCuPc on GO are much wider and the intensities of characteristic peaks decrease considerably. The reasons for the pH dependence of GO-based Raman spectra were explored by comparing the wettability of molecule droplet on GO and the absorbance of different pH-adjusted TSCuPc films. It is found that the effect of molecule's pH value on SERS can be contributed to the differences of concentration and distributions on GO surface for varied pH-treated molecule.

Molecular near-field antenna effect in resonance hyper-Raman scattering: Intermolecular vibronic intensity borrowing of solvent from solute through dipole-dipole and dipole-quadrupole interactions

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

Shimada, Rintaro; Hamaguchi, Hiro-o, E-mail: hhama@nctu.edu.tw

2014-05-28

We quantitatively interpret the recently discovered intriguing phenomenon related to resonance Hyper-Raman (HR) scattering. In resonance HR spectra of all-trans-β-carotene (β-carotene) in solution, vibrations of proximate solvent molecules are observed concomitantly with the solute β-carotene HR bands. It has been shown that these solvent bands are subject to marked intensity enhancements by more than 5 orders of magnitude under the presence of β-carotene. We have called this phenomenon the molecular-near field effect. Resonance HR spectra of β-carotene in benzene, deuterated benzene, cyclohexane, and deuterated cyclohexane have been measured precisely for a quantitative analysis of this effect. The assignments of themore » observed peaks are made by referring to the infrared, Raman, and HR spectra of neat solvents. It has been revealed that infrared active and some Raman active vibrations are active in the HR molecular near-field effect. The observed spectra in the form of difference spectra (between benzene/deuterated benzene and cyclohexane/deuterated cyclohexane) are quantitatively analyzed on the basis of the extended vibronic theory of resonance HR scattering. The theory incorporates the coupling of excited electronic states of β-carotene with the vibrations of a proximate solvent molecule through solute–solvent dipole–dipole and dipole–quadrupole interactions. It is shown that the infrared active modes arise from the dipole–dipole interaction, whereas Raman active modes from the dipole–quadrupole interaction. It is also shown that vibrations that give strongly polarized Raman bands are weak in the HR molecular near-field effect. The observed solvent HR spectra are simulated with the help of quantum chemical calculations for various orientations and distances of a solvent molecule with respect to the solute. The observed spectra are best simulated with random orientations of the solvent molecule at an intermolecular distance of 10 Å.« less

The molecular cues for the biological effects of ionizing radiation dose and post-irradiation time on human breast cancer SKBR3 cell line: A Raman spectroscopy study.

PubMed

Jafarzadeh, Naser; Mani-Varnosfaderani, Ahmad; Gilany, Kambiz; Eynali, Samira; Ghaznavi, Habib; Shakeri-Zadeh, Ali

2018-03-01

Radiotherapy is one of the main modalities of cancer treatment. The utility of Raman spectroscopy (RS) for detecting the distinct radiobiological responses in human cancer cells is currently under investigation. RS holds great promises to provide good opportunities for personalizing radiotherapy treatments. Here, we report the effects of the radiation dose and post-irradiation time on the molecular changes in the human breast cancer SKBR3 cells, using RS. The SKBR3 cells were irradiated by gamma radiation with different doses of 0, 1, 2, 4, and 6 Gy. The Raman signals were acquired 24 and 48 h after the gamma radiation. The collected Raman spectra were analyzed by different statistical methods such as principal component analysis, linear discriminant analysis, and genetic algorithm. A thorough analysis of the obtained Raman signals revealed that 2 Gy of gamma radiation induces remarkable molecular and structural changes in the SKBR3 cells. We found that the wavenumbers in the range of 1000-1400 cm -1 in Raman spectra are selective for discriminating between the effects of the different doses of irradiation. The results also revealed that longer post-irradiation time leads to the relaxation of the cells to their initial state. The molecular changes that occurred in the 2Gy samples were mostly reversible. On the other hand, the exposure to doses higher than 4Gy induced serious irreversible changes, mainly seen in 2700-2800 cm -1 in Raman spectra. The classification models developed in this study would help to predict the radiation-based molecular changes induced in the cancer cells by only using RS. Also, this designed framework may facilitate the process of biodosimetry. Copyright © 2018 Elsevier B.V. All rights reserved.

Infrared and Raman spectroscopic studies on alkali borate glasses: evidence of mixed alkali effect.

PubMed

Padmaja, G; Kistaiah, P

2009-03-19

A lithium-potassium-borate glass system containing manganese and iron cations has been thoroughly investigated in order to obtain information about the mixed alkali effect and the structural role of both the manganese and iron in such glass hosts. Mixed alkali borate glasses of the (30 - x)Li(2)O - xK(2)O - 10CdO/ZnO - 59B(2)O(3) (x = 0, 10, 15, 20, and 30) doped with 1MnO(2)/1Fe(2)O(3) system were prepared by a melt quench technique. The amorphous phase of the prepared glass samples was confirmed from their X-ray diffraction. The spectroscopic properties of glass samples were studied using infrared (IR) and Raman spectroscopic techniques. The density of all the prepared glasses was measured using Archimedes principle. Molar volumes were estimated from the density data. IR spectra of these glasses revealed a dramatic variation of three- and four-coordinated boron structures as a function of mixed alkali concentration. The vibrations due to Li-O, K-O, and MnO(4)/FeO(4) arrangements are consistent in all the compositions and show a nonlinear variation in the intensity with alkali content. Raman spectra of different alkali combinations with CdO and ZnO present drastic changes in the intensity of various Raman bands. The observation of disappearance and reappearance of IR and Raman bands as a function of various alkali concentrations is an important result pertaining to the mixed alkali effect in borate glasses. Acting as complementary spectroscopic techniques, both types of measurements, IR and Raman, revealed that the network structure of the studied glasses is mainly based on BO(3) and BO(4) units placed in different structural groups, the BO(3) units being dominant. The measured IR and Raman spectra of different glasses are used to clarify the optical properties of the present glasses correlating them with their structure and composition.

Raman Amplification and Tunable Pulse Delays in Silicon Waveguides

NASA Astrophysics Data System (ADS)

Rukhlenko, Ivan D.; Garanovich, Ivan L.; Premaratne, Malin; Sukhorukov, Andrey A.; Agrawal, Govind P.

2010-10-01

The nonlinear process of stimulated Raman scattering is important for silicon photonics as it enables optical amplification and lasing. However, generally employed numerical approaches provide very little insight into the contribution of different silicon Raman amplifier (SRA) parameters. In this paper, we solve the coupled pump-signal equations analytically and derive an exact formula for the envelope of a signal pulse when picosecond optical pulses are amplified inside a SRA pumped by a continuous-wave laser beam. Our solution is valid for an arbitrary pulse shape and fully accounts for the Raman gain-dispersion effects, including temporal broadening and group-velocity reduction. Our results are useful for optimizing the performance of SRAs and for engineering controllable signal delays.

Characterization and Discrimination of Gram-Positive Bacteria Using Raman Spectroscopy with the Aid of Principal Component Analysis.

PubMed

Colniță, Alia; Dina, Nicoleta Elena; Leopold, Nicolae; Vodnar, Dan Cristian; Bogdan, Diana; Porav, Sebastian Alin; David, Leontin

2017-09-01

Raman scattering and its particular effect, surface-enhanced Raman scattering (SERS), are whole-organism fingerprinting spectroscopic techniques that gain more and more popularity in bacterial detection. In this work, two relevant Gram-positive bacteria species, Lactobacillus casei ( L. casei ) and Listeria monocytogenes ( L. monocytogenes ) were characterized based on their Raman and SERS spectral fingerprints. The SERS spectra were used to identify the biochemical structures of the bacterial cell wall. Two synthesis methods of the SERS-active nanomaterials were used and the recorded spectra were analyzed. L. casei and L. monocytogenes were successfully discriminated by applying Principal Component Analysis (PCA) to their specific spectral data.

Characterization and Discrimination of Gram-Positive Bacteria Using Raman Spectroscopy with the Aid of Principal Component Analysis

PubMed Central

Leopold, Nicolae; Vodnar, Dan Cristian; Bogdan, Diana; Porav, Sebastian Alin; David, Leontin

2017-01-01

Raman scattering and its particular effect, surface-enhanced Raman scattering (SERS), are whole-organism fingerprinting spectroscopic techniques that gain more and more popularity in bacterial detection. In this work, two relevant Gram-positive bacteria species, Lactobacillus casei (L. casei) and Listeria monocytogenes (L. monocytogenes) were characterized based on their Raman and SERS spectral fingerprints. The SERS spectra were used to identify the biochemical structures of the bacterial cell wall. Two synthesis methods of the SERS-active nanomaterials were used and the recorded spectra were analyzed. L. casei and L. monocytogenes were successfully discriminated by applying Principal Component Analysis (PCA) to their specific spectral data. PMID:28862655

Temperature performance analysis of intersubband Raman laser in quantum cascade structures

NASA Astrophysics Data System (ADS)

Yousefvand, Hossein Reza

2017-06-01

In this paper we investigate the effects of temperature on the output characteristics of the intersubband Raman laser (RL) that integrated monolithically with a quantum cascade (QC) laser as an intracavity optical pump. The laser bandstructure is calculated by a self-consistent solution of Schrodinger-Poisson equations, and the employed physical model of carrier transport is based on a five-level carrier scattering rates; a two-level rate equations for the pump laser and a three-level scattering rates to include the stimulated Raman process in the RL. The temperature dependency of the relevant physical effects such as thermal broadening of the intersubband transitions (ISTs), thermally activated phonon emission lifetimes, and thermal backfilling of the final lasing state of the Raman process from the injector are included in the model. Using the presented model, the steady-state, small-signal modulation response and transient device characteristics are investigated for a range of sink temperatures (80-220 K). It is found that the main characteristics of the device such as output power, threshold current, Raman modal gain, turn-on delay time and 3-dB optical bandwidth are remarkably affected by the temperature.

A Raman scattering and FT-IR spectroscopic study on the effect of the solar radiation in Antarctica on bovine cornea

NASA Astrophysics Data System (ADS)

Yamamoto, Tatsuyuki; Murakami, Naoki; Yoshikiyo, Keisuke; Takahashi, Tetsuya; Yamamoto, Naoyuki

2010-01-01

The Raman scattering and FT-IR spectra of the corneas, transported to the Syowa station in Antarctica and exposed to the solar radiation of the mid-summer for four weeks, were studied to reveal that type IV collagen involved in corneas were fragmented. The amide I and III Raman bands were observed at 1660 and 1245 cm -1, respectively, and the amide I and II infrared bands were observed at 1655 and 1545 cm -1, respectively, for original corneas before exposure. The background of Raman signals prominently increased and the ratio of amide II infrared band versus amide I decreased by the solar radiation in Antarctica. The control experiment using an artificial UV lamp was also performed in laboratory. The decline rate of the amide II/amide I was utilized for estimating the degree of fragmentation of collagen, to reveal that the addition of vitamin C suppressed the reaction while the addition of sugars promoted it. The effect of the solar radiation in Antarctica on the corneas was estimated as the same as the artificial UV lamp of four weeks (Raman) or one week (FT-IR) exposure.

Effect of Intermolecular Distance on Surface-Plasmon-Assisted Catalysis.

PubMed

Wu, Shiwei; Liu, Yu; Ma, Caiqing; Wang, Jing; Zhang, Yao; Song, Peng; Xia, Lixin

2018-06-26

4-Aminothiophenol (PATP) and 4-aminophenyl disulfide (APDS) in contact with silver will form H 2 N-C 6 H 4 -S-Ag (PATP-Ag), and under the conditions of surface-enhanced Raman spectroscopy (SERS), a coupling reaction will generate 4,4-dimercaptoazobenzene (DMAB). DMAB is strongly Raman-active, showing strong peaks at ν ≈ 1140, 1390, and 1432 cm -1 , and is widely used in surface-plasmon-assisted catalysis. Using APDS, PATP, p-nitrothiophenol (PNTP), and p-nitrodiphenyl disulfide (NPDS) as probe molecules, Raman spectroscopy and imaging techniques have been used to study the effect of intermolecular distance on surface-plasmon-assisted catalysis. Theoretically, PATP-Ag formed from APDS will be bound at proximal Ag atoms on the Ag surface due to S-S bond cleavage. The results show that APDS is more prone to surface-plasmon-assisted catalytic coupling due to the smaller distance between surface PATP-Ag moieties than those derived from PATP. Therefore, APDS has a higher reaction efficiency, better Raman activity, and better Raman imaging than does PATP. Analogous experiments with PNTP and NPDS gave similar results. Thus, this technique has great application prospects in the fields of surface chemistry and materials chemistry.

Following the mechanisms of bacteriostatic versus bactericidal action using Raman spectroscopy.

PubMed

Bernatová, Silvie; Samek, Ota; Pilát, Zdeněk; Serý, Mojmír; Ježek, Jan; Jákl, Petr; Siler, Martin; Krzyžánek, Vladislav; Zemánek, Pavel; Holá, Veronika; Dvořáčková, Milada; Růžička, Filip

2013-10-24

Antibiotics cure infections by influencing bacterial growth or viability. Antibiotics can be divided to two groups on the basis of their effect on microbial cells through two main mechanisms, which are either bactericidal or bacteriostatic. Bactericidal antibiotics kill the bacteria and bacteriostatic antibiotics suppress the growth of bacteria (keep them in the stationary phase of growth). One of many factors to predict a favorable clinical outcome of the potential action of antimicrobial chemicals may be provided using in vitro bactericidal/bacteriostatic data (e.g., minimum inhibitory concentrations-MICs). Consequently, MICs are used in clinical situations mainly to confirm resistance, and to determine the in vitro activities of new antimicrobials. We report on the combination of data obtained from MICs with information on microorganisms' "fingerprint" (e.g., DNA/RNA, and proteins) provided by Raman spectroscopy. Thus, we could follow mechanisms of the bacteriostatic versus bactericidal action simply by detecting the Raman bands corresponding to DNA. The Raman spectra of Staphylococcus epidermidis treated with clindamycin (a bacteriostatic agent) indeed show little effect on DNA which is in contrast with the action of ciprofloxacin (a bactericidal agent), where the Raman spectra show a decrease in strength of the signal assigned to DNA, suggesting DNA fragmentation.

Periodic driving control of Raman-induced spin-orbit coupling in Bose-Einstein condensates: The heating mechanisms

NASA Astrophysics Data System (ADS)

Gomez Llorente, J. M.; Plata, J.

2016-06-01

We focus on a technique recently implemented for controlling the magnitude of synthetic spin-orbit coupling (SOC) in ultracold atoms in the Raman-coupling scenario. This technique uses a periodic modulation of the Raman-coupling amplitude to tune the SOC. Specifically, it has been shown that the effect of a high-frequency sinusoidal modulation of the Raman-laser intensity can be incorporated into the undriven Hamiltonian via effective parameters, whose adiabatic variation can therefore be used to tune the SOC. Here, we characterize the heating mechanisms that can be relevant to this method. We identify the main mechanism responsible for the heating observed in the experiments as basically rooted in driving-induced transfer of population to excited states. Characteristics of that process determined by the harmonic trapping, the decay of the excited states, and the technique used for preparing the system are discussed. Additional heating, rooted in departures from adiabaticity in the variation of the effective parameters, is also described. Our analytical study provides some clues that may be useful in the design of strategies for curbing the effects of heating on the efficiency of the control methods.

Gap-enhanced Raman tags for high-contrast sentinel lymph node imaging.

PubMed

Bao, Zhouzhou; Zhang, Yuqing; Tan, Ziyang; Yin, Xia; Di, Wen; Ye, Jian

2018-05-01

The sentinel lymph node (SLN) biopsy is gaining in popularity as a procedure to investigate the lymphatic metastasis of malignant tumors. The commonly used techniques to identify the SLNs in clinical practice are blue dyes-guided visualization, radioisotope-based detection and near-infrared fluorescence imaging. However, all these methods have not been found to perfectly fit the clinical criteria with issues such as short retention time in SLN, poor spatial resolution, autofluorescence, low photostability and high cost. In this study, we have reported a new type of nanoprobes, named, gap-enhanced Raman tags (GERTs) for the SLN Raman imaging. With the advantageous features including unique "fingerprint" Raman signal, strong Raman enhancement, high photostability, good biocompatibility and extra-long retention time, we have demonstrated that GERTs are greatly favorable for high-contrast and deep SLN Raman imaging, which meanwhile reveals the dynamic migration behavior of the probes entering the SLN. In addition, a quantitative volumetric Raman imaging (qVRI) data-processing method is employed to acquire a high-resolution 3-dimensional (3D) margin of SLN as well as the content variation of GERTs in the SLN. Moreover, SLN detection could be realized via a cost-effective commercial portable Raman scanner. Therefore, GERTs hold the great potential to be translated in clinical application for accurate and intraoperative location of the SLN. Copyright © 2018 Elsevier Ltd. All rights reserved.

Polarized Raman spectroscopic characterization of normal and oral cancer blood plasma

NASA Astrophysics Data System (ADS)

Pachaiappan, Rekha; Prakasarao, Aruna; Singaravelu, Ganesan

2017-02-01

In India oral cancer ranks the top due to the habitual usage of tobacco in its various forms and remains the major burden. Hence priority is given for early diagnosis as it is the better solution for cure or to improve the survival rate. For the past three decades, optical spectroscopic techniques have shown its capacity in the discrimination of normal and malignant samples. Many research works have conventional Raman in the effective detection of cancer using the variations in bond vibrations of the molecules. However in addition polarized Raman provides the orientation and symmetry of biomolecules. If so can polarized Raman be the better choice than the conventional Raman in the detection of cancer? The present study aimed to found the answer for the above query. The conventional and polarized Raman spectra were acquired for the same set of blood plasma samples of normal subjects and oral malignant (OSCC) patients. Thus, obtained Raman spectral data were compared using linear discriminant analysis coupled with artificial neural network (LDA-ANN). The depolarization ratio of biomolecules such as antioxidant, amino acid, protein and nucleic acid bases present in blood plasma was proven to be the best attributes in the categorization of the groups. The polarized Raman results were promising in discriminating oral cancer blood plasma from that of normal blood plasma with improved efficiency. The results will be discussed in detail.

Improved molecular fingerprint analysis employing multi-branched gold nanoparticles in conjunction with surface-enhanced Raman scattering.

PubMed

Johnston, Jencilin; Taylor, Erik N; Gilbert, Richard J; Webster, Thomas J

2016-01-01

Vibrational spectroscopy is a powerful analytical tool that assesses molecular properties based on spectroscopic signatures. In this study, the effect of gold nanoparticle morphology (spherical vs multi-branched) was assessed for the characterization of a Raman signal (ie, molecular fingerprint) that may be helpful for numerous medical applications. Multi-branched gold nanoparticles (MBAuNPs) were fabricated using a green chemistry method which employed the reduction of gold ion solute by 2-[4-(2-hydroxyethyl)-1-piperazyl] ethane sulfonic acid. Two types of reporter dyes, indocyanine (IR820 and IR792) and carbocyanine (DTTC [3,3'-diethylthiatricarbocyanine iodide] and DTDC [3,3'-diethylthiadicarbocyanine iodide]), were functionalized to the surface of the MBAuNPs and stabilized with denatured bovine serum albumin, thus forming the surface-enhanced Raman spectroscopy tag. Fluorescein isothiocyanate-conjugated anti-epidermal growth factor receptor to the surface-enhanced Raman spectroscopy tags and the properties of the resulting conjugates were assessed through determination of the Raman signal. Using the MBAuNP Raman probes synthesized in this manner, we demonstrated that MBAuNP provided significantly more surface-enhanced Raman scattering signal when compared with the associated spherical gold nanoparticle of similar size and concentration. MBAuNP enhancements were retained in the surface-enhanced Raman spectroscopy tags complexed to anti-epidermal growth factor receptor, providing evidence that this could be a useful biological probe for enhanced Raman molecular fingerprinting. Furthermore, while utilizing IR820 as a novel reporter dye linked with MBAuNP, superior Raman signal fingerprint results were obtained. Such results provide significant promise for the use of MBAuNP in the detection of numerous diseases for which biologically specific surface markers exist.

Improved molecular fingerprint analysis employing multi-branched gold nanoparticles in conjunction with surface-enhanced Raman scattering

PubMed Central

Johnston, Jencilin; Taylor, Erik N; Gilbert, Richard J; Webster, Thomas J

2016-01-01

Vibrational spectroscopy is a powerful analytical tool that assesses molecular properties based on spectroscopic signatures. In this study, the effect of gold nanoparticle morphology (spherical vs multi-branched) was assessed for the characterization of a Raman signal (ie, molecular fingerprint) that may be helpful for numerous medical applications. Multi-branched gold nanoparticles (MBAuNPs) were fabricated using a green chemistry method which employed the reduction of gold ion solute by 2-[4-(2-hydroxyethyl)-1-piperazyl] ethane sulfonic acid. Two types of reporter dyes, indocyanine (IR820 and IR792) and carbocyanine (DTTC [3,3′-diethylthiatricarbocyanine iodide] and DTDC [3,3′-diethylthiadicarbocyanine iodide]), were functionalized to the surface of the MBAuNPs and stabilized with denatured bovine serum albumin, thus forming the surface-enhanced Raman spectroscopy tag. Fluorescein isothiocyanate-conjugated anti-epidermal growth factor receptor to the surface-enhanced Raman spectroscopy tags and the properties of the resulting conjugates were assessed through determination of the Raman signal. Using the MBAuNP Raman probes synthesized in this manner, we demonstrated that MBAuNP provided significantly more surface-enhanced Raman scattering signal when compared with the associated spherical gold nanoparticle of similar size and concentration. MBAuNP enhancements were retained in the surface-enhanced Raman spectroscopy tags complexed to anti-epidermal growth factor receptor, providing evidence that this could be a useful biological probe for enhanced Raman molecular fingerprinting. Furthermore, while utilizing IR820 as a novel reporter dye linked with MBAuNP, superior Raman signal fingerprint results were obtained. Such results provide significant promise for the use of MBAuNP in the detection of numerous diseases for which biologically specific surface markers exist. PMID:26730189

Fe-Ti-Cr-Oxides in Martian Meteorite EETA79001 Studied by Point-counting Procedure Using Raman Spectroscopy

NASA Technical Reports Server (NTRS)

Wang, Alian; Kuebler, Karla E.; Jolliff, Bradley L.; Haskin, Larry A.

2003-01-01

Fe-Ti-Cr-Oxide minerals contain much information about rock petrogenesis and alteration. Among the most important in the petrology of common intrusive and extrusive rocks are those of the FeO-TiO2-Cr2O3 compositional system chromite, ulv spinel-magnetite, and ilmenite-hematite. These minerals retain memories of oxygen fugacity. Their exsolution into companion mineral pairs give constraints on formation temperature and cooling rate. Laser Raman spectroscopy is anticipated to be a powerful technique for characterization of materials on the surface of Mars. A Mars Microbeam Raman Spectrometer (MMRS) is under development. It combines a micro sized laser beam and an automatic point-counting mechanism, and so can detect minor minerals or weak Raman-scattering phases such as Fe- Ti-Cr-oxides in mixtures (rocks & soils), and provide information on grain size and mineral mode. Most Fe-Ti-Cr-oxides produce weaker Raman signals than those from oxyanionic minerals, e.g. carbonates, sulfates, phosphates, and silicates, partly because most of them are intrinsically weaker Raman scatters, and partly because their dark colors limit the penetration depth of the excitation laser beam (visible wavelength) and of the Raman radiation produced. The purpose of this study is to show how well the Fe-Ti-Cr-oxides can be characterized by on-surface planetary exploration using Raman spectroscopy. We studied the basic Raman features of common examples of these minerals using well-characterized individual mineral grains. The knowledge gained was then used to study the Fe-Ti-Cr-oxides in Martian meteorite EETA79001, especially effects of compositional and structural variations on their Raman features.

Study of spin-ordering and spin-reorientation transitions in hexagonal manganites through Raman spectroscopy

PubMed Central

Chen, Xiang-Bai; Hien, Nguyen Thi Minh; Han, Kiok; Nam, Ji-Yeon; Huyen, Nguyen Thi; Shin, Seong-Il; Wang, Xueyun; Cheong, S. W.; Lee, D.; Noh, T. W.; Sung, N. H.; Cho, B. K.; Yang, In-Sang

2015-01-01

Spin-wave (magnon) scattering, when clearly observed by Raman spectroscopy, can be simple and powerful for studying magnetic phase transitions. In this paper, we present how to observe magnon scattering clearly by Raman spectroscopy, then apply the Raman method to study spin-ordering and spin-reorientation transitions of hexagonal manganite single crystal and thin films and compare directly with the results of magnetization measurements. Our results show that by choosing strong resonance condition and appropriate polarization configuration, magnon scattering can be clearly observed, and the temperature dependence of magnon scattering can be simple and powerful quantity for investigating spin-ordering as well as spin-reorientation transitions. Especially, the Raman method would be very helpful for investigating the weak spin-reorientation transitions by selectively probing the magnons in the Mn3+ sublattices, while leaving out the strong effects of paramagnetic moments of the rare earth ions. PMID:26300075

Bioanalytical applications of SERS (surface-enhanced Raman spectroscopy).

PubMed

Hudson, Stephen D; Chumanov, George

2009-06-01

Surface-enhanced Raman scattering (SERS) is a powerful technique for analyzing biological samples as it can rapidly and nondestructively provide chemical and, in some cases, structural information about molecules in aqueous environments. In the Raman scattering process, both visible and near-infrared (NIR) wavelengths of light can be used to induce polarization of Raman-active molecules, leading to inelastic light scattering that yields specific molecular vibrational information. The development of surface enhancement has enabled Raman scattering to be an effective tool for qualitative as well as quantitative measurements with high sensitivity and specificity. Recent advances have led to many novel applications of SERS for biological analyses, resulting in new insights for biochemistry and molecular biology, the detection of biological warfare agents, and medical diagnostics for cancer, diabetes, and other diseases. This trend article highlights many of these recent investigations and provides a brief outlook in order to assess possible future directions of SERS as a bioanalytical tool.

Raman scattering from TO phonons in (GaAs)n/(AlAs)n superlattices

NASA Astrophysics Data System (ADS)

Wang, Z. P.; Han, H. X.; Li, G. H.; Jiang, D. S.; Ploog, K.

1988-10-01

(GaAS)n/(AlAs)n superlattices with n=4, 6, and 8 grown by molecular-beam epitaxy on (001)-oriented GaAs substrates were investigated by Raman scattering. In a strict backscattering geometry, confined TO-phonon modes with E symmetry are Raman forbidden. However, the effects due to near-Brewster-angle incidence and a large aperture of the scattering-light collecting lens create a small wave-vector component along the (110) orientation, and thus induce a Raman activity of TO phonons. When we take X∥[11¯0], Y∥[110], and Z∥[001], in the near-Z(YX)Z¯ backscattering configuration confined LO-phonon modes are Raman inactive. Using this configuration, we have for the first time observed both GaAs-like and AlAs-like confined TO-phonon modes at room temperature and under off-resonance conditions.

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.

Monitoring electrostatically-induced deflection, strain and doping in suspended graphene using Raman spectroscopy

NASA Astrophysics Data System (ADS)

Metten, Dominik; Froehlicher, Guillaume; Berciaud, Stéphane

2017-03-01

Electrostatic gating offers elegant ways to simultaneously strain and dope atomically thin membranes. Here, we report on a detailed in situ Raman scattering study on graphene, suspended over a Si/SiO2 substrate. In such a layered structure, the intensity of the Raman G- and 2D-mode features of graphene are strongly modulated by optical interference effects and allow an accurate determination of the electrostatically-induced membrane deflection, up to irreversible collapse. The membrane deflection is successfully described by an electromechanical model, which we also use to provide useful guidelines for device engineering. In addition, electrostatically-induced tensile strain is determined by examining the softening of the Raman features. Due to a small residual charge inhomogeneity, we find that non-adiabatic anomalous phonon softening is negligible compared to strain-induced phonon softening. These results open perspectives for innovative Raman scattering-based readout schemes in two-dimensional nanoresonators.

Resonance Raman and UV-visible spectroscopy of black dyes on textiles.

PubMed

Abbott, Laurence C; Batchelor, Stephen N; Smith, John R Lindsay; Moore, John N

2010-10-10

Resonance Raman and UV-visible diffuse reflectance spectra were recorded from samples of cotton, viscose, polyester, nylon, and acrylic textile swatches dyed black with one of seven single dyes, a mixture of two dyes, or one of seven mixtures of three dyes. The samples generally gave characteristic Raman spectra of the dyes, demonstrating that the technique is applicable for the forensic analysis of dyed black textiles. Survey studies of the widely used dye Reactive Black 5 show that essentially the same Raman spectrum is obtained on bulk sampling from the dye in solution, on viscose, on cotton at different uptakes, and on microscope sampling from the dye in cotton threads and single fibres. The effects of laser irradiation on the Raman bands and emission backgrounds from textile samples with and without dye are also reported. Copyright © 2010 Elsevier Ireland Ltd. All rights reserved.

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.

Picosecond transient backward stimulated Raman scattering and pumping of femtosecond dye lasers

NASA Astrophysics Data System (ADS)

Arrivo, Steven M.; Spears, Kenneth G.; Sipior, Jeffrey

1995-02-01

We report studies of transient, backward stimulated, Raman scattering (TBSRS) in solvents with a 10 Hz, 27 ps, 532 nm pump laser. The TBSRS effect was used to create pulses at 545 nm and 630 nm with durations of 2-3 ps and 5-10 μJ of energy. The duration, energy and fluctuations of the Raman pulse were studied as a function of pump energy and focal parameters. A 5 μJ Raman pulse was amplified in either a Raman amplifier or two stage dye amplifier to 1 mJ levels. A 545 nm pulse of 3 ps duration was generated in CCl 4 and was then used to pump a short cavity dye laser (SCDL). The SCDL oscillator and a 5 stage dye amplifier provided a pulse of 700 fs and 400 μJ that was tunable near 590 nm.

Resonance electronic Raman scattering in rare earth crystals

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

Williams, G.M.

1988-11-10

The intensities of Raman scattering transitions between electronic energy levels of trivalent rare earth ions doped into transparent crystals were measured and compared to theory. A particle emphasis was placed on the examination of the effect of intermediate state resonances on the Raman scattering intensities. Two specific systems were studied: Ce/sup 3 +/(4f/sup 1/) in single crystals of LuPO/sub 4/ and Er/sup 3 +/(4f/sup 11/) in single crystals of ErPO/sub 4/. 134 refs., 92 figs., 33 tabs.

Raman Scattering at Plasmonic Junctions Shorted by Conductive Molecular Bridges

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

El-Khoury, Patrick Z.; Hu, Dehong; Apkarian, V. Ara

2013-04-10

Intensity spikes in Raman scattering, accompanied by switching between line spectra and band spectra, can be assigned to shorting the junction plasmon through molecular conductive bridges. This is demonstrated through Raman trajectories recorded at a plasmonic junction formed by a gold AFM tip in contact with a silver surface coated either with biphenyl-4,4’-dithiol or biphenyl-4-thiol. The fluctuations are absent in the monothiol. In effect, the making and breaking of chemical bonds is tracked.

Study on the noncoincidence effect phenomenon using matrix isolated Raman spectra and the proposed structural organization model of acetone in condense phase

NASA Astrophysics Data System (ADS)

Xu, Wenwen; Wu, Fengqi; Zhao, Yanying; Zhou, Ran; Wang, Huigang; Zheng, Xuming; Ni, Bukuo

2017-03-01

The isotropic and anisotropic Raman spectra of acetone and deuterated acetone isolated in an argon matrix have been recorded for the understanding of noncoincidence effect (NCE) phenomenon. According to the matrix isolated Raman spectra and DFT calculations, we proposed aggregated model for the explanations of the acetone C=O vibration NCE phenomenon and its concentration effect. The experimental data were in consistence with the DFT calculations performed at the B3LYP-D3/6-311 G (d,p) levels based on the proposed model. The experimental identification of the monomer, dimer and trimer are reported here, and the dynamic of the transformation from monomer to aggregated structure can be easily controlled by tuning annealing temperature.

Temperature dependent Raman investigation of multiwall carbon nanotubes

NASA Astrophysics Data System (ADS)

Dilawar Sharma, Nita; Singh, Jasveer; Vijay, Aditi

2018-04-01

We report anomalous observations in our investigations of the temperature dependent Raman spectroscopic measurement of multiwall carbon nanotubes. The Micro-Raman spectra were recorded with the laser source having 514.5 nm wavelength and within the temperature range of 80-440 K. The major Raman bands, the G and D band, are observed at 1584 and 1348 cm-1, respectively, at ambient. The absence of the radial breathing mode confirms the multiwall nature of carbon nanotubes. It has been observed that with an increase in the temperature above 120 K, there is a shift in Raman bands towards the higher wave-number region. However, a drop in the G and D bands is observed from 80 to 120 K which was not observed for the second order band. Thereafter, all Raman modes exhibited mode hardening up to about 320 K followed by mild softening of the phonon modes. Linear temperature coefficients were found to have higher contribution to mode hardening as compared to higher order terms. Total anharmonicity estimation shows a predominant effect of the quasi-harmonic term as compared to the true anharmonic term.

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.

A New Way to Measure Cirrus Ice Water Content by Using Ice Raman Scatter with Raman Lidar

NASA Technical Reports Server (NTRS)

Wang, Zhien; Whiteman, David N.; Demoz, Belay; Veselovskii, Igor

2004-01-01

High and cold cirrus clouds mainly contain irregular ice crystals, such as, columns, hexagonal plates, bullet rosettes, and dendrites, and have different impacts on the climate system than low-level clouds, such as stratus, stratocumulus, and cumulus. The radiative effects of cirrus clouds on the current and future climate depend strongly on cirrus cloud microphysical properties including ice water content (IWC) and ice crystal sizes, which are mostly an unknown aspect of cinus clouds. Because of the natural complexity of cirrus clouds and their high locations, it is a challenging task to get them accurately by both remote sensing and in situ sampling. This study presents a new method to remotely sense cirrus microphysical properties by using ice Raman scatter with a Raman lidar. The intensity of Raman scattering is fundamentally proportional to the number of molecules involved. Therefore, ice Raman scattering signal provides a more direct way to measure IWC than other remote sensing methods. Case studies show that this method has the potential to provide essential information of cirrus microphysical properties to study cloud physical processes in cirrus clouds.

Error and uncertainty in Raman thermal conductivity measurements

DOE PAGES

Thomas Edwin Beechem; Yates, Luke; Graham, Samuel

2015-04-22

We investigated error and uncertainty in Raman thermal conductivity measurements via finite element based numerical simulation of two geometries often employed -- Joule-heating of a wire and laser-heating of a suspended wafer. Using this methodology, the accuracy and precision of the Raman-derived thermal conductivity are shown to depend on (1) assumptions within the analytical model used in the deduction of thermal conductivity, (2) uncertainty in the quantification of heat flux and temperature, and (3) the evolution of thermomechanical stress during testing. Apart from the influence of stress, errors of 5% coupled with uncertainties of ±15% are achievable for most materialsmore » under conditions typical of Raman thermometry experiments. Error can increase to >20%, however, for materials having highly temperature dependent thermal conductivities or, in some materials, when thermomechanical stress develops concurrent with the heating. A dimensionless parameter -- termed the Raman stress factor -- is derived to identify when stress effects will induce large levels of error. Together, the results compare the utility of Raman based conductivity measurements relative to more established techniques while at the same time identifying situations where its use is most efficacious.« less

Raman Studies on Pre- and Post-Processed CVD Graphene Films Grown under Various Nitrogen Carrier Gas Flows

NASA Astrophysics Data System (ADS)

Beh, K. P.; Yam, F. K.; Abdalrheem, Raed; Ng, Y. Z.; Suhaimi, F. H. A.; Lim, H. S.; Mat Jafri, M. Z.

2018-04-01

In this work, graphene films were grown on copper substrates using chemical vapour deposition method under various N2 carrier flow rate. The samples were characterized using Raman spectroscopy. Three sets of Raman measurements have been performed: graphene/Cu (as-grown samples), pre-annealed graphene/glass, and post-annealed graphene/glass. It was found that the Raman spectra of graphene/Cu samples possessed a hump-shaped baseline, additionally higher signal-to-noise ratio (SNR) that leads to attenuation graphene-related bands. Significant improvement of SNR and flat baseline were observed for graphene films transferred on glass substrate. Further analysis on the remaining sets of Raman spectra highlighted minute traces of polymethyl methacrylate (PMMA) could yield misleading results. Hence, the set of Raman spectra on annealed graphene/glass samples would be suitable in further elucidating the effects of N2 carrier flow towards graphene growth. From there, higher N2 flow implied dilution of methanol/H2 mixture, limiting interactions between reactants and substrate. This leads to smaller crystallite size and lesser graphene layers.

Surface enhanced Raman optical activity of molecules on orientationally averaged substrates: theory of electromagnetic effects.

PubMed

Janesko, Benjamin G; Scuseria, Gustavo E

2006-09-28

We present a model for electromagnetic enhancements in surface enhanced Raman optical activity (SEROA) spectroscopy. The model extends previous treatments of SEROA to substrates, such as metal nanoparticles in solution, that are orientationally averaged with respect to the laboratory frame. Our theoretical treatment combines analytical expressions for unenhanced Raman optical activity with molecular polarizability tensors that are dressed by the substrate's electromagnetic enhancements. We evaluate enhancements from model substrates to determine preliminary scaling laws and selection rules for SEROA. We find that dipolar substrates enhance Raman optical activity (ROA) scattering less than Raman scattering. Evanescent gradient contributions to orientationally averaged ROA scale to first or higher orders in the gradient of the incident plane-wave field. These evanescent gradient contributions may be large for substrates with quadrupolar responses to the plane-wave field gradient. Some substrates may also show a ROA contribution that depends only on the molecular electric dipole-electric dipole polarizability. These conclusions are illustrated via numerical calculations of surface enhanced Raman and ROA spectra from (R)-(-)-bromochlorofluoromethane on various model substrates.

Integrated waveguide and nanostructured sensor platform for surface-enhanced Raman spectroscopy

NASA Astrophysics Data System (ADS)

Pearce, Stuart J.; Pollard, Michael E.; Oo, SweZin; Chen, Ruiqi; Kalsi, Sumit; Charlton, Martin D. B.

2014-01-01

Limitations of current sensors include large dimensions, sometimes limited sensitivity and inherent single-parameter measurement capability. Surface-enhanced Raman spectroscopy can be utilized for environment and pharmaceutical applications with the intensity of the Raman scattering enhanced by a factor of 10. By fabricating and characterizing an integrated optical waveguide beneath a nanostructured precious metal coated surface a new surface-enhanced Raman spectroscopy sensing arrangement can be achieved. Nanostructured sensors can provide both multiparameter and high-resolution sensing. Using the slab waveguide core to interrogate the nanostructures at the base allows for the emission to reach discrete sensing areas effectively and should provide ideal parameters for maximum Raman interactions. Thin slab waveguide films of silicon oxynitride were etched and gold coated to create localized nanostructured sensing areas of various pitch, diameter, and shape. These were interrogated using a Ti:Sapphire laser tuned to 785-nm end coupled into the slab waveguide. The nanostructured sensors vertically projected a Raman signal, which was used to actively detect a thin layer of benzyl mercaptan attached to the sensors.

Ps laser pulse induced stimulated Raman scattering of ammonium nitrate dissolved in water

NASA Astrophysics Data System (ADS)

Kumar, V. Rakesh; Kiran, P. Prem

2018-04-01

An intense picosecond laser pulse focused into a liquid medium generates a shock wave in the focal region. This shock wave while propagating into the medium varies the pressure and temperature of the liquid locally leading to the appearance of novel phases which are manifested by the appearance of Raman peaks. We present the phase changes of ammonium nitrate (AN) dissolved in water by studying the forward and backward stimulated Raman Scattering (FSRS and BSRS) signals due to propagation of 30 ps laser pulse induced shockwaves. The dominant peak corresponding to the NO3- symmetric stretching mode is observed with a Raman shift of 1045 cm-1 which represents phase IV of AN with an orthogonal crystalline structure. Apart from this peak, the dominant mode of liquid phase of water with a Raman shift of 3400 cm-1 and an ice VII peak at a Raman shift of 3050 cm-1 confirming the pressure of 10 GPa is observed. The effect of the concentration and input energy on the appearance of the phases will be presented.

Tunable and highly reproducible surface-enhanced Raman scattering substrates made from large-scale nanoparticle arrays based on periodically poled LiNbO3 templates

NASA Astrophysics Data System (ADS)

Liu, Xiaoyan; Kitamura, Kenji; Yu, Qiuming; Xu, Jiajie; Osada, Minoru; Takahiro, Nagata; Li, Jiangyu; Cao, Guozhong

2013-10-01

This work describes novel surface-enhanced Raman scattering (SERS) substrates based on ferroelectric periodically poled LiNbO3 templates. The templates comprise silver nanoparticles (AgNPs), the size and position of which are tailored by ferroelectric lithography. The substrate has uniform and large sampling areas that show SERS effective with excellent signal reproducibility, for which the fabrication protocol is advantageous in its simplicity. We demonstrate ferroelectric-based SERS substrates with particle sizes ranging from 30 to 70 nm and present tunable SERS effect from Raman active 4-mercaptopyridine molecules attached to AgNPs when excited by a laser source at 514 nm.

Laser remote sensing of tropospheric aerosol over Southern Ireland using a backscatter Raman LIDAR

NASA Astrophysics Data System (ADS)

Ruth, Albert A.; Acheson, Karen; Apituley, Arnoud; Chaikovsky, Anatoli; Nicolae, Doina; Ortiz-Amezcua, Pablo; Stoyanov, Dimitar; Trickl, Thomas

2016-04-01

Raman backscatter coefficients, extinction coefficients and lidar ratios were measured with a ground based Raman lidar system at University College Cork, Ireland, during the periods of July 2012 - August 2012, April 2013 - December 2013 and March 2014 - May 2014. Statistical analysis of these parameters in this time provided information about seasonal effects of Raman backscatter coefficients and the altitude of the top of the planetary boundary layer. The mean of the altitude of the top of the planetary boundary layer over these time periods is 950 ± 302 m. The values are larger in summer, 1206 ± 367 m, than in winter, 735 m. The altitude of the top of the planetary boundary layer measured at Cork is lower than most EARLINET stations. Raman backscatter coefficients above and altitude of 2 km are highest in summer and spring where the values are greater than 0.28 Mm-1 sr-1. Winter values of Raman backscatter coefficient are less than 0.06 Mm-1 sr-1. These seasonal effects are consistent with most EARLINET stations. Large aerosol loads were detected in July 2013 due to a Canadian forest fire event. HYSPLIT air-mass back trajectory models were used to trace the origin of the detected aerosol layers. The aerosol forecast model, MACC, was used to further investigate and verify the propagation of the smoke. The Lidar ratio values and Klett and Raman backscatter coefficients at Cork, for the 4th July, the 7th to 9th of July and the 11th July were compared with observations at Cabauw, Minsk, Granada, Bucharest, Sofia and Garmisch. Lidar ratio values for the smoke detected at Cork were determined to be between 33 sr and 62 sr. The poster will discuss the seasonal changes of Raman backscatter coefficients and the altitude of the top of the planetary boundary layer at Cork. An investigation of a Canadian forest fire event measured at Cork will be compared with other data from the EARLINET database.

Stimulated Raman scattering in AsSe2-As2S5 microstructured optical fiber

NASA Astrophysics Data System (ADS)

Gao, Weiqing; Ni, Chenquan; Xu, Qiang; Li, Xue; Chen, Xiangcai; Chen, Li; Wen, Zhenqiang; Cheng, Tonglei; Xue, Xiaojie; Suzuki, Takenobu; Ohishi, Yasutake

2017-02-01

We demonstrate the effects of stimulated Raman scattering (SRS) in the all-solid-core chalcogenide microstructured optical fibers (MOFs) with AsSe2 core and As2S5 cladding, which are fabricated by the rod-in-tube drawing technique. The core diameters of the MOFs are 6.3 (Fiber I), 3.0 (Fiber II), 2.6 (Fiber III) and 2.2 (Fiber IV) μm, respectively. The chromatic dispersion of the fundamental mode in Fibers I-IV is simulated by the full-vectorial mode solver technique. The first-order Stokes wave is investigated in the fibers with different core diameters pumped by the picosecond pulses at 1958 nm. In Fiber I, no obvious Raman peak is observed with the pump power increasing, because the effective nonlinearity is not high. In Fiber II, a Raman Stokes peak at 2065 nm begins to emerge at the pump power of 110 mW. The conversion efficiency is as weak as -36.6 dB at 150 mW pumping. In Fiber III, the first-order Raman peak at 2060 nm begins to emerge at 40 mW pumping. The conversion efficiency is -15.0 dB, which is 21.6 dB higher than that in Fiber II. In Fiber IV, the Stokes peak at 2070 nm begins to appear at 56 mW pumping. The maximum conversion efficiency of the first-order Stokes wave is obtained in the MOF with the core diameter of 2.6 μm. The evolution of the first-order Stokes wave with pump power and fiber length is investigated. This is the first demonstration of Raman effects in the AsSe2-As2S5 MOF, to the best of our knowledge.

Effect of the crushing process on Raman analyses: consequences for the Mars 2018 mission

NASA Astrophysics Data System (ADS)

Foucher, F.; López Reyes, G.; Bost, N.; Rull, F.; Rüßmann, P.; Westall, F.

2012-04-01

The Pasteur payload of the international 2018 Mars mission comprises a Raman spectrometer as part of its instrument suite. Analyses with this instrument will be made on crushed samples. The crushing process will cause loss of important structural context and could change the physical properties of the studied materials resulting in misinterpretation of the data. We therefore investigated the influence of granulometry on the Raman spectrum of various minerals and rocks using laboratory equipment and the Raman instrument being developed for the Pasteur payload. The aim was to determine what influence the crushing process could have on the correct identification of rocks and minerals and the detection of possible traces of life. Whatever the sample type, our study shows that the crushing process leads to a strong increase in the background level and to a decrease in the signal/noise ratio. This effect is all the more important when the grain size is small. Moreover, for certain minerals, the Raman spectra can be significantly modified: the peaks are shifted and broadened and new peaks can appear, implying a change in the crystal structure of the material. This effect is mainly due to the decrease of the thermal diffusion in the powder which leads to an increase in the heat induced by the laser. Since mineral identification using Raman spectroscopy is made by comparison with database spectra, this kind of change could lead to misinterpretation of the spectra and thus must be taken into account during the in situ investigation. The loss of texture is also shown to complicate identification of rocks with subsequent consequences for the eventual detection and interpretation of past traces of life. On the other hand, mixing of the components in the powder facilitates the detection of minor phases.

Rapid detection of benzoyl peroxide in wheat flour by using Raman scattering spectroscopy

NASA Astrophysics Data System (ADS)

Zhao, Juan; Peng, Yankun; Chao, Kuanglin; Qin, Jianwei; Dhakal, Sagar; Xu, Tianfeng

2015-05-01

Benzoyl peroxide is a common flour additive that improves the whiteness of flour and the storage properties of flour products. However, benzoyl peroxide adversely affects the nutritional content of flour, and excess consumption causes nausea, dizziness, other poisoning, and serious liver damage. This study was focus on detection of the benzoyl peroxide added in wheat flour. A Raman scattering spectroscopy system was used to acquire spectral signal from sample data and identify benzoyl peroxide based on Raman spectral peak position. The optical devices consisted of Raman spectrometer and CCD camera, 785 nm laser module, optical fiber, prober, and a translation stage to develop a real-time, nondestructive detection system. Pure flour, pure benzoyl peroxide and different concentrations of benzoyl peroxide mixed with flour were prepared as three sets samples to measure the Raman spectrum. These samples were placed in the same type of petri dish to maintain a fixed distance between the Raman CCD and petri dish during spectral collection. The mixed samples were worked by pretreatment of homogenization and collected multiple sets of data of each mixture. The exposure time of this experiment was set at 0.5s. The Savitzky Golay (S-G) algorithm and polynomial curve-fitting method was applied to remove the fluorescence background from the Raman spectrum. The Raman spectral peaks at 619 cm-1, 848 cm-1, 890 cm-1, 1001 cm-1, 1234 cm-1, 1603cm-1, 1777cm-1 were identified as the Raman fingerprint of benzoyl peroxide. Based on the relationship between the Raman intensity of the most prominent peak at around 1001 cm-1 and log values of benzoyl peroxide concentrations, the chemical concentration prediction model was developed. This research demonstrated that Raman detection system could effectively and rapidly identify benzoyl peroxide adulteration in wheat flour. The experimental result is promising and the system with further modification can be applicable for more products in near future.

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 Elsevier B.V. All rights reserved.

Raman spectra of adsorbed layers on space shuttle and AOTV thermal protection system surface

NASA Technical Reports Server (NTRS)

Willey, Ronald J.

1987-01-01

Surfaces of interest to space vehicle heat shield design were struck by a 2 W argon ion laser line while subjected to supersonic arc jet flow conditions. Emission spectra were taken at 90 deg to the angle of laser incidence on the test object. Results showed possible weak Raman shifts which could not be directly tied to any particular parameter such as surface temperature or gas composition. The investigation must be considered exploratory in terms of findings. Many undesirable effects were found and corrected as the project progressed. For instance, initial spectra settings led to ghosts which were eliminated by closing the intermediate of filter slit of the Spex from 8 to 3 mm. Further, under certain conditions, plasma lines from the laser were observed. Several materials were also investigated at room temperature for Raman shifts. Results showed Raman shifts for RCC and TEOS coated materials. The HRSI materials showed only weak Raman shifts, however, substantial efforts were made in studying these materials. Baseline materials showed the technique to be sound. The original goal was to find a Raman shift for the High-temperature Reusable Surface Insulation (HRSI) Reaction Cured borosilicate Glass (RCG) coated material and tie the amplitude of this peak to Arc jet conditions. Weak Raman shifts may be present, however, time limitations prevented confirmation.

Detecting Kerogen as a Biosignature Using Co-located UV Time-Gated Raman and Fuorescence Spectroscopy

NASA Astrophysics Data System (ADS)

Shkolyar, S.; Eshelman, E.; Farmer, J. D.; Hamilton, D.; Daly, M. G.; Youngbull, C.

2017-12-01

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 containing fossil biosignatures as aromatic carbon (kerogen). In this study, we analyze non-extracted, naturally preserved kerogen in a diverse suite of realistic Mars analogs using combined UV excitation time-gated (UV-TG) Raman and laser-induced fluorescence spectroscopy. We interrogated kerogen and its host matrix in samples to: (1) explore the capabilities of UV-TG Raman and fluorescence spectroscopy for detecting kerogen in high-priority targets in the search for a Martian fossil record; (2) assess the effectiveness of time-gating and UV laser wavelength in reducing fluorescence; and (3) identify sample-specific issues which could challenge rover-based identifications of kerogen using UV-TG Raman spectroscopy. We found that ungated UV Raman is suited to identify diagnostic kerogen Raman bands without interfering fluorescence and that fluorescence features indicating kerogen are detectable. These data highlight the value of using both co-located Raman and fluorescence data sets together to strengthen the confidence of kerogen detection as a potential biosignature and are obtainable by SHERLOC onboard Mars 2020.

The lipid-reactive oxygen species phenotype of breast cancer. Raman spectroscopy and mapping, PCA and PLSDA for invasive ductal carcinoma and invasive lobular carcinoma. Molecular tumorigenic mechanisms beyond Warburg effect.

PubMed

Surmacki, Jakub; Brozek-Pluska, Beata; Kordek, Radzislaw; Abramczyk, Halina

2015-04-07

Vibrational signatures of human breast tissue (invasive ductal carcinoma and invasive lobular carcinoma) were used to identify, characterize and discriminate structures in normal (noncancerous) and cancerous tissues by confocal Raman imaging, Raman spectroscopy and IR spectroscopy. The most important differences between normal and cancerous tissues were found in regions characteristic for vibrations of carotenoids, fatty acids, proteins, and interfacial water. Particular attention was paid to the role played by unsaturated fatty acids and their derivatives. K-means clustering and basis analysis followed by PCA and PLSDA is employed to analyze Raman spectroscopic maps of human breast tissue and for a statistical analysis of the samples (82 patients, 164 samples). Raman maps successfully identify regions of carotenoids, fatty acids, and proteins. The intensities, frequencies and profiles of the average Raman spectra differentiate the biochemical composition of normal and cancerous tissues. The paper demonstrates that Raman imaging has reached a clinically relevant level in regard to breast cancer diagnosis applications. The sensitivity and specificity obtained directly from PLSLD and cross validation are equal to 90.5% and 84.8% for calibration and 84.7% and 71.9% for cross-validation respectively.

Infrared and Raman Spectroscopic Studies of the Antimicrobial Effects of Garlic Concentrates and Diallyl Constituents on Foodborne Pathogens

PubMed Central

Lu, Xiaonan; Rasco, Barbara A.; Kang, Dong-Hyun; Jabal, Jamie M.F.; Aston, D. Eric; Konkel, Michael E.

2012-01-01

The antimicrobial effects of garlic (Allium sativum) extract (25, 50, 75, 100, and 200 μl/ml) and diallyl sulfide (5, 10 and 20 μM) on Listeria monocytogenes and Escherichia coli O157:H7 cultivated in tryptic soy broth at 4, 22 and 35°C for up to 7 days were investigated. L. monocytogenes was more resistant to garlic extract and diallyl compounds treatment than E. coli O157:H7. Fourier transform Infrared (FT-IR) spectroscopy indicated that diallyl constituents contributed more to the antimicrobial effect than phenolic compounds. This effect was verified by Raman spectroscopy and Raman mapping on single bacteria. Scanning electron microscope (SEM) and transmission electron microscope (TEM) showed cell membrane damage consistent with spectroscopic observation. The degree of bacterial cell injury could be quantified using chemometric methods. PMID:21553849

Raman spectroscopic study of hydrogen ordered ice XIII and of its reversible phase transition to disordered ice V.

PubMed

Salzmann, Christoph G; Hallbrucker, Andreas; Finney, John L; Mayer, Erwin

2006-07-14

Raman spectra of recovered ordered H(2)O (D(2)O) ice XIII doped with 0.01 M HCl (DCl) recorded in vacuo at 80 K are reported in the range 3600-200 cm(-1). The bands are assigned to the various types of modes on the basis of isotope ratios. On thermal cycling between 80 and 120 K, the reversible phase transition to disordered ice V is observed. The remarkable effect of HCl (DCl) on orientational ordering in ice V and its phase transition to ordered ice XIII, first reported in a powder neutron diffraction study of DCl doped D(2)O ice V (C. G. Salzmann, P. G. Radaelli, A. Hallbrucker, E. Mayer, J. L. Finney, Science, 2006, 311, 1758), is demonstrated by Raman spectroscopy and discussed. The dopants KOH and HF have only a minor effect on hydrogen ordering in ice V, as shown by the Raman spectra.

Determination of chemical changes in heat-treated wood using ATR-FTIR and FT Raman spectrometry

NASA Astrophysics Data System (ADS)

Özgenç, Özlem; Durmaz, Sefa; Boyaci, Ismail Hakki; Eksi-Kocak, Haslet

2017-01-01

In this study, attenuated total reflectance-Fourier transform infrared (ATR-FTIR) and Fourier-transform Raman (FT-Raman) spectroscopy techniques were used to determine changes in the chemical structure of heat-treated woods. For this purpose, scots pine (Pinus sylvestris L.), oriental beech (Fagus orientalis L.), and oriental spruce (Picea orientalis L.) wood species were heat-treated at different temperatures. The effect of chemical changes on the FT-Raman and ATR-FTIR bands or ratios of heat-treated wood was related with the OH association of cellulose, functional groups, and the aromatic system of lignin. The effects of heat treatment on the carbohydrate and lignin peaks varied depending on the wood species. The spectral changes that occurred after heat treatment reflected the progress of the condensation reaction of lignin. Degradation of hemicelluloses led to a decrease in free hydroxyl groups. High temperature caused crystalline cellulose to increase due to the degradation of amorphous cellulose.

Determination of chemical changes in heat-treated wood using ATR-FTIR and FT Raman spectrometry.

PubMed

Özgenç, Özlem; Durmaz, Sefa; Boyaci, Ismail Hakki; Eksi-Kocak, Haslet

2017-01-15

In this study, attenuated total reflectance-Fourier transform infrared (ATR-FTIR) and Fourier-transform Raman (FT-Raman) spectroscopy techniques were used to determine changes in the chemical structure of heat-treated woods. For this purpose, scots pine (Pinus sylvestris L.), oriental beech (Fagus orientalis L.), and oriental spruce (Picea orientalis L.) wood species were heat-treated at different temperatures. The effect of chemical changes on the FT-Raman and ATR-FTIR bands or ratios of heat-treated wood was related with the OH association of cellulose, functional groups, and the aromatic system of lignin. The effects of heat treatment on the carbohydrate and lignin peaks varied depending on the wood species. The spectral changes that occurred after heat treatment reflected the progress of the condensation reaction of lignin. Degradation of hemicelluloses led to a decrease in free hydroxyl groups. High temperature caused crystalline cellulose to increase due to the degradation of amorphous cellulose. Copyright © 2016 Elsevier B.V. All rights reserved.

Raman effect in icosahedral boron-rich solids

PubMed Central

Werheit, Helmut; Filipov, Volodymyr; Kuhlmann, Udo; Schwarz, Ulrich; Armbrüster, Marc; Leithe-Jasper, Andreas; Tanaka, Takaho; Higashi, Iwami; Lundström, Torsten; Gurin, Vladimir N; Korsukova, Maria M

2010-01-01

We present Raman spectra of numerous icosahedral boron-rich solids having the structure of α-rhombohedral, β-rhombohedral, α-tetragonal, β-tetragonal, YB66, orthorhombic or amorphous boron. The spectra were newly measured and, in some cases, compared with reported data and discussed. We emphasize the importance of a high signal-to-noise ratio in the Raman spectra for detecting weak effects evoked by the modification of compounds, accommodation of interstitial atoms and other structural defects. Vibrations of the icosahedra, occurring in all the spectra, are interpreted using the description of modes in α-rhombohedral boron by Beckel et al. The Raman spectrum of boron carbide is largely clarified. Relative intra- and inter-icosahedral bonding forces are estimated for the different structural groups and for vanadium-doped β-rhombohedral boron. The validity of Badger's rule is demonstrated for the force constants of inter-icosahedral B–B bonds, whereas the agreement is less satisfactory for the intra-icosahedral B–B bonds. PMID:27877328

Resonant-Raman Intensities of N-layer Transition Metal Dichalcogenides from First Principles

NASA Astrophysics Data System (ADS)

Miranda, Henrique; Froehlicher, Guillaume; Lorchat, Ettienne; Fernique, François; Molina-Sánchez, Alejandro; Berciaud, Stéphane; Wirtz, Ludger

Transition metal dichalcogenides (TMDs) have interesting optical and electronic properties that make them good candidates for nano-engineering applications. Raman spectroscopy provides information about the vibrational modes and optical spectrum at the same time: when the laser energy is close to an electronic transition, the intensity is increased due to resonance. We investigate these effects combining different ab initio methods: we obtain ground-state and vibrational properties from density functional theory and the optical absorption spectrum using GW corrections and the Bethe-Salpeter equation to account for the excitonic effects which are known to play an important role in TMDs. Using a quasi-static finite differences approach, we calculate the dielectric susceptibility for different light polarizations and different phonon modes in order to determine the Raman tensor of TMDs, in particular of multi-layer and bulk MoTe2. We explain recent experimental results for the splitting of high-frequency modes and deviations from the non-resonant Raman model. We also give a brief outlook on possible improvements of the methodology.

Surface-enhanced Raman spectroscopy detection of polybrominated diphenylethers using a portable Raman spectrometer.

PubMed

Jiang, Xiaohong; Lai, Yongchao; Wang, Wei; Jiang, Wei; Zhan, Jinhua

2013-11-15

Polybrominated diphenylethers (PBDEs), one of the most common brominated flame retardants, are toxic and persistent, generally detected by the chromatographic method. In this work, qualitative and quantitative detection of PBDEs were explored based on surface-enhanced Raman spectroscopy (SERS) technique using a portable Raman spectrometer. Alkanethiol modified silver nanoparticle aggregates were used as the substrate and PBDEs could be pre-concentrated close to the substrate surface through their hydrophobic interactions with alkanethiol. The effect of alkanethiols with different chain length on the SERS detection of PBDEs was evaluated. It was shown that 1-hexanethiol (HT) modified substrate has higher sensitivity, good stability and reusability. Qualitative and quantitative SERS detection of PBDEs in real sea water was accomplished, with the measured detection limits at 1.2×10(2) μg L(-1). These results illustrate SERS could be used as an effective method for the detection of PBDEs. Copyright © 2013 Elsevier B.V. All rights reserved.

Hollow fiber-optic Raman probes for small experimental animals

NASA Astrophysics Data System (ADS)

Katagiri, Takashi; Hattori, Yusuke; Suzuki, Toshiaki; Matsuura, Yuji; Sato, Hidetoshi

2007-02-01

Two types of hollow fiber-optic probes are developed to measure the in vivo Raman spectra of small animals. One is the minimized probe which is end-sealed with the micro-ball lens. The measured spectra reflect the information of the sample's sub-surface. This probe is used for the measurement of the esophagus and the stomach via an endoscope. The other probe is a confocal Raman probe which consists of a single fiber and a lens system. It is integrated into the handheld microscope. A simple and small multimodal probe is realized because the hollow optical fiber requires no optical filters. The performance of each probe is examined and the effectiveness of these probes for in vivo Raman spectroscopy is shown by animal tests.

Ocean Raman Scattering in Satellite Backscatter UV Measurements

NASA Technical Reports Server (NTRS)

Vasilkov, Alexander P.; Joiner, Joanna; Gleason, James; Bhartia, Pawan; Bhartia, P. K. (Technical Monitor)

2002-01-01

Ocean Raman scattering significantly contributes to the filling-in of solar Fraunhofer lines measured by satellite backscatter ultraviolet (buy) instruments in the cloudless atmosphere over clear ocean waters. A model accounting for this effect in buy measurements is developed and compared with observations from the Global Ozone Monitoring Experiment (GONE). The model extends existing models for ocean Raman scattering to the UV spectral range. Ocean Raman scattering radiance is propagated through the atmosphere using a concept of the Lambert equivalent reflectively and an accurate radiative transfer model for Rayleigh scattering. The model and observations can be used to evaluate laboratory measurements of pure water absorption in the UV. The good agreement between model and observations suggests that buy instruments may be useful for estimating chlorophyll content.

Non-invasive detection of cocaine dissolved in beverages using displaced Raman spectroscopy.

PubMed

Eliasson, C; Macleod, N A; Matousek, P

2008-01-21

We demonstrate the potential of Raman spectroscopy to detect cocaine concealed inside transparent glass bottles containing alcoholic beverages. A clear Raman signature of cocaine with good signal-to-noise was obtained from a approximately 300 g solution of adulterated cocaine (purity 75%) in a 0.7 L authentic brown bottle of rum with 1 s acquisition time. The detection limit was estimated to be of the order of 9 g of pure cocaine per 0.7 L (approximately 0.04 moles L(-1)) with 1 s acquisition time. The technique holds great promise for the fast, non-invasive, detection of concealed illicit compounds inside beverages using portable Raman instruments, thus permitting drug trafficking to be combated more effectively.

Efficient "on-the-fly" calculation of Raman spectra from ab-initio molecular dynamics: Application to hydrophobic/hydrophilic solutes in bulk water.

PubMed

Partovi-Azar, Pouya; Kühne, Thomas D

2015-11-05

We present a novel computational method to accurately calculate Raman spectra from first principles. Together with an extension of the second-generation Car-Parrinello method of Kühne et al. (Phys. Rev. Lett. 2007, 98, 066401) to propagate maximally localized Wannier functions together with the nuclei, a speed-up of one order of magnitude can be observed. This scheme thus allows to routinely calculate finite-temperature Raman spectra "on-the-fly" by means of ab-initio molecular dynamics simulations. To demonstrate the predictive power of this approach we investigate the effect of hydrophobic and hydrophilic solutes in water solution on the infrared and Raman spectra. © 2015 Wiley Periodicals, Inc.

Raman Spectral Band Oscillations in Large Graphene Bubbles

NASA Astrophysics Data System (ADS)

Huang, Yuan; Wang, Xiao; Zhang, Xu; Chen, Xianjue; Li, Baowen; Wang, Bin; Huang, Ming; Zhu, Chongyang; Zhang, Xuewei; Bacsa, Wolfgang S.; Ding, Feng; Ruoff, Rodney S.

2018-05-01

Raman spectra of large graphene bubbles showed size-dependent oscillations in spectral intensity and frequency, which originate from optical standing waves formed in the vicinity of the graphene surface. At a high laser power, local heating can lead to oscillations in the Raman frequency and also create a temperature gradient in the bubble. Based on Raman data, the temperature distribution within the graphene bubble was calculated, and it is shown that the heating effect of the laser is reduced when moving from the center of a bubble to its edge. By studying graphene bubbles, both the thermal conductivity and chemical reactivity of graphene were assessed. When exposed to hydrogen plasma, areas with bubbles are found to be more reactive than flat graphene.

Fourier-Transform Raman Spectroscopy Of Biological Assemblies

NASA Astrophysics Data System (ADS)

Levin, Ira W.; Lewis, E. Neil

1989-12-01

Although the successful coupling of Raman scattered near-infrared radiation to a Michelson interferometer has recently created an outburst of intense interest in Fourier-transform (FT) Raman spectrometry," extended applications of the technique to macromolecular assemblies of biochemical and biophysical relevance have not progressed as rapidly as studies directed primarily at more conventional chemical characterizations. Since biological materials sampled with visible laser excitation sources typically emit a dominant fluorescence signal originating either from the intrinsic fluorescence of the molecular scatterer or from unrelenting contaminants, the use of near-infrared Nd:YAG laser excitation offers a convenient approach for avoiding this frequently overwhelming effect. In addition, the FT-Raman instrumentation provides a means of eliminating the deleterious resonance and decomposition effects often observed with the more accessible green and blue laser emissions. However, in choosing the incident near-infrared wavelength at, for example, 1064nm, the Raman scattered intensity decreases by factors of eighteen to forty from the Raman emissions induced by the shorter, visible excitations. Depending upon the experiment, this disadvantage is offset by the throughput and multiplex advantages afforded by the interferometric design. Thus, for most chemical systems, near-infrared FT-Raman spectroscopy, clearly provides a means for obtaining vibrational Raman spectra from samples intractable to the use of visible laser sources. In particular, for neat liquids, dilute solutions or polycrystalline materials, the ability to achieve high quality, reproducible spectra is, with moderate experience and perhaps relatively high laser powers, as straightforward as the conventional methods used to obtain Raman spectra with visible excitation and dispersive monochromators. In using near-infrared FT techniques to determine the Raman spectra of biological samples, one encounters new sets of experimental problems that may entail an initial, relatively steep learning curve. These difficulties originate particularly from the fragility of the weakly scattering aggregate paired with the dilute nature of the biochemical or cellular dispersion. Often, the Raman scattered intensity from these samples can be increased by carefully peileting the biological suspension using ultracentrifugation techniques. Since the overtone region of water, the usual medium for biological samples, absorbs radiation from both the Rayleigh signal at the exciting wavelength of the Nd:YAG laser and the longer wavelength Raman scattering from the sample, reproducible temperature measurements and temperature control become significant concerns. In these cases one appeals to internal temperature calibrations, use of deuterium oxide (D20) as a solvent (since absorptions of the laser exciting wavelength and Raman scattered photons are minimized), manipulation of incident laser spot size and the use of fiber optic bundles to carry the exciting and scattered radiation. In the present discussion we briefly cite some of the experimental approaches we have developed and experiences we have encountered in adapting near-infrared FT-Raman spectroscopy to the more challenging biophysical and biochemical systems amenable to vibrational analysis. We emphasize here the determination of the spectra of membrane assemblies and membrane related materials; in particular, we elucidate the interaction of several polyene antibiotics, including amphotericin A, amphotericin B and nystatin, with a model membrane system composed of dipalmitoylphosphatidylcholine bilayers.

Detection of chemical warfare simulants using Raman excitation at 1064 nm

NASA Astrophysics Data System (ADS)

Dentinger, Claire; Mabry, Mark W.; Roy, Eric G.

2014-05-01

Raman spectroscopy is a powerful technique for material identification. The technique is sensitive to primary and higher ordered molecular structure and can be used to identify unknown materials by comparison with spectral reference libraries. Additionally, miniaturization of opto-electronic components has permitted development of portable Raman analyzers that are field deployable. Raman scattering is a relatively weak effect compared to a competing phenomenon, fluorescence. Even a moderate amount of fluorescence background interference can easily prevent identification of unknown materials. A long wavelength Raman system is less likely to induce fluorescence from a wider variety of materials than a higher energy visible laser system. Compounds such as methyl salicylate (MS), diethyl malonate (DEM), and dimethyl methylphosphonate (DMMP) are used as chemical warfare agent (CWA) simulants for development of analytical detection strategies. Field detection of these simulants however poses unique challenges because threat identification must be made quickly without the turnaround time usually required for a laboratory based analysis. Fortunately, these CWA simulants are good Raman scatterers, and field based detection using portable Raman instruments is promising. Measurements of the CWA simulants were done using a 1064 nm based portable Raman spectrometer. The longer wavelength excitation laser was chosen relative to a visible based laser systems because the 1064 nm based spectrometer is less likely to induce fluorescence and more suitable to a wider range of materials. To more closely mimic real world measurement situations, different sample presentations were investigated.

Mildly reduced graphene oxide-Ag nanoparticle hybrid films for surface-enhanced Raman scattering

PubMed Central

2012-01-01

Large-area mildly reduced graphene oxide (MR-GO) monolayer films were self-assembled on SiO2/Si surfaces via an amidation reaction strategy. With the MR-GO as templates, MR-GO-Ag nanoparticle (MR-GO-Ag NP) hybrid films were synthesized by immersing the MR-GO monolayer into a silver salt solution with sodium citrate as a reducing agent under UV illumination. SEM image indicated that Ag NPs with small interparticle gap are uniformly distributed on the MR-GO monolayer. Raman spectra demonstrated that the MR-GO monolayer beneath the Ag NPs can effectively quench the fluorescence signal emitted from the Ag films and dye molecules under laser excitation, resulting in a chemical enhancement (CM). The Ag NPs with narrow gap provided numerous hot spots, which are closely related with electromagnetic mechanism (EM), and were believed to remarkably enhance the Raman signal of the molecules. Due to the co-contribution of the CM and EM effects as well as the coordination mechanism between the MR-GO and Ag NPs, the MR-GO-Ag NP hybrid films showed more excellent Raman signal enhancement performance than that of either Ag films or MR-GO monolayer alone. This will further enrich the application of surface-enhanced Raman scattering in molecule detection. PMID:22471923

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.

Effect of infrared light on live blood cells: Role of β-carotene.

PubMed

Barkur, Surekha; Bankapur, Aseefhali; Chidangil, Santhosh; Mathur, Deepak

2017-06-01

We have utilized Raman tweezers to measure and assign micro-Raman spectra of optically trapped, live red blood cells (RBCs), white blood cells (WBCs) and platelets. Various types of WBCs- both granulocytes, lymphocytes, and their different types have been studied. The Raman bands are assigned to different biomolecules of blood cells. The Raman spectra thus obtained has been enabled detection of β-carotene in these blood cells, the spectral features of which act as a signature that facilitates experimental probing of the effect of 785nm laser light on different blood cells as a function of incident laser power in the mW range. The spectral changes that we obtain upon laser irradiation indicate that, both haemoglobin as well as the cell membrane sustains damage. In case of lymphocytes and platelets the peaks corresponding to β-carotene showed drastic changes. Thorough analysis of the spectral changes indicates possibility of free radical induced damage of β-carotene in lymphocytes and platelets. Among different blood cells, RBCs have a power threshold of only 10mW. The power threshold for other types of blood cells is somewhat higher, but always below about 30mW. These values are likely to serve as useful guides for Raman tweezers based experiments on live cells. Copyright © 2017. Published by Elsevier B.V.

IR absorption and surface-enhanced Raman spectra of the isoquinoline alkaloid berberine

NASA Astrophysics Data System (ADS)

Strekal', N. D.; Motevich, I. G.; Nowicky, J. W.; Maskevich, S. A.

2007-01-01

We present the IR absorption and surface-enhanced Raman scattering (SERS) spectra of the isoquinoline alkaloid berberine adsorbed on a silver hydrosol and on the surface of a silver electrode for different potentials. Based on quantum chemical calculations, for the first time we have assigned the vibrations in the berberine molecule according to vibrational mode. The effect of the potential of the silver electrode on the geometry of sorption of the molecule on the surface is considered, assuming a short-range mechanism for enhancement of Raman scattering.

Resonant Raman scattering from silicon nanoparticles enhanced by magnetic response.

PubMed

Dmitriev, Pavel A; Baranov, Denis G; Milichko, Valentin A; Makarov, Sergey V; Mukhin, Ivan S; Samusev, Anton K; Krasnok, Alexander E; Belov, Pavel A; Kivshar, Yuri S

2016-05-05

Enhancement of optical response with high-index dielectric nanoparticles is attributed to the excitation of their Mie-type magnetic and electric resonances. Here we study Raman scattering from crystalline silicon nanoparticles and reveal that magnetic dipole modes have a much stronger effect on the scattering than electric modes of the same order. We demonstrate experimentally a 140-fold enhancement of the Raman signal from individual silicon spherical nanoparticles at the magnetic dipole resonance. Our results confirm the importance of the optically-induced magnetic response of subwavelength dielectric nanoparticles for enhancing light-matter interactions.

Raman and infrared studies of nucleosides at high pressures: II. Cytidine.

PubMed

Li, J; Lee, S A; Pinnick, D A; Anderson, A; Smith, W; Griffey, R H; Mohan, V

2002-06-01

Raman and mid-infrared (MIR) spectra have been recorded for crystalline cytidine at pressures up to 10 GPa at room temperature. Broadening and positive wavenumber shifts are observed for most of the Raman and MIR peaks with increasing pressure. However, some of the MIR peaks associated with hydrogen-stretching modes display a negative wavenumber shift as a result of charge transfer effects. Evidence of a phase transition near 4 GPa is presented and attributed to a change in the conformation of the five membered sugar ring.

TiO2 induced structural modifications in Cs containing borosilicate glasses: Raman and infrared studies

NASA Astrophysics Data System (ADS)

Pandey, M.; Banerjee, D.; Sudarsan, V.; Kshirsagar, R. J.

2018-04-01

Effect of TiO2 addition in Cs containing Sodium-borosilicate glasses is studied using Raman and infrared spectroscopic techniques. As revealed from infrared and Raman studies, TiO2 does not form segregated phase, but instead enters into the borosilicate network. It is further observed that TiO2 addition results in modifications of the borate and silicate structural units by transforming into tetraborates and metasilicate structural units. These structural modifications are responsible for Cs immobilization, leach rate and chemical durability of these glasses.

Geometry of GLP on silver surface by surface-enhanced Raman spectroscopy

NASA Astrophysics Data System (ADS)

Bao, PeiDi; Bao, Lang; Huang, TianQuan; Liu, XinMing; Wu, GuoFeng

2000-05-01

Leptospirosis is one of the most harmful zoonosis, it is a serious public health issue in some area of Sichuan province. Surface-Enhance Raman Scattering (SERS) Spectroscopy is an effective approach for the study of biomolecular adsorption on metal surface and provides information about the adsorbed species. Two samples of Leptospiral Glycolipoprotein (GLP-1) and GLP-2 which have different toxic effects have been obtained and investigated.

Raman Investigation of the Effects on Fused Silica Fibers

DTIC Science & Technology

1983-01-12

Howard University NR-051-733 Washington, D.C. 20059v=4 1- CO-NTROLLING OFFICE NAME AND ADDRESS 12. RIEPORT DATE Office of Naval Research January 12, 1983...0.. Chemistry Department Howard University Washington, D.C. 20059 r P" -2- The application of... Howard University , 1981. (4) Scrambled laser polarization was used prior to Raman excitation, Figs. l(c) and l(d), to counteract effects of

Raman effect, structural and dielectric properties of sol-gel synthesized polycrystalline GaFe{sub 1-x}Zr{sub x}O{sub 3} (0≤x≤0.15)

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

Kumar, Rajeev, E-mail: rajeevgiitk@gmail.com; Mall, Ashish Kumar; Gupta, Rajeev

2016-05-23

Polycrystalline ceramic samples of Zirconium (Zr)-doped GaFeO{sub 3} (GaFe{sub 1-x}Zr{sub x}O{sub 3}) were studied using powder X-ray diffraction, complex impedance spectroscopy and Raman spectroscopic measurements to understand the effect of Zr doping on the structural and dielectric properties. The samples with varying Zr content were prepared by Sol-Gel method. X-ray data analysis confirmed the formation of single phase material without formation of any secondary phases and all are crystallized in Pc2{sub 1}n orthorhombic symmetry. Rietveld refinement of the X-ray data suggested an increase in the lattice constants due to size effect and decreases on x = 0.15 due to themore » effect of change in interplanner spacing. Impedance studies on the samples showed that the dielectric constant increases while loss tangent decrease as the Zr content increases. Raman scattering on GaFe{sub 1-x}Zr{sub x}O{sub 3} (x = 0, 0.05, 0.10, & 0.15) used to understand the composition dependence on phonon modes at room temperature. On Zr doping, Raman modes frequencies shifts to lower energies consistent with the X-ray data.« less

Transfer of monolayer TMD WS2 and Raman study of substrate effects

PubMed Central

Mlack, Jerome T.; Masih Das, Paul; Danda, Gopinath; Chou, Yung-Chien; Naylor, Carl H.; Lin, Zhong; López, Néstor Perea; Zhang, Tianyi; Terrones, Mauricio; Johnson, A. T. Charlie; Drndić, Marija

2017-01-01

A facile transfer process for transition metal dichalcogenide WS2 flakes is reported and the effect of the underlying substrate on the flake properties is investigated using Raman spectroscopy. The flakes are transferred from their growth substrate using polymethyl methacrylate (PMMA) and a wet etch to allow the user to transfer the flakes to a final substrate using a microscope and micromanipulator combined with semi-transparent Kapton tape. The substrates used range from insulators such as industry standard high-k dielectric HfO2 and “green polymer” parylene-C, to conducting chemical vapor deposition (CVD) grown graphene. Raman spectroscopy is used first to confirm the material quality of the transferred flakes to the substrates and subsequently to analyze and separate the effects arising from material transfer from those arising from interactions with the substrate. We observe changes in the Raman spectra associated with the interactions between the substrates in the flakes. These interactions affect both in-plane and out-of-plane modes in different ways depending on their sources, for example strain or surface charge. These changes vary with final substrate, with the strongest effects being observed for WS2 transferred onto graphene and HfO2, demonstrating the importance of understanding substrate interaction for fabrication of future devices. PMID:28220852

A multimode vibronic treatment of absorption, resonance Raman, and hyper-Rayleigh scattering of excitonically coupled molecular dimers

NASA Astrophysics Data System (ADS)

Myers Kelley, Anne

2003-08-01

The linear absorption spectra, resonance Raman excitation profiles and depolarization dispersion curves, and hyper-Rayleigh scattering profiles are calculated for excitonically coupled homodimers of a model electron donor-acceptor "push-pull" conjugated chromophore as a function of dimer geometry. The vibronic eigenstates of the dimer are calculated by diagonalizing the matrix of transition dipole couplings among the vibronic transitions of the constituent monomers. The absorption spectra show the usual red- or blueshifted transitions for J-type or H-type dimers, respectively. When the electronic coupling is large compared with the vibronic width of the monomer spectrum, the dimer absorption spectra exhibit simple Franck-Condon progressions having reduced vibronic intensities compared with the monomer, and the resonance Raman excitation profiles are shifted but otherwise only weakly perturbed. When the coupling is comparable to the vibronic width, the H-dimer absorption spectra exhibit irregular vibronic frequency spacings and intensity patterns and the effects on the Raman excitation profiles are larger. There is strong dispersion in the Raman depolarization ratios for dimer geometries in which both transitions carry oscillator strength. The first hyperpolarizabilities are somewhat enhanced in J-dimers and considerably reduced in H-dimers. These effects on the molecular β will amplify the effects of dimerization on the ground-state dipole moment in electro-optic materials formed from chromophore-doped polymers that must be electric field poled to obtain the net alignment needed for a macroscopic χ(2).

Detection of Vero Cells Infected with Herpes Simplex Types 1 and 2 and Varicella Zoster Viruses Using Raman Spectroscopy and Advanced Statistical Methods.

PubMed

Huleihel, Mahmoud; Shufan, Elad; Zeiri, Leila; Salman, Ahmad

2016-01-01

Of the eight members of the herpes family of viruses, HSV1, HSV2, and varicella zoster are the most common and are mainly involved in cutaneous disorders. These viruses usually are not life-threatening, but in some cases they might cause serious infections to the eyes and the brain that can lead to blindness and possibly death. An effective drug (acyclovir and its derivatives) is available against these viruses. Therefore, early detection and identification of these viral infections is highly important for an effective treatment. Raman spectroscopy, which has been widely used in the past years in medicine and biology, was used as a powerful spectroscopic tool for the detection and identification of these viral infections in cell culture, due to its sensitivity, rapidity and reliability. Our results showed that it was possible to differentiate, with a 97% identification success rate, the uninfected Vero cells that served as a control, from the Vero cells that were infected with HSV-1, HSV-2, and VZV. For that, linear discriminant analysis (LDA) was performed on the Raman spectra after principal component analysis (PCA) with a leave one out (LOO) approach. Raman spectroscopy in tandem with PCA and LDA enable to differentiate among the different herpes viral infections of Vero cells in time span of few minutes with high accuracy rate. Understanding cell molecular changes due to herpes viral infections using Raman spectroscopy may help in early detection and effective treatment.

Thermal effect on structure organizations in cobalt-fullerene nanocomposition.

PubMed

Lavrentiev, Vasily; Vacik, Jiri; Naramoto, Hiroshi; Sakai, Seiji

2010-04-01

Effect of deposition temperature (Ts) on structure of Co-C60 nanocomposite (NC) prepared by simultaneous deposition of cobalt and fullerene on sapphire is presented. The NC structure variations with Ts increasing from room temperature (RT) to 400 degrees C have been analyzed using scanning electron microscopy (SEM), atomic force microscopy (AFM) and Raman spectroscopy. AFM and SEM show granule-like structure of the Co-C60 film. The mixture film deposited at RT includes the hills on the surface suggesting accumulation of internal stress during phase separation. Raman spectra show 25 cm(-1) downshift of Ag(2) C60 peak suggesting -Co-C60- polymerization in C60-based matrix of the NC film. Analysis of Raman spectra has revealed existence of amorphous carbon (a-C) in the NC matrix that argues C60 decomposition. The Ts increase to 200 degrees C causes the surface hills smoothing. In parallel, downshift of the Ag(2) peak decreases to 16 cm(-1) that implies more pronounced phase separation and lower -Co-C60- polymerization efficiency. Also, amount of a-C content slightly increases. Further Ts increasing to 400 degrees C changes the NC structure dramatically. AFM shows evident enlargement of the granules. According to Raman spectra the high Ts deposition yields pronounced C60 decomposition increasing the a-C content. Features of a-C Raman peak imply nucleation of graphitic islands at the NC interfaces. Abundant decomposition of C60 in the mixture film deposited at 400 degrees C is referred to cobalt catalytic effect.

Through tissue imaging of a live breast cancer tumour model using handheld surface enhanced spatially offset resonance Raman spectroscopy (SESORRS).

PubMed

Nicolson, Fay; Jamieson, Lauren E; Mabbott, Samuel; Plakas, Konstantinos; Shand, Neil C; Detty, Michael R; Graham, Duncan; Faulds, Karen

2018-04-21

In order to improve patient survival and reduce the amount of unnecessary and traumatic biopsies, non-invasive detection of cancerous tumours is of imperative and urgent need. Multicellular tumour spheroids (MTS) can be used as an ex vivo cancer tumour model, to model in vivo nanoparticle (NP) uptake by the enhanced permeability and retention (EPR) effect. Surface enhanced spatially offset Raman spectroscopy (SESORS) combines both surface enhanced Raman spectroscopy (SERS) and spatially offset Raman spectroscopy (SORS) to yield enhanced Raman signals at much greater sub-surface levels. By utilizing a reporter that has an electronic transition in resonance with the laser frequency, surface enhanced resonance Raman scattering (SERRS) yields even greater enhancement in Raman signal. Using a handheld SORS spectrometer with back scattering optics, we demonstrate the detection of live breast cancer 3D MTS containing SERRS active NPs through 15 mm of porcine tissue. False color 2D heat intensity maps were used to determine tumour model location. In addition, we demonstrate the tracking of SERRS-active NPs through porcine tissue to depths of up to 25 mm. This unprecedented performance is due to the use of red-shifted chalcogenpyrylium-based Raman reporters to demonstrate the novel technique of surface enhanced spatially offset resonance Raman spectroscopy (SESORRS) for the first time. Our results demonstrate a significant step forward in the ability to detect vibrational fingerprints from a tumour model at depth through tissue. Such an approach offers significant promise for the translation of NPs into clinical applications for non-invasive disease diagnostics based on this new chemical principle of measurement.

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.

Bose-Einstein condensate in an optical lattice with Raman-assisted two-dimensional spin-orbit coupling

NASA Astrophysics Data System (ADS)

Pan, Jian-Song; Zhang, Wei; Yi, Wei; Guo, Guang-Can

2016-10-01

In a recent experiment (Z. Wu, L. Zhang, W. Sun, X.-T. Xu, B.-Z. Wang, S.-C. Ji, Y. Deng, S. Chen, X.-J. Liu, and J.-W. Pan, arXiv:1511.08170 [cond-mat.quant-gas]), a Raman-assisted two-dimensional spin-orbit coupling has been realized for a Bose-Einstein condensate in an optical lattice potential. In light of this exciting progress, we study in detail key properties of the system. As the Raman lasers inevitably couple atoms to high-lying bands, the behaviors of the system in both the single- and many-particle sectors are significantly affected. In particular, the high-band effects enhance the plane-wave phase and lead to the emergence of "roton" gaps at low Zeeman fields. Furthermore, we identify high-band-induced topological phase boundaries in both the single-particle and the quasiparticle spectra. We then derive an effective two-band model, which captures the high-band physics in the experimentally relevant regime. Our results not only offer valuable insights into the two-dimensional lattice spin-orbit coupling, but also provide a systematic formalism to model high-band effects in lattice systems with Raman-assisted spin-orbit couplings.

Raman spectroscopy-based detection of chemical contaminants in food powders

NASA Astrophysics Data System (ADS)

Chao, Kuanglin; Dhakal, Sagar; Qin, Jianwei; Kim, Moon; Bae, Abigail

2016-05-01

Raman spectroscopy technique has proven to be a reliable method for qualitative detection of chemical contaminants in food ingredients and products. For quantitative imaging-based detection, each contaminant particle in a food sample must be detected and it is important to determine the necessary spatial resolution needed to effectively detect the contaminant particles. This study examined the effective spatial resolution required for detection of maleic acid in tapioca starch and benzoyl peroxide in wheat flour. Each chemical contaminant was mixed into its corresponding food powder at a concentration of 1% (w/w). Raman spectral images were collected for each sample, leveled across a 45 mm x 45 mm area, using different spatial resolutions. Based on analysis of these images, a spatial resolution of 0.5mm was selected as effective spatial resolution for detection of maleic acid in starch and benzoyl peroxide in flour. An experiment was then conducted using the 0.5mm spatial resolution to demonstrate Raman imaging-based quantitative detection of these contaminants for samples prepared at 0.1%, 0.3%, and 0.5% (w/w) concentrations. The results showed a linear correlation between the detected numbers of contaminant pixels and the actual concentrations of contaminant.

Near field plasmonic gradient effects on high vacuum tip-enhanced Raman spectroscopy.

PubMed

Fang, Yurui; Zhang, Zhenglong; Chen, Li; Sun, Mengtao

2015-01-14

Near field gradient effects in high vacuum tip-enhanced Raman spectroscopy (HV-TERS) are a recent developing ultra-sensitive optical and spectral analysis technology on the nanoscale, based on the plasmons and plasmonic gradient enhancement in the near field and under high vacuum. HV-TERS can not only be used to detect ultra-sensitive Raman spectra enhanced by surface plasmon, but also to detect clear molecular IR-active modes enhanced by strongly plasmonic gradient. Furthermore, the molecular overtone modes and combinational modes can also be experimentally measured, where the Fermi resonance and Darling-Dennison resonance were successfully observed in HV-TERS. Theoretical calculations using electromagnetic field theory firmly supported experimental observation. The intensity ratio of the plasmon gradient term over the linear plasmon term can reach values greater than 1. Theoretical calculations also revealed that with the increase in gap distance between tip and substrate, the decrease in the plasmon gradient was more significant than the decrease in plasmon intensity, which is the reason that the gradient Raman can be only observed in the near field. Recent experimental results of near field gradient effects on HV-TERS were summarized, following the section of the theoretical analysis.

First-principles study of excitonic effects in Raman intensities

NASA Astrophysics Data System (ADS)

Gillet, Yannick; Giantomassi, Matteo; Gonze, Xavier

2013-09-01

The ab initio prediction of Raman intensities for bulk solids usually relies on the hypothesis that the frequency of the incident laser light is much smaller than the band gap. However, when the photon frequency is a sizable fraction of the energy gap, or higher, resonance effects appear. In the case of silicon, when excitonic effects are neglected, the response of the solid to light increases by nearly three orders of magnitude in the range of frequencies between the static limit and the gap. When excitonic effects are taken into account, an additional tenfold increase in the intensity is observed. We include these effects using a finite-difference scheme applied on the dielectric function obtained by solving the Bethe-Salpeter equation. Our results for the Raman susceptibility of silicon show stronger agreement with experimental data compared with previous theoretical studies. For the sampling of the Brillouin zone, a double-grid technique is proposed, resulting in a significant reduction in computational effort.

The determination of captopril in Solution by Raman spectroscopy

NASA Astrophysics Data System (ADS)

Gao, Junxiang; Gu, Huaimin; Dong, Xiao; liu, fangfang

2011-01-01

Captopril, 1-[(2S)-3-mercapto-2-methyl propionyl]-Lproline, is an angiotensin converting enzyme (ACE) inhibitor, which reduces peripheral resistance and lowers blood pressure. It is widely used in the hypertensive ailments and incongestive heart failure treatment. Due to such crucial pharmacological importance, development of simple and accurate methods for the determination of captopril is desired. In this work, the normal Raman spectra of the captopril in different concentrations were studied, and the relationship between the Raman intensity and the concentrations of the captopril was quantificationally analysed. By selecting appropriate characteristic Raman bands of the cptopril, the solution of some captopril purchased in a local pharmacy was quantificationally determined. A quantificational linear relationship between the Raman intensity and the concentrations of captopril was obtained, and it is little affected by other compounds in the solution of captopril. This study provides an effective technique for the quantificational determination of captopril in solutions, and it has a potential application in the analysis of medicament.

Preanalytical considerations in detection of colorectal cancer in blood serum using Raman molecular imaging (Conference Presentation)

NASA Astrophysics Data System (ADS)

Treado, Patrick J.; Stewart, Shona D.; Smith, Aaron; Kirschner, Heather; Post, Christopher; Overholt, Bergein F.

2016-03-01

Colorectal cancer (CRC) is the third most common cancer in men and women in the United States. Raman Molecular Imaging (RMI) is an effective technique to evaluate human tissue, cells and bodily fluids, including blood serum for disease diagnosis. ChemImage Corporation, in collaboration with clinicians, has been engaged in development of an in vitro diagnostic Raman assay focused on CRC detection. The Raman Assay for Colorectal Cancer (RACC) exploits the high specificity of Raman imaging to distinguish diseased from normal dried blood serum droplets without additional reagents. Pilot Study results from testing of hundreds of biobank patient samples have demonstrated that RACC detects CRC with high sensitivity and specificity. However, expanded clinical trials, which are ongoing, are revealing a host of important preanalytical considerations associated with sample collection, sample storage and stability, sample shipping, sample preparation and sample interferents, which impact detection performance. Results from recent clinical studies will be presented.

Efficient Raman sideband cooling of trapped ions to their motional ground state

NASA Astrophysics Data System (ADS)

Che, H.; Deng, K.; Xu, Z. T.; Yuan, W. H.; Zhang, J.; Lu, Z. H.

2017-07-01

Efficient cooling of trapped ions is a prerequisite for various applications of the ions in precision spectroscopy, quantum information, and coherence control. Raman sideband cooling is an effective method to cool the ions to their motional ground state. We investigate both numerically and experimentally the optimization of Raman sideband cooling strategies and propose an efficient one, which can simplify the experimental setup as well as reduce the number of cooling pulses. Several cooling schemes are tested and compared through numerical simulations. The simulation result shows that the fixed-width pulses and varied-width pulses have almost the same efficiency for both the first-order and the second-order Raman sideband cooling. The optimized strategy is verified experimentally. A single 25Mg+ ion is trapped in a linear Paul trap and Raman sideband cooled, and the achieved average vibrational quantum numbers under different cooling strategies are evaluated. A good agreement between the experimental result and the simulation result is obtained.

Oncologic photodynamic diagnosis and therapy: confocal Raman/fluorescence imaging of metal phthalocyanines in human breast cancer tissue in vitro.

PubMed

Abramczyk, Halina; Brozek-Pluska, Beata; Surmacki, Jakub; Musial, Jacek; Kordek, Radzislaw

2014-11-07

Raman microspectroscopy and confocal Raman imaging combined with confocal fluorescence were used to study the distribution and aggregation of aluminum tetrasulfonated phthalocyanine (AlPcS4) in noncancerous and cancerous breast tissues. The results demonstrate the ability of Raman spectroscopy to distinguish between noncancerous and cancerous human breast tissue and to identify differences in the distribution and aggregation of aluminum phthalocyanine, which is a potential photosensitizer in photodynamic therapy (PDT), photodynamic diagnosis (PDD) and photoimmunotherapy (PIT) of cancer. We have observed that the distribution of aluminum tetrasulfonated phthalocyanine confined in cancerous tissue is markedly different from that in noncancerous tissue. We have concluded that Raman imaging can be treated as a new and powerful technique useful in cancer photodynamic therapy, increasing our understanding of the mechanisms and efficiency of photosensitizers by better monitoring localization in cancer cells as well as the clinical assessment of the therapeutic effects of PDT and PIT.

Competition Between Extinction and Enhancement in Surface Enhanced Raman Spectroscopy.

PubMed

van Dijk, Thomas; Sivapalan, Sean T; Devetter, Brent M; Yang, Timothy K; Schulmerich, Matthew V; Murphy, Catherine J; Bhargava, Rohit; Carney, P Scott

2013-04-04

Conjugated metallic nanoparticles are a promising means to achieve ultrasensitive and multiplexed sensing in intact three-dimensional samples, especially for biological applications, via surface enhanced Raman scattering (SERS). We show that enhancement and extinction are linked and compete in a collection of metallic nanoparticles. Counterintuitively, the Raman signal vanishes when nanoparticles are excited at their plasmon resonance, while increasing nanoparticle concentrations at off-resonance excitation sometimes leads to decreased signal. We develop an effective medium theory that explains both phenomena. Optimal choices of excitation wavelength, individual particle enhancement factor and concentrations are indicated. The same processes which give rise to enhancement also lead to increased extinction of both the illumination and the Raman scattered light. Nanoparticles attenuate the incident field (blue) and at the same time provide local enhancement for SERS. Likewise the radiation of the Raman-scattered field (green) is enhanced by the near-by sphere but extinguished by the rest of the spheres in the suspension on propagation.

Raman shifts in electron-irradiated monolayer MoS 2

DOE PAGES

Parkin, William M.; Balan, Adrian; Liang, Liangbo; ...

2016-03-21

Here, we report how the presence of electron-beam-induced sulfur vacancies affects first-order Raman modes and correlate the effects with the evolution of the in situ transmission-electron microscopy (TEM) two-terminal conductivity of monolayer MoS 2 under electron irradiation. We observe a redshift in the E Raman peak and a less pronounced blueshift in the A' 1 peak with increasing electron dose. Using energy-dispersive X-ray spectroscopy (EDS), we show that irradiation causes partial removal of sulfur and correlate the dependence of the Raman peak shifts with S vacancy density (a few %), which is confirmed by first-principles density functional theory calculations. Inmore » situ device current measurements show exponential decrease in channel current upon irradiation. Our analysis demonstrates that the observed frequency shifts are intrinsic properties of the defective systems and that Raman spectroscopy can be used as a quantitative diagnostic tool to characterize MoS 2-based transport channels.« less

Raman Spectrum of Er-Y-codoped ZrO2 and Fluorescence Properties of Er3+

NASA Astrophysics Data System (ADS)

He, Jun; Luo, Meng-fei; Jin, Ling-yun; He, Mai; Fang, Ping; Xie, Yun-long

2007-02-01

Er-Y-codoped ZrO2 mixed oxides with monoclinic, tetragonal and cubic structures were prepared by a sol-gel method. The crystal structure of ZrO2 matrix and the effect of the ZrO2 phases on the fluorescence properties of Er3+ were studied using Raman spectroscopy. The results indicated that the fluorescence properties of Er3+ depend on its local ZrO2 crystal structures. As ZrO2 matrix transferred from monoclinic to tetragonal and cubic phase, the Raman and fluorescence bands of Er3+ decreased in intensities and tended to form a single peak. With 632.8 nm excitation, the bands between 640 and 680 nm were attributed to the fluorescence of Er3+ in the ZrO2 environment. However, only the fluorescence was observed and no Raman spectra were seen under 514.5 nm excitation, while only Raman spectra were observed under 325 nm excitation. UV Raman spectroscopy was found to be more sensitive in the surface region while the information provided by XRD mainly came from the bulk. The phase with lower symmetry forms more easily on the surface than in the bulk.

Enhanced Uranium Ore Concentrate Analysis by Handheld Raman Sensor: FY15 Status Report

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

Bryan, Samuel A.; Johnson, Timothy J.; Orton, Christopher R.

2015-11-11

High-purity uranium ore concentrates (UOC) represent a potential proliferation concern. A cost-effective, “point and shoot” in-field analysis capability to identify ore types, phases of materials present, and impurities, as well as estimate the overall purity would be prudent. Handheld, Raman-based sensor systems are capable of identifying chemical properties of liquid and solid materials. While handheld Raman systems have been extensively applied to many other applications, they have not been broadly studied for application to UOC, nor have they been optimized for this class of chemical compounds. PNNL was tasked in Fiscal Year 2015 by the Office of International Safeguards (NA-241)more » to explore the use of Raman for UOC analysis and characterization. This report summarizes the activities in FY15 related to this project. The following tasks were included: creation of an expanded library of Raman spectra of a UOC sample set, creation of optimal chemometric analysis methods to classify UOC samples by their type and level of impurities, and exploration of the various Raman wavelengths to identify the ideal instrument settings for UOC sample interrogation.« less

Effect of Red Light-Emitting Diodes Irradiation on Hemoglobin for Potential Hypertension Treatment Based on Confocal Micro-Raman Spectroscopy.

PubMed

Qiu, Xuejun; Huang, Hanchuan; Huang, Zhitong; Zhuang, Zhengfei; Guo, Zhouyi; Liu, Songhao

2017-01-01

Red light-emitting diodes (LED) were used to irradiate the isolated hypertension hemoglobin (Hb) and Raman spectra difference was recorded using confocal micro-Raman spectroscopy. Differences were observed between the controlled and irradiated Hb by comparing the spectra records. The Raman spectrum at the 1399 cm -1 band decreased following prolonged LED irradiation. The intensity of the 1639 cm -1 band decreased dramatically in the first five minutes and then gradually increased in a time-dependent manner. This observation indicated that LED irradiation increased the ability of oxygen binding in Hb. The appearance of the heme aggregation band at 1399 cm -1 , in addition to the oxygen marker band at 1639 cm -1 , indicated that, in our study, 30 min of irradiation with 15.0 mW was suitable for inhibiting heme aggregation and enhancing the oxygen-carrying capacity of Hb. Principal component analysis showed a one-to-one relationship between irradiated Hb at different time points and the corresponding Raman spectra. Our approach could be used to analyze the hemoglobin from patients with confocal micro-Raman spectroscopy and is helpful for developing new nondrug hypertension therapy.

SU-E-T-771: Two Dimensional Raman Mapping of Carbon Bonds of Radiochromic Films: An Approach to Micro-Dosimetry

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

Heo, T; Ye, S

2015-06-15

Purpose: To study a feasibility of micro-dosimetry with high dose-sensitivity and resolution using two-dimensional Raman mapping on the basis of carbon bonds concentration of radiochromic films Methods: Unlaminated EBT3 films with the purpose of maximal Raman data acquisition were irradiated by 6 MV beam from 5 MU to 1000 MU at the reference condition. Each film was irradiated with shielding material of lead blocking on the half of film as well as the jaw open in half for distinct dose contrast. Raman peaks of 2070 cm-1, 2095 cm-1, and 2115 cm-1 were major subjects to study, which are assumed tomore » be the spectroscopy of carbon triple bonds of monomers, carbon double bonds of polymers, and carbon triple bonds of polymers, respectively. Laser exposure for Raman spectroscopy generated peak’s trend due to polymerization by laser output and this trend was utilized to find out basic peaks related to polymerization process. The relative dose contrast in each one film was detected by Raman spectroscopy with the aid of an auto-scanning stage, comparing the dose contrast between non-irradiated area and irradiated area. Raman spatial resolution was enhanced up to 20 micrometers, assuming the spatial uniformity of radio¬active rod-shaped LiPCDA crystals. An optical scanner with 9600 dpi was used to scan the red-channel intensity to read the dose contrast for 5 MU delivered film. Results: The peak intensity for Raman wavenumber of 2070 cm-1 was used for mapping since it reflected the different peak intensities based on polymerization degree by irradiation. Dose contrast from 1000MU to 5 MU was distinguished by Raman mapping analysis, whereas optical intensity of red-channel didn’t show any difference. Conclusion: In consideration of laser effect, the quantitative analysis based on raw data of Raman mapping could provide more statistically reliable dosimetry than point measurements.« less

Application of Raman Spectroscopy for the Detection of Acetone Dissolved in Transformer Oil

NASA Astrophysics Data System (ADS)

Gu, Z.; Chen, W.; Du, L.; Shi, H.; Wan, F.

2018-05-01

The CLRS detection characteristics of acetone dissolved in transformer oil were analyzed. Raman spectral peak at 780 cm-1 was used as the characteristic spectral peak for qualitative and quantitative analyses. The effect of the detection depth and the temperature was investigated in order to obtain good Raman signals. The optimal detection depth and temperature were set as 3 mm and room temperature. A quantitative model relation between concentration and the Raman peak intensity ratio I 780/I 893 was constructed via the least-squares method. The results demonstrated that CLRS can quantitatively detect the concentration of acetone in transformer oil and CLRS has potential as a useful alternative for accelerating the in-situ analysis of the concentration of acetone in transformer oil.

Effect of surface density silver nanoplate films toward surface-enhanced Raman scattering enhancement for bisphenol A detection

NASA Astrophysics Data System (ADS)

Bakar, N. A.; Salleh, M. M.; Umar, A. A.; Shapter, J. G.

2018-03-01

This paper reports a study on surface-enhanced Raman scattering (SERS) phenomenon of triangular silver nanoplate (NP) films towards bisphenol A (BPA) detection. The NP films were prepared using self-assembly technique with four different immersion times; 1 hour, 2 hours, 5 hours, and 8 hours. The SERS measurement was studied by observing the changes in Raman spectra of BPA after BPA absorbed on the NP films. It was found that the Raman intensity of BPA peaks was enhanced by using the prepared SERS substrates. This is clearly indicated that these SERS silver substrates are suitable to sense industrial chemical and potentially used as SERS detector. However, the rate of SERS enhancement is depended on the distribution of NP on the substrate surface.

Application of Raman Spectroscopy for the Detection of Acetone Dissolved in Transformer Oil

NASA Astrophysics Data System (ADS)

Gu, Z.; Chen, W.; Du, L.; Shi, H.; Wan, F.

2018-05-01

The CLRS detection characteristics of acetone dissolved in transformer oil were analyzed. Raman spectral peak at 780 cm-1 was used as the characteristic spectral peak for qualitative and quantitative analyses. The effect of the detection depth and the temperature was investigated in order to obtain good Raman signals. The optimal detection depth and temperature were set as 3 mm and room temperature. A quantitative model relation between concentration and the Raman peak intensity ratio I 780/ I 893 was constructed via the least-squares method. The results demonstrated that CLRS can quantitatively detect the concentration of acetone in transformer oil and CLRS has potential as a useful alternative for accelerating the in-situ analysis of the concentration of acetone in transformer oil.

Effects of Raman scattering on the water-leaving radiance

NASA Technical Reports Server (NTRS)

Waters, Kirk J.

1995-01-01

The contribution of Raman scattering to the water-leaving radiance is examined using Monte Carlo simulations. Exit angle information is retained, allowing a comparison of different satellite viewing directions. Chlorophyll values of 0.0, 0.01, 0.1, and 1.0 mg Chl/cu m are simulated. Little directional variability is found, with the exception of the direct solar backscatter direction. The wavelength variability is greatest for low chlorophyll concentrations and is negligible for 1.0 mg Chl/cu m. At 550 nm the Raman contribution ranges from approximately 18% of the total water-leaving radiance for pure water to 3% for 1.0 mg Chl/cu m. At 440 nm the range is from 6% to 2%, indicating that Raman scattering will impact radiance ratios for ocean color satellite algorithms.

The influence of adsorbed molecules on the framework vibrations of Na-Faujasites studied with FT Raman spectroscopy

NASA Astrophysics Data System (ADS)

Ferwerda, R.; van der Maas, J. H.

1995-11-01

The use of FT Raman spectroscopy in the elucidation of the structural parameters of Faujasitic zeolites is investigated. Because fluorescence is less of a problem on excitation with a near-infrared laser, FT Raman spectroscopy allows one to probe the effects of in situ heat treatments on the zeolite structure. A correlation is found between the bending vibrations of the Y zeolites and their unit cell size. The vibrations, however, are severely influenced by the charge distribution within the zeolite. Hence, the position of the charge-balancing cations and the water content affect the Raman spectra. Pyridine adsorption results in a rearrangement of the cations or water molecules still present in the structure after activation, and thus alters the vibrations of the zeolite lattice.

Raman spectroscopic study of plasma-treated salmon DNA

NASA Astrophysics Data System (ADS)

Joon Lee, Geon; Kwon, Young-Wan; Hee Kim, Yong; Ha Choi, Eun

2013-01-01

In this research, we studied the effect of plasma treatment on the optical/structural properties of the deoxyribonucleic acid (DNA) extracted from salmon sperm. DNA-cetyltrimethylammonium (CTMA) films were obtained by complexation of DNA with CTMA. Circular dichroism (CD) and Raman spectra indicated that DNA retained its double helical structure in the solid film. The Raman spectra exhibited several vibration modes corresponding to the nuclear bases and the deoxyribose-phosphate backbones of the DNA, as well as the alkylchains of CTMA. Dielectric-barrier-discharge (DBD) plasma treatment induced structural modification and damage to the DNA, as observed by changes in the ultraviolet-visible absorption, CD, and Raman spectra. The optical emission spectra of the DBD plasma confirmed that DNA modification was induced by plasma ions such as reactive oxygen species and reactive nitrogen species.

Temperature induced phonon behaviour in germanium selenide thin films probed by Raman spectroscopy

NASA Astrophysics Data System (ADS)

Taube, A.; Łapińska, A.; Judek, J.; Wochtman, N.; Zdrojek, M.

2016-08-01

Here we report a detailed study of temperature-dependent phonon properties of exfoliated germanium selenide thin films (several tens of nanometers thick) probed by Raman spectroscopy in the 70-350 K temperature range. The temperature-dependent behavior of the positions and widths of the Raman modes was nonlinear. We concluded that the observed effects arise from anharmonic phonon-phonon interactions and are explained by the phenomenon of optical phonon decay into acoustic phonons. At temperatures above 200 K, the position of the Raman modes tended to be linearly dependent, and the first order temperature coefficients χ were  -0.0277, -0.0197 and  -0.031 cm-1 K-1 for B 3g , A g(1) and A g(2) modes, respectively.

Glioblastoma cells labeled by robust Raman tags for enhancing imaging contrast.

PubMed

Huang, Li-Ching; Chang, Yung-Ching; Wu, Yi-Syuan; Sun, Wei-Lun; Liu, Chan-Chuan; Sze, Chun-I; Chen, Shiuan-Yeh

2018-05-01

Complete removal of a glioblastoma multiforme (GBM), a highly malignant brain tumor, is challenging due to its infiltrative characteristics. Therefore, utilizing imaging agents such as fluorophores to increase the contrast between GBM and normal cells can help neurosurgeons to locate residual cancer cells during image guided surgery. In this work, Raman tag based labeling and imaging for GBM cells in vitro is described and evaluated. The cell membrane of a GBM adsorbs a substantial amount of functionalized Raman tags through overexpression of the epidermal growth factor receptor (EGFR) and "broadcasts" stronger pre-defined Raman signals than normal cells. The average ratio between Raman signals from a GBM cell and autofluorescence from a normal cell can be up to 15. In addition, the intensity of these images is stable under laser illuminations without suffering from the severe photo-bleaching that usually occurs in fluorescent imaging. Our results show that labeling and imaging GBM cells via robust Raman tags is a viable alternative method to distinguish them from normal cells. This Raman tag based method can be used solely or integrated into an existing fluorescence system to improve the identification of infiltrative glial tumor cells around the boundary, which will further reduce GBM recurrence. In addition, it can also be applied/extended to other types of cancer to improve the effectiveness of image guided surgery.

Glioblastoma cells labeled by robust Raman tags for enhancing imaging contrast

PubMed Central

Huang, Li-Ching; Chang, Yung-Ching; Wu, Yi-Syuan; Sun, Wei-Lun; Liu, Chan-Chuan; Sze, Chun-I; Chen, Shiuan-Yeh

2018-01-01

Complete removal of a glioblastoma multiforme (GBM), a highly malignant brain tumor, is challenging due to its infiltrative characteristics. Therefore, utilizing imaging agents such as fluorophores to increase the contrast between GBM and normal cells can help neurosurgeons to locate residual cancer cells during image guided surgery. In this work, Raman tag based labeling and imaging for GBM cells in vitro is described and evaluated. The cell membrane of a GBM adsorbs a substantial amount of functionalized Raman tags through overexpression of the epidermal growth factor receptor (EGFR) and “broadcasts” stronger pre-defined Raman signals than normal cells. The average ratio between Raman signals from a GBM cell and autofluorescence from a normal cell can be up to 15. In addition, the intensity of these images is stable under laser illuminations without suffering from the severe photo-bleaching that usually occurs in fluorescent imaging. Our results show that labeling and imaging GBM cells via robust Raman tags is a viable alternative method to distinguish them from normal cells. This Raman tag based method can be used solely or integrated into an existing fluorescence system to improve the identification of infiltrative glial tumor cells around the boundary, which will further reduce GBM recurrence. In addition, it can also be applied/extended to other types of cancer to improve the effectiveness of image guided surgery. PMID:29760976

Probing Pharmaceutical Mixtures during Milling: The Potency of Low-Frequency Raman Spectroscopy in Identifying Disorder.

PubMed

Walker, Greg; Römann, Philipp; Poller, Bettina; Löbmann, Korbinian; Grohganz, Holger; Rooney, Jeremy S; Huff, Gregory S; Smith, Geoffrey P S; Rades, Thomas; Gordon, Keith C; Strachan, Clare J; Fraser-Miller, Sara J

2017-12-04

This study uses a multimodal analytical approach to evaluate the rates of (co)amorphization of milled drug and excipient and the effectiveness of different analytical methods in detecting these changes. Indomethacin and tryptophan were the model substances, and the analytical methods included low-frequency Raman spectroscopy (785 nm excitation and capable of measuring both low- (10 to 250 cm -1 ) and midfrequency (450 to 1800 cm -1 ) regimes, and a 830 nm system (5 to 250 cm -1 )), conventional (200-3000 cm -1 ) Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR), and X-ray powder diffraction (XRPD). The kinetics of amorphization were found to be faster for the mixture, and indeed, for indomethacin, only partial amorphization occurred (after 360 min of milling). Each technique was capable of identifying the transformations, but some, such as low-frequency Raman spectroscopy and XRPD, provided less ambiguous signatures than the midvibrational frequency techniques (conventional Raman and FTIR). The low-frequency Raman spectra showed intense phonon mode bands for the crystalline and cocrystalline samples that could be used as a sensitive probe of order. Multivariate analysis has been used to further interpret the spectral changes. Overall, this study demonstrates the potential of low-frequency Raman spectroscopy, which has several practical advantages over XRPD, for probing (dis-)order during pharmaceutical processing, showcasing its potential for future development, and implementation as an in-line process monitoring method.

Structural analysis of the antimalarial drug halofantrine by means of Raman spectroscopy and density functional theory calculations

NASA Astrophysics Data System (ADS)

Frosch, Torsten; Popp, Jürgen

2010-07-01

The structure of the antimalarial drug halofantrine is analyzed by means of density functional theory (DFT) calculations, IR, and Raman spectroscopy. Strong, selective enhancements of the Raman bands of halofantrine at 1621 and 1590 cm-1 are discovered by means of UV resonance Raman spectroscopy with excitation wavelength λexc=244 nm. These signal enhancements can be exploited for a localization of small concentrations of halofantrine in a biological environment. The Raman spectrum of halofantrine is calculated by means of DFT calculations [B3LYP/6-311+G(d,p)]. The calculation is very useful for a thorough mode assignment of the Raman bands of halofantrine. The strong bands at 1621 and 1590 cm-1 in the UV Raman spectrum are assigned to combined C=C stretching vibrations in the phenanthrene ring of halofantrine. These bands are considered as putative marker bands for ππ interactions with the biological target molecules. The calculation of the electron density demonstrates a strong distribution across the phenanthrene ring of halofantrine, besides the electron withdrawing effect of the Cl and CF3 substituents. This strong and even electron density distribution supports the hypothesis of ππ stacking as a possible mode of action of halofantrine. Complementary IR spectroscopy is performed for an investigation of vibrations of polar functional groups of the halofantrine molecule.

Electron and donor-impurity-related Raman scattering and Raman gain in triangular quantum dots under an applied electric field

NASA Astrophysics Data System (ADS)

Tiutiunnyk, Anton; Akimov, Volodymyr; Tulupenko, Viktor; Mora-Ramos, Miguel E.; Kasapoglu, Esin; Morales, Alvaro L.; Duque, Carlos Alberto

2016-04-01

The differential cross-section of electron Raman scattering and the Raman gain are calculated and analysed in the case of prismatic quantum dots with equilateral triangle base shape. The study takes into account their dependencies on the size of the triangle, the influence of externally applied electric field as well as the presence of an ionized donor center located at the triangle's orthocenter. The calculations are made within the effective mass and parabolic band approximations, with a diagonalization scheme being applied to obtain the eigenfunctions and eigenvalues of the x- y Hamiltonian. The incident and secondary (scattered) radiation have been considered linearly-polarized along the y-direction, coinciding with the direction of the applied electric field. For the case with an impurity center, Raman scattering with the intermediate state energy below the initial state one has been found to show maximum differential cross-section more than by an order of magnitude bigger than that resulting from the scheme with lower intermediate state energy. The Raman gain has maximum magnitude around 35 nm dot size and electric field of 40 kV/cm for the case without impurity and at maximum considered values of the input parameters for the case with impurity. Values of Raman gain of the order of up to 104cm-1 are predicted in both cases.

Structure-selective hot-spot Raman enhancement for direct identification and detection of trace penicilloic acid allergen in penicillin.

PubMed

Zhang, Liying; Jin, Yang; Mao, Hui; Zheng, Lei; Zhao, Jiawei; Peng, Yan; Du, Shuhu; Zhang, Zhongping

2014-08-15

Trace penicilloic acid allergen frequently leads to various fatal immune responses to many patients, but it is still a challenge to directly discriminate and detect its residue in penicillin by a chemosensing way. Here, we report that silver-coated gold nanoparticles (Au@Ag NPs) exhibit a structure-selective hot-spot Raman enhancement capability for direct identification and detection of trace penicilloic acid in penicillin. It has been demonstrated that penicilloic acid can very easily link Au@Ag NPs together by its two carboxyl groups, locating itself spontaneously at the interparticle of Au@Ag NPs to form strong Raman hot-spot. At the critical concentration inducing the nanoparticle aggregation, Raman-enhanced effect of penicilloic acid is ~60,000 folds higher than that of penicillin. In particular, the selective Raman enhancement to the two carboxyl groups makes the peak of carboxyl group at C6 of penicilloic acid appear as a new Raman signal due to the opening of β-lactam ring of penicillin. The surface-enhanced Raman scattering (SERS) nanoparticle sensor reaches a sensitive limit lower than the prescribed 1.0‰ penicilloic acid residue in penicillin. The novel strategy to examine allergen is more rapid, convenient and inexpensive than the conventional separation-based assay methods. Copyright © 2014 Elsevier B.V. All rights reserved.

Enhancement of local surface plasmon resonance (LSPR) effect by biocompatible metal clustering based on ZnO nanorods in Raman measurements.

PubMed

Lee, Sanghwa; Lee, Seung Ho; Paulson, Bjorn; Lee, Jae-Chul; Kim, Jun Ki

2018-06-20

The development of size-selective and non-destructive detection techniques for nanosized biomarkers has many reasons, including the study of living cells and diagnostic applications. We present an approach for Raman signal enhancement on biocompatible sensing chips based on surface enhancement Raman spectroscopy (SERS). A sensing chip was fabricated by forming a ZnO-based nanorod structure so that the Raman enhancement occurred at a gap of several tens to several hundred nanometers. The effect of coffee-ring formation was eliminated by introducing the porous ZnO nanorods for the bio-liquid sample. A peculiarity of this approach is that the gold sputtered on the ZnO nanorods initially grows at their heads forming clusters, as confirmed by secondary electron microscopy. This clustering was verified by finite element analysis to be the main factor for enhancement of local surface plasmon resonance (LSPR). This clustering property and the ability to adjust the size of the nanorods enabled the signal acquisition points to be refined using confocal based Raman spectroscopy, which could be applied directly to the sensor chip based on the optimization process in this experiment. It was demonstrated by using common cancer cell lines that cell growth was high on these gold-clad ZnO nanorod-based surface-enhanced Raman substrates. The porosity of the sensing chip, the improved structure for signal enhancement, and the cell assay make these gold-coated ZnO nanorods substrates promising biosensing chips with excellent potential for detecting nanometric biomarkers secreted by cells. Copyright © 2018 Elsevier B.V. All rights reserved.

The influence of ionic strength on carbonate-based spectroscopic barometry for aqueous fluids: an in-situ Raman study on Na2CO3-NaCl solutions

PubMed Central

Wu, Jia; Wang, Shixia; Zheng, Haifei

2016-01-01

The Raman wavenumber of the symmetric stretching vibration of carbonate ion (ν1-CO32−) was measured in three aqueous solutions containing 2.0 mol·L−1 Na2CO3 and 0.20, 0.42, or 0.92 mol·L−1 NaCl, respectively, from 122 to 1538 MPa at 22 °C using a moissanite anvil cell. The ν1 Raman signal linearly shifted to higher wavenumbers with increasing pressure. Most importantly, the slope of ν1-CO32− Raman frequency shift (∂ν1/∂P)I was independent of NaCl concentration. Moreover, elevated ionic strength was found to shift the apparent outline of the carbonate peak toward low wavenumbers, possibly by increasing the proportion of the contact ion pair NaCO3−. Further investigations revealed no cross-interaction between the pressure effect and the ionic strength effect on the Raman spectra, possibly because the distribution of different ion-pair species in the carbonate equilibrium was largely pressure-independent. These results suggested that the ionic strength should be incorporated as an additional constraint for measuring the internal pressure of various solution-based systems. Combining the ν1-CO32− Raman frequency slope with the pressure herein with the values for the temperature or the ionic strength dependencies determined from previous studies, we developed an empirical equation that can be used to estimate the pressure of carbonate-bearing aqueous solutions. PMID:27982064

Origin of the monolayer Raman signature in hexagonal boron nitride: a first-principles analysis.

PubMed

Ontaneda, Jorge; Singh, Anjali; Waghmare, Umesh V; Grau-Crespo, Ricardo

2018-05-10

Monolayers of hexagonal boron nitride (h-BN) can in principle be identified by a Raman signature, consisting of an upshift in the frequency of the E 2g vibrational mode with respect to the bulk value, but the origin of this shift (intrinsic or support-induced) is still debated. Herein we use density functional theory calculations to investigate whether there is an intrinsic Raman shift in the h-BN monolayer in comparison with the bulk. There is universal agreement among all tested functionals in predicting the magnitude of the frequency shift upon a variation in the in-plane cell parameter. It is clear that a small in-plane contraction can explain the Raman peak upshift from bulk to monolayer. However, we show that the larger in-plane parameter in the bulk (compared to the monolayer) results from non-local correlation effects, which cannot be accounted for by local functionals or those with empirical dispersion corrections. Using a non-local-correlation functional, we then investigate the effect of finite temperatures on the Raman signature. We demonstrate that bulk h-BN thermally expands in the direction perpendicular to the layers, while the intralayer distances slightly contract, in agreement with observed experimental behavior. Interestingly, the difference in in-plane cell parameter between bulk and monolayer decreases with temperature, and becomes very small at room temperature. We conclude that the different thermal expansion of bulk and monolayer partially 'erases' the intrinsic Raman signature, accounting for its small magnitude in recent experiments on suspended samples.

Raman spectroscopy application in frozen carrot cooked in different ways and the relationship with carotenoids.

PubMed

Camorani, Paolo; Chiavaro, Emma; Cristofolini, Luigi; Paciulli, Maria; Zaupa, Maria; Visconti, Attilio; Fogliano, Vincenzo; Pellegrini, Nicoletta

2015-08-30

Raman spectroscopy, in its confocal micro-Raman variation, has been recently proposed as a spatially resolved method to identify carotenoids in various food matrices, being faster, non-destructive, and avoiding sample extraction, but no data are present in the literature concerning its application to the evaluation of carotenoid pattern changes after thermal treatment of carrots. The effect of three cooking methods (i.e. boiling, steaming and microwaving) was evaluated on frozen carrot, comparing changes on carotenoid profiles measured by means of Raman spectroscopy with their high-performance liquid chromatographic determination and colour. A more pronounced detrimental effect on carotenoids was detected in steamed carrots, in accordance with colour data. Conversely, boiling and, to a lesser extent, microwaving caused an increase in carotenoid concentration. Cooking procedures affected the Raman spectral features of carotenoids, causing a shift of vibration frequencies towards a higher energy, increase in the spectral baseline and peak intensities as well as a broadening of their width, probably in relation to the thermal degradation of longer carotenoids (i.e. the all-trans form) and the isomerization process. In particular, steamed samples showed a significantly higher increase of centre frequency, in accordance with a more pronounced isomerization and changes in colour parameters. This work showed that the evolution of Raman spectral parameters could provide information on carotenoid bioaccessibility for carrots cooked using various methods. This paves the way for a future use of this technique to monitor and optimize cooking processes aimed at maximizing carotenoid bioaccessibility and bioavailability. © 2014 Society of Chemical Industry.

Origin of the monolayer Raman signature in hexagonal boron nitride: a first-principles analysis

NASA Astrophysics Data System (ADS)

Ontaneda, Jorge; Singh, Anjali; Waghmare, Umesh V.; Grau-Crespo, Ricardo

2018-05-01

Monolayers of hexagonal boron nitride (h-BN) can in principle be identified by a Raman signature, consisting of an upshift in the frequency of the E2g vibrational mode with respect to the bulk value, but the origin of this shift (intrinsic or support-induced) is still debated. Herein we use density functional theory calculations to investigate whether there is an intrinsic Raman shift in the h-BN monolayer in comparison with the bulk. There is universal agreement among all tested functionals in predicting the magnitude of the frequency shift upon a variation in the in-plane cell parameter. It is clear that a small in-plane contraction can explain the Raman peak upshift from bulk to monolayer. However, we show that the larger in-plane parameter in the bulk (compared to the monolayer) results from non-local correlation effects, which cannot be accounted for by local functionals or those with empirical dispersion corrections. Using a non-local-correlation functional, we then investigate the effect of finite temperatures on the Raman signature. We demonstrate that bulk h-BN thermally expands in the direction perpendicular to the layers, while the intralayer distances slightly contract, in agreement with observed experimental behavior. Interestingly, the difference in in-plane cell parameter between bulk and monolayer decreases with temperature, and becomes very small at room temperature. We conclude that the different thermal expansion of bulk and monolayer partially ‘erases’ the intrinsic Raman signature, accounting for its small magnitude in recent experiments on suspended samples.

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.

Laser irradiation of carbon nanotube films: Effects and heat dissipation probed by Raman spectroscopy

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

Mialichi, J. R.; Brasil, M. J. S. P.; Iikawa, F.

We investigate the thermal properties of thin films formed by single- and multi-walled carbon nanotubes submitted to laser irradiation using Raman scattering as a probe of both the tube morphology and the local temperature. The nanotubes were submitted to heating/cooling cycles attaining high laser intensities ({approx}1.4 MW/cm{sup 2}) under vacuum and in the presence of an atmosphere, with and without oxygen. We investigate the heat diffusion of the irradiated nanotubes to their surroundings and the effect of laser annealing on their properties. The presence of oxygen during laser irradiation gives rise to an irreversible increase of the Raman efficiency ofmore » the carbon nanotubes and to a remarkable increase of the thermal conductivity of multi-walled films. The second effect can be applied to design thermal conductive channels in devices based on carbon nanotube films using laser beams.« less

Confocal Raman microspectrometry: a vectorial electromagnetic treatment of the light focused and collected through a planar interface and its application to the study of a thin coating.

PubMed

Sourisseau, C; Maraval, P

2003-11-01

In-depth confocal Raman microspectrometry (CRM) studies through a planar interface between materials of mismatched refraction indices are known to be affected by a decrease of both the collected Raman intensity and the axial resolution as a function of the penetration depth. Following a previous model, which takes the refraction, diffraction, and spherical aberration effects into account when focusing a Gaussian incident laser beam with a high numerical aperture objective lens, a complete vectorial treatment of these phenomena is considered. It is demonstrated that off-axis refraction effects cannot be neglected and that the dimension of the confocal pinhole aperture plays a crucial role on the effective focal plane position and on the collection efficiency. We thus propose a more rigorous and complete approach to the problem, and we find a very good agreement between experimental and theoretical Raman intensity variations for a thick polyethylene sample as a function of the penetration depth. As compared with calculations where only refraction was considered, we confirm that the lengthening of the focus even for a large penetration depth is significantly reduced upon diffraction effects. As an illustrative example, the theoretical Raman responses for a thin coating of approximately 20 microns on a polymer substrate were investigated and compared to experimental results already published. Even though the interfacial region is spread over approximately 5-6 microns when using a 100x objective and a confocal pinhole of 200 microns diameter, it is definitively concluded that the apparent axial resolution is not drastically deteriorated with increasing depth and that the coating thickness may be directly estimated with a precision of approximately 1.0 micron (5%).

Investigation of Ferroelectric Domain Walls by Raman Spectroscopy

NASA Astrophysics Data System (ADS)

Stone, Gregory A.

Ferroelectric materials are characterized by an intrinsic spontaneous electric dipole moment that can be manipulated by the application of an electric field. Regions inside the crystal, known as domains, can have the spontaneous dipole moments oriented in a different direction than the surrounding crystal. Due to favorable piezoelectric, pyroelectric, electro-optic, and nonlinear optical properties, ferroelectric materials are attractive for commercial applications. Many devices, such as nonlinear frequency converters, require precisely engineered domain patterns. The properties of domains and their boundaries, known as domain walls, are vital to the performance and limitations of these devices. As a result, ferroelectric domains and the domain walls have been the focus of many scientific studies. Despite all this work, questions remain regarding their properties. This work is aimed at developing a better understanding of the properties of the domain wall using confocal Raman spectroscopy. Raman spectra taken from domain walls in Lithium Niobate and Lithium Tantalate reveal two distinct changes in the Raman spectra: (1) Shifts in frequency of the bulk Raman modes, which persists over a range of 0.2-0.5 mu m from the domain wall. The absence of this effect in defect free stoichiometric Lithium Tantalate indicates that the shifts are related to defects inside the crystal. (2) The presence of Raman modes corresponding to phonons propagating orthogonal to the laser beam axis, which are not collected in the bulk crystal. The phonons also preferential propagate normal to the domain wall. These modes are detected up to 0.35 mum from the domain wall. The observation and separation of these effects was made possible by the optimized spatial resolution (0.23 mum) of a home-built scanning confocal microscope and the fact that degeneracy of the transverse and longitudinal phonon polarization is lifted by polar phonons in Lithium Niobate and Lithium Tantalate. Raman investigations on other interfaces such as front, side and bottom surfaces revealed a similar appearance of modes due to distortion of wave fronts and reflection. These surfaces are studied to provide insight into mechanism that give rise to Raman modes typically absent for the particular orientation of the crystal.

Raman Spectroscopic Signature Markers of Dopamine-Human Dopamine Transporter Interaction in Living Cells.

PubMed

Silwal, Achut P; Yadav, Rajeev; Sprague, Jon E; Lu, H Peter

2017-07-19

Dopamine (DA) controls many psychological and behavioral activities in the central nervous system (CNS) through interactions with the human dopamine transporter (hDAT) and dopamine receptors. The roles of DA in the function of the CNS are affected by the targeted binding of drugs to hDAT; thus, hDAT plays a critical role in neurophysiology and neuropathophysiology. An effective experimental method is necessary to study the DA-hDAT interaction and effects of variety of drugs like psychostimulants and antidepressants that are dependent on this interaction. In searching for obtaining and identifying the Raman spectral signatures, we have used surface enhanced Raman scattering (SERS) spectroscopy to record SERS spectra from DA, human embryonic kidney 293 cells (HEK293), hDAT-HEK293, DA-HEK293, and DA-hDAT-HEK293. We have demonstrated a specific 2D-distribution SERS spectral analytical approach to analyze DA-hDAT interaction. Our study shows that the Raman modes at 807, 839, 1076, 1090, 1538, and 1665 cm -1 are related to DA-hDAT interaction, where Raman shifts at 807 and 1076 cm -1 are the signature markers for the bound state of DA to probe DA-hDAT interaction. On the basis of density function theory (DFT) calculation, Raman shift of the bound state of DA at 807 cm -1 is related to combination of bending modes α(C3-O10-H21), α(C2-O11-H22), α(C7-C8-H18), α(C6-C4-H13), α(C7-C8-H19), and α(C7-C8-N9), and Raman shift at 1076 cm -1 is related to combination of bending modes α(H19-N9-C8), γ(N9-H19), γ(C8-H19), γ(N9-H20), γ(C8-H18), and α(C7-C8-H18). These findings demonstrate that protein-ligand interactions can be confirmed by probing change in Raman shift of ligand molecules, which could be crucial to understanding molecular interactions between neurotransmitters and their receptors or transporters.

A parameter selection for Raman spectroscopy-based detection of chemical contaminants in food powders

USDA-ARS?s Scientific Manuscript database

Raman spectroscopy technique has proven to be a reliable method for detection of chemical contaminants in food ingredients and products. To detect each contaminant particle in a food sample, it is important to determine the effective depth of penetration of laser through the food sample and the corr...

Near-Ir surface-enhanced Raman spectrum of lignin

Treesearch

Umesh P. Agarwal; Richard S. Reiner

2009-01-01

Compacted powders of commercially available nano- and microparticles of silver were used to successfully induce the surface enhanced Raman scattering (SERS) effect in spruce milled-wood lignin (MWL). For the two silver particle sizes used in this investigation, the spectra were mostly similar. Some general characteristics of the lignin SERS spectrum are described. The...

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

PdSe2: Pentagonal Two-Dimensional Layers with High Air Stability for Electronics.

PubMed

Oyedele, Akinola D; Yang, Shize; Liang, Liangbo; Puretzky, Alexander A; Wang, Kai; Zhang, Jingjie; Yu, Peng; Pudasaini, Pushpa R; Ghosh, Avik W; Liu, Zheng; Rouleau, Christopher M; Sumpter, Bobby G; Chisholm, Matthew F; Zhou, Wu; Rack, Philip D; Geohegan, David B; Xiao, Kai

2017-10-11

Most studied two-dimensional (2D) materials exhibit isotropic behavior due to high lattice symmetry; however, lower-symmetry 2D materials such as phosphorene and other elemental 2D materials exhibit very interesting anisotropic properties. In this work, we report the atomic structure, electronic properties, and vibrational modes of few-layered PdSe 2 exfoliated from bulk crystals, a pentagonal 2D layered noble transition metal dichalcogenide with a puckered morphology that is air-stable. Micro-absorption optical spectroscopy and first-principles calculations reveal a wide band gap variation in this material from 0 (bulk) to 1.3 eV (monolayer). The Raman-active vibrational modes of PdSe 2 were identified using polarized Raman spectroscopy, and a strong interlayer interaction was revealed from large, thickness-dependent Raman peak shifts, agreeing with first-principles Raman simulations. Field-effect transistors made from the few-layer PdSe 2 display tunable ambipolar charge carrier conduction with a high electron field-effect mobility of ∼158 cm 2 V -1 s -1 , indicating the promise of this anisotropic, air-stable, pentagonal 2D material for 2D electronics.

Material for surface-enhanced Raman spectroscopy, and SER sensors and method for preparing same

NASA Technical Reports Server (NTRS)

Farquharson, Stuart (Inventor); Nelson, Chad (Inventor); Lee, Yuan-Hsiang (Inventor)

2003-01-01

Metal-doped sol-gel materials, suitable for use as sensors for surface-enhanced Raman spectroscopic analysis for trace chemical detection, are produced by effecting gelation and solvent removal of a doped sol-gel under mild temperature conditions. At least in certain instances reaction and drying will desirably be effected in an oxygen-starved environment. The metal of the sol-gel material functions, when irradiated, to produce a plasmon field for interaction with molecules of an analyte in contact therewith, increasing by orders of magnitude Raman photons that are generate by excitation radiation, and the method allows matching of the metal and metal particle size to a wavelength of light (or incident radiation, e.g., laser radiation) to generate surface plasmons. The porosity of the sol-gel material dramatically increases the surface area, and thereby the amount of metal exposed for analyte interaction. The sensors provided may be in the form of glass vials, fiber optics, multi-well micro-sample plates, etc., having surface coatings of the doped sol-gel material, to provide sampling systems for use in a Raman instrument.

Thermally generated metals for plasmonic coloring and surface-enhanced Raman sensing

NASA Astrophysics Data System (ADS)

Huang, Zhenping; Chen, Jian; Liu, Guiqiang; Wang, Yan; Liu, Yi; Tang, Li; Liu, Zhengqi

2018-03-01

Spectral coloring glass and its application on the surface-enhanced Raman scattering are demonstrated experimentally via a simple and moderate heat-treating of the top ultrathin gold film to create discrete nanoparticles, which can produce localized surface plasmon resonances and strong plasmonic near-field coupling effects. Ultrathin metal films with a wide range of thicknesses are investigated by different heat-treatment processes. The annealed metal films have been demonstrated with a series of spectral coloring responses. Moreover, the microscopy images of the metal film structures confirm the formation of distinct geometry features in these operation procedures. Densely packed nanoparticles are observed for the ultrathin metal film with the single-digit level of thickness. With increasing the film thickness over 10 nm, metallic clusters and porous morphologies can be obtained. Importantly, the metallic resonators can provide enhanced Raman scattering with the detection limit down to 10 - 7 molL - 1 of Rhodamine 6G molecules due to the excitation of plasmon resonances and strong near-field coupling effects. These features hold great potential for large-scale and low-cost production of colored glass and Raman substrate.

Control of ultrafast pulses in a hydrogen-filled hollow-core photonic-crystal fiber by Raman coherence

NASA Astrophysics Data System (ADS)

Belli, F.; Abdolvand, A.; Travers, J. C.; Russell, P. St. J.

2018-01-01

We present the results of an experimental and numerical investigation into temporally nonlocal coherent interactions between ultrashort pulses, mediated by Raman coherence, in a gas-filled kagome-style hollow-core photonic-crystal fiber. A pump pulse first sets up the Raman coherence, creating a refractive index spatiotemporal grating in the gas that travels at the group velocity of the pump pulse. Varying the arrival time of a second, probe, pulse allows a high degree of control over its evolution as it propagates along the fiber through the grating. Of particular interest are soliton-driven effects such as self-compression and dispersive wave (DW) emission. In the experiments reported, a DW is emitted at ˜300 nm and exhibits a wiggling effect, with its central frequency oscillating periodically with pump-probe delay. The results demonstrate that a strong Raman coherence, created in a broadband guiding gas-filled kagome photonic-crystal fiber, can be used to control the nonlinear dynamics of ultrashort probe pulses, even in difficult-to-access spectral regions such as the deep and vacuum ultraviolet.

Three-dimensional hybrid silicon nanostructures for surface enhanced Raman spectroscopy based molecular detection

NASA Astrophysics Data System (ADS)

Vendamani, V. S.; Nageswara Rao, S. V. S.; Venugopal Rao, S.; Kanjilal, D.; Pathak, A. P.

2018-01-01

Three-dimensional silver nanoparticles decorated vertically aligned Si nanowires (Si NWs) are effective surface-enhanced Raman spectroscopy (SERS) substrates for molecular detection at low concentration levels. The length of Si NWs prepared by silver assisted electroless etching is increased with an increase in etching time, which resulted in the reduced optical reflection in the visible region. These substrates were tested and optimized by measuring the Raman spectrum of standard dye Rhodamine 6G (R6G) of 10 nM concentration. Further, effective SERS enhancements of ˜105 and ˜104 were observed for the cytosine protein (concentration of 50 μM) and ammonium perchlorate (oxidizer used in explosives composition with a concentration of 10 μM), respectively. It is established that these three-dimensional SERS substrates yielded considerably higher enhancement factors for the detection of R6G when compared to previous reports. The sensitivity can further be increased and optimized since the Raman enhancement was found to increase with an increase in the density of silver nanoparticles decorated on the walls of Si NWs.

Anharmonic Effects on Vibrational Spectra Intensities: Infrared, Raman, Vibrational Circular Dichroism and Raman Optical Activity

PubMed Central

Bloino, Julien; Biczysko, Malgorzata; Barone, Vincenzo

2017-01-01

The aim of this paper is twofold. First, we want to report the extension of our virtual multifrequency spectrometer (VMS) to anharmonic intensities for Raman Optical Activity (ROA) with the full inclusion of first- and second-order resonances for both frequencies and intensities in the framework of the generalized second-order vibrational perturbation theory (GVPT2) for all kinds of vibrational spectroscopies. Then, from a more general point of view, we want to present and validate the performance of VMS for the parallel analysis of different vibrational spectra for medium-sized molecules (IR, Raman, VCD, ROA) including both mechanical and electric/magnetic anharmonicity. For the well-known methyloxirane benchmark, careful selection of density functional, basis set, and resonance tresholds permitted to reach qualitative and quantitative vis-à-vis comparison between experimental and computed band positions and shapes. Next, the whole series of halogenated azetidinones is analyzed, showing that it is now possible to interpret different spectra in terms of electronegativity, polarizability, and hindrance variation between closely related substituents, chiral spectroscopies being particular effective in this connection. PMID:26580121

Molecular alignment and orientation with a hybrid Raman scattering technique

NASA Astrophysics Data System (ADS)

Bustard, Philip J.; Lausten, R.; Sussman, Benjamin J.

2012-11-01

We demonstrate a scheme for the preparation of molecular alignment and angular momentum orientation using a hybrid combination of two limits of Raman scattering. First a weak, impulsive pump pulse initializes the system via the nonresonant dynamic Stark effect. Then, having overcome the influence of the vacuum fluctuations, an amplification pulse selectively enhances the initial coherences by transient stimulated Raman scattering, generating alignment and angular momentum orientation of molecular hydrogen. The amplitude and phase of the resulting coherent dynamics are experimentally probed, indicating an amplification factor of 4.5. An analytic theory is developed to model the dynamics.

Electron Raman scattering in a strained ZnO/MgZnO double quantum well

NASA Astrophysics Data System (ADS)

Mojab-abpardeh, M.; Karimi, M. J.

2018-02-01

In this work, the electron Raman scattering in a strained ZnO / MgZnO double quantum wells is studied. The energy eigenvalues and the wave functions are obtained using the transfer matrix method. The effects of Mg composition, well width and barrier width on the internal electric field in well and barrier layers are investigated. Then, the influences of these parameters on the differential cross-section of electron Raman scattering are studied. Results indicate that the position, magnitude and the number of the peaks depend on the Mg composition, well width and barrier width.

Two-Dimensional Raman Correlation Analysis of Diseased Esophagus in a Rat

NASA Astrophysics Data System (ADS)

Takanezawa, Sota; Morita, Shin-ichi; Maruyama, Atsushi; Murakami, Takurou N.; Kawashima, Norimichi; Endo, Hiroyuki; Iijima, Katsunori; Asakura, Tohru; Shimosegawa, Tooru; Sato, Hidetoshi

2010-07-01

Generalized two-dimensional (2D) Raman correlation analysis effectively distinguished a benign tumor from normal tissue. Line profiling Raman spectra of a rat esophagus, including a benign tumor, were measured and the generalized 2D synchronous and asynchronous spectra were calculated. In the autocorrelation area of the amide I band of proteins in the asynchronous map, a cross-like pattern was observed. A simulation study indicated that the pattern was caused by a sharp band component in the amide I band region. We considered that the benign tumor corresponded to the sharp component.

Raman spectroscopy detects biomolecular changes associated with nanoencapsulated hesperetin treatment in experimental oral carcinogenesis

NASA Astrophysics Data System (ADS)

Gurushankar, K.; Gohulkumar, M.; Kumar, Piyush; Krishna, C. Murali; Krishnakumar, N.

2016-03-01

Recently it has been shown that Raman spectroscopy possesses great potential in the investigation of biomolecular changes of tumor tissues with therapeutic drug response in a non-invasive and label-free manner. The present study is designed to investigate the antitumor effect of hespertin-loaded nanoparticles (HETNPs) relative to the efficacy of native hesperetin (HET) in modifying the biomolecular changes during 7,12-dimethyl benz(a)anthracene (DMBA)-induced oral carcinogenesis using a Raman spectroscopic technique. Significant differences in the intensity and shape of the Raman spectra between the control and the experimental tissues at 1800-500 cm-1 were observed. Tumor tissues are characterized by an increase in the relative amount of proteins, nucleic acids, tryptophan and phenylalanine and a decrease in the percentage of lipids when compared to the control tissues. Further, oral administration of HET and its nanoparticulates restored the status of the lipids and significantly decreased the levels of protein and nucleic acid content. Treatment with HETNPs showed a more potent antitumor effect than treatment with native HET, which resulted in an overall reduction in the intensity of several biochemical Raman bands in DMBA-induced oral carcinogenesis being observed. Principal component and linear discriminant analysis (PC-LDA), together with leave-one-out cross validation (LOOCV) on Raman spectra yielded diagnostic sensitivities of 100%, 80%, 91.6% and 65% and specificities of 100%, 65%, 60% and 55% for classification of control versus DMBA, DMBA versus DMBA  +  HET, DMBA versus DMBA  +  HETNPs and DMBA  +  HET versus DMBA  +  HETNPs treated tissue groups, respectively. These results further demonstrate that Raman spectroscopy associated with multivariate statistical algorithms could be a valuable tool for developing a comprehensive understanding of the process of biomolecular changes, and could reveal the signatures of the antitumor response of drugs.

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 piezoelectric effect in wurtzite GaN, which has been predicted theoretically in zinc blende gallium arsenide (GaAs).

Study of corrosion in archaeological gilded irons by Raman imaging and a coupled scanning electron microscope-Raman system.

PubMed

Veneranda, Marco; Costantini, Ilaria; de Vallejuelo, Silvia Fdez-Ortiz; Garcia, Laura; García, Iñaki; Castro, Kepa; Azkarate, Agustín; Madariaga, Juan Manuel

2016-12-13

In this work, analytical and chemical imaging tools have been applied to the study of a gilded spur found in the medieval necropolis of Erenozar (Bizkaia, Spain). As a first step, a lot of portable equipment has been used to study the object in a non-invasive way. The hand-held energy-dispersive X-ray fluorescence equipment allowed us to characterize the artefact as a rare example of an iron matrix item decorated by means of a fire gilding technique. On the other hand, the use of a portable Raman system helped us to detect the main degradation compounds affecting the spur. Afterwards, further information was acquired in the laboratory by analysing detached fragments. The molecular images obtained using confocal Raman microscopy permitted us to characterize the stratigraphic succession of iron corrosions. Furthermore, the combined use of this technique with a scanning electron microscope (SEM) was achieved owing to the use of a structural and chemical analyser interface. In this way, the molecular characterization, enhanced by the magnification feature of the SEM, allowed us to identify several micrometric degradation compounds. Finally, the effectiveness of one of the most used desalination baths (NaOH) was evaluated by comparing its effects with those provided by a reference bath (MilliQ). The comparison proved that basic treatment avoided any side effects on the spur decorated by fire gilding, compensating for the lack of bibliographic documentation in this field.This article is part of the themed issue 'Raman spectroscopy in art and archaeology'. © 2016 The Author(s).

Study of corrosion in archaeological gilded irons by Raman imaging and a coupled scanning electron microscope-Raman system

NASA Astrophysics Data System (ADS)

Veneranda, Marco; Costantini, Ilaria; de Vallejuelo, Silvia Fdez-Ortiz; Garcia, Laura; García, Iñaki; Castro, Kepa; Azkarate, Agustín; Madariaga, Juan Manuel

2016-12-01

In this work, analytical and chemical imaging tools have been applied to the study of a gilded spur found in the medieval necropolis of Erenozar (Bizkaia, Spain). As a first step, a lot of portable equipment has been used to study the object in a non-invasive way. The hand-held energy-dispersive X-ray fluorescence equipment allowed us to characterize the artefact as a rare example of an iron matrix item decorated by means of a fire gilding technique. On the other hand, the use of a portable Raman system helped us to detect the main degradation compounds affecting the spur. Afterwards, further information was acquired in the laboratory by analysing detached fragments. The molecular images obtained using confocal Raman microscopy permitted us to characterize the stratigraphic succession of iron corrosions. Furthermore, the combined use of this technique with a scanning electron microscope (SEM) was achieved owing to the use of a structural and chemical analyser interface. In this way, the molecular characterization, enhanced by the magnification feature of the SEM, allowed us to identify several micrometric degradation compounds. Finally, the effectiveness of one of the most used desalination baths (NaOH) was evaluated by comparing its effects with those provided by a reference bath (MilliQ). The comparison proved that basic treatment avoided any side effects on the spur decorated by fire gilding, compensating for the lack of bibliographic documentation in this field. This article is part of the themed issue "Raman spectroscopy in art and archaeology".

Study of corrosion in archaeological gilded irons by Raman imaging and a coupled scanning electron microscope–Raman system

PubMed Central

Veneranda, Marco; Costantini, Ilaria; de Vallejuelo, Silvia Fdez-Ortiz; Garcia, Laura; García, Iñaki; Azkarate, Agustín; Madariaga, Juan Manuel

2016-01-01

In this work, analytical and chemical imaging tools have been applied to the study of a gilded spur found in the medieval necropolis of Erenozar (Bizkaia, Spain). As a first step, a lot of portable equipment has been used to study the object in a non-invasive way. The hand-held energy-dispersive X-ray fluorescence equipment allowed us to characterize the artefact as a rare example of an iron matrix item decorated by means of a fire gilding technique. On the other hand, the use of a portable Raman system helped us to detect the main degradation compounds affecting the spur. Afterwards, further information was acquired in the laboratory by analysing detached fragments. The molecular images obtained using confocal Raman microscopy permitted us to characterize the stratigraphic succession of iron corrosions. Furthermore, the combined use of this technique with a scanning electron microscope (SEM) was achieved owing to the use of a structural and chemical analyser interface. In this way, the molecular characterization, enhanced by the magnification feature of the SEM, allowed us to identify several micrometric degradation compounds. Finally, the effectiveness of one of the most used desalination baths (NaOH) was evaluated by comparing its effects with those provided by a reference bath (MilliQ). The comparison proved that basic treatment avoided any side effects on the spur decorated by fire gilding, compensating for the lack of bibliographic documentation in this field. This article is part of the themed issue ‘Raman spectroscopy in art and archaeology’. PMID:27799430

Operando plasmon-enhanced Raman spectroscopy in silicon anodes for Li-ion battery

NASA Astrophysics Data System (ADS)

Miroshnikov, Yana; Zitoun, David

2017-11-01

Silicon, an attractive candidate for high-energy lithium-ion batteries (LIBs), displays an alloying mechanism with lithium and presents several unique characteristics which make it an interesting scientific topic and also a technological challenge. In situ local probe measurements have been recently developed to understand the lithiation process and propose an effective remedy to the failure mechanisms. One of the most specific techniques, which is able to follow the phase changes in poorly crystallized electrode materials, makes use of Raman spectroscopy within the battery, i.e., in operando mode. Such an approach has been successful but is still limited by the rather signal-to-noise ratio of the spectroscopy. Herein, the operando Raman signal from the silicon anodes is enhanced by plasmonic nanoparticles following the known surface-enhanced Raman spectroscopy (SERS). Coinage metals (Ag and Au) display a surface plasmon resonance in the visible and allow the SERS effect to take place. We have found that the as-prepared materials reach high specific capacities over 1000 mAh/g with stability over more than 1000 cycles at 1C rate and can be suitable to perform as anodes in LIB. Moreover, the incorporation of coinage metals enables SERS to take place specifically on the surface of silicon. Consequently, by using a specially designed Raman cell, it is possible to follow the processes in a silicon-coinage metal-based battery trough operando SERS measurements.

Correlative SEM SERS for quantitative analysis of dimer nanoparticles.

PubMed

Timmermans, F J; Lenferink, A T M; van Wolferen, H A G M; Otto, C

2016-11-14

A Raman microscope integrated with a scanning electron microscope was used to investigate plasmonic structures by correlative SEM-SERS analysis. The integrated Raman-SEM microscope combines high-resolution electron microscopy information with SERS signal enhancement from selected nanostructures with adsorbed Raman reporter molecules. Correlative analysis is performed for dimers of two gold nanospheres. Dimers were selected on the basis of SEM images from multi aggregate samples. The effect of the orientation of the dimer with respect to the polarization state of the laser light and the effect of the particle gap size on the Raman signal intensity is observed. Additionally, calculations are performed to simulate the electric near field enhancement. These simulations are based on the morphologies observed by electron microscopy. In this way the experiments are compared with the enhancement factor calculated with near field simulations and are subsequently used to quantify the SERS enhancement factor. Large differences between experimentally observed and calculated enhancement factors are regularly detected, a phenomenon caused by nanoscale differences between the real and 'simplified' simulated structures. Quantitative SERS experiments reveal the structure induced enhancement factor, ranging from ∼200 to ∼20 000, averaged over the full nanostructure surface. The results demonstrate correlative Raman-SEM microscopy for the quantitative analysis of plasmonic particles and structures, thus enabling a new analytical method in the field of SERS and plasmonics.

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

Effective characterization of polymer residues on two-dimensional materials by Raman spectroscopy

NASA Astrophysics Data System (ADS)

Park, Ji-Hoon; Choi, Soo Ho; Chae, Won Uk; Stephen, Boandoh; Park, Hyeon Ki; Yang, Woochul; Kim, Soo Min; Lee, Joo Song; Kim, Ki Kang

2015-12-01

Large-area two-dimensional (2D) materials grown by chemical vapor deposition need to be transferred onto a target substrate for real applications. Poly(methyl methacrylate) as a supporting layer is widely used during the transfer process and removed after finishing it. However, it is a challenge to diminish the polymer layer completely. It is necessary to readily characterize the polymer residues on 2D materials to facilitate the removal process. Here, we report a method that characterizes the polymer residues on 2D materials by tracking the presence of G-band of amorphous carbons (a-Cs) in the Raman spectrum after forming carbonized a-Cs through thermal annealing. The 13C-graphene is employed to separate the Raman signal G-band between 12C-a-Cs and 13C-graphene in the Raman spectrum. The residence of the polymer residues is clearly confirmed by the different Raman signals of two different isotopes (12C and 13C) due to differences in mass. Our effective method recognizes that while the polymer residue is not easily removed on graphene, those on hexagonal boron nitride and molybdenum disulfide are almost diminished under optimum thermal annealing conditions. Our method will not only contribute to the development of a new transfer process, but also help to achieve a clean surface of 2D materials.

Accelerated detection of viral particles by combining AC electric field effects and micro-Raman spectroscopy.

PubMed

Tomkins, Matthew Robert; Liao, David Shiqi; Docoslis, Aristides

2015-01-08

A detection method that combines electric field-assisted virus capture on antibody-decorated surfaces with the "fingerprinting" capabilities of micro-Raman spectroscopy is demonstrated for the case of M13 virus in water. The proof-of-principle surface mapping of model bioparticles (protein coated polystyrene spheres) captured by an AC electric field between planar microelectrodes is presented with a methodology for analyzing the resulting spectra by comparing relative peak intensities. The same principle is applied to dielectrophoretically captured M13 phage particles whose presence is indirectly confirmed with micro-Raman spectroscopy using NeutrAvidin-Cy3 as a labeling molecule. It is concluded that the combination of electrokinetically driven virus sampling and micro-Raman based signal transduction provides a promising approach for time-efficient and in situ detection of viruses.

Raman Enhancement and Photo-Bleaching of Organic Dyes in the Presence of Chemical Vapor Deposition-Grown Graphene.

PubMed

Weng, Jiaxin; Zhao, Shichao; Li, Zhiting; Ricardo, Karen B; Zhou, Feng; Kim, Hyojeong; Liu, Haitao

2017-10-19

Fluorescent organic dyes photobleach under intense light. Graphene has been shown to improve the photo-stability of organic dyes. In this paper, we investigated the Raman spectroscopy and photo-bleaching kinetics of dyes in the absence/presence of chemical vapor deposition (CVD)-grown graphene. We show that graphene enhances the Raman signal of a wide range of dyes. The photo-bleaching of the dyes was reduced when the dyes were in contact with graphene. In contrast, monolayer hexagonal boron nitride (h-BN) was much less effective in reducing the photo-bleaching rate of the dyes. We attribute the suppression of photo-bleaching to the energy or electron transfer from dye to graphene. The results highlight the potential of CVD graphene as a substrate for protecting and enhancing Raman response of organic dyes.

Raman gain and nonlinear optical absorption measurements in a low-loss silicon waveguide

NASA Astrophysics Data System (ADS)

Rong, Haisheng; Liu, Ansheng; Nicolaescu, Remus; Paniccia, Mario; Cohen, Oded; Hak, Dani

2004-09-01

We fabricated a low-loss (˜0.22dB/cm) rib waveguide (WG) in silicon-on-insulator with a small effective core area of ˜1.57μm2 and measured the stimulated Raman scattering gain in the WG. We obtained 2.3dB Raman gain in a 4.8-cm-long S-shaped WG using a 1455nm pump laser with a cw power of 0.9W measured before the WG. In addition, we observed nonlinear dependence of Raman gain and optical propagation loss as a function of the pump power. Our study shows that this mainly is due to two-photon absorption (TPA) induced free carrier absorption in the silicon WG. We experimentally determined the TPA induced free carrier lifetime of 25ns, which agrees well with our modeling.

Surface-enhanced Raman scattering from finite arrays of gold nano-patches

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

Vincenti, M. A.; Ceglia, D. de; US Army-Charles M. Bowden Research Laboratory, 35898 Redstone Arsenal, Huntsville, Alabama

We experimentally investigate the surface-enhanced Raman scattering (SERS) response of a 2D-periodic array of square gold nano-patches, functionalized by means of a conjugated, rigid thiol. We measure a Raman signal enhancement up to 200 times more intense compared to other plasmon-based nanostructures functionalized with the same molecule, and show that the enhancement is not strictly correlated to the presence of plasmonic resonances. The agreement between experimental and theoretical results reveals the importance of a full-wave analysis based on the inclusion of the actual scattering cross section of the molecule. The proposed numerical approach may serve not only as a toolmore » to predict the enhancement of Raman signal scattered from strongly resonant nanostructure but also as an effective instrument to engineer SERS platforms that target specific molecules.« less

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.

Quantitative Raman spectrum and reliable thickness identification for atomic layers on insulating substrates.

PubMed

Li, Song-Lin; Miyazaki, Hisao; Song, Haisheng; Kuramochi, Hiromi; Nakaharai, Shu; Tsukagoshi, Kazuhito

2012-08-28

We demonstrate the possibility in quantifying the Raman intensities for both specimen and substrate layers in a common stacked experimental configuration and, consequently, propose a general and rapid thickness identification technique for atomic-scale layers on dielectric substrates. Unprecedentedly wide-range Raman data for atomically flat MoS(2) flakes are collected to compare with theoretical models. We reveal that all intensity features can be accurately captured when including optical interference effect. Surprisingly, we find that even freely suspended chalcogenide few-layer flakes have a stronger Raman response than that from the bulk phase. Importantly, despite the oscillating intensity of specimen spectrum versus thickness, the substrate weighted spectral intensity becomes monotonic. Combined with its sensitivity to specimen thickness, we suggest this quantity can be used to rapidly determine the accurate thickness for atomic layers.

Zn(II), Cd(II) and Hg(I) complexes of cinnamic acid: FT-IR, FT-Raman, 1H and 13C NMR studies

NASA Astrophysics Data System (ADS)

Kalinowska, M.; Świsłocka, R.; Lewandowski, W.

2011-05-01

The effect of zinc, cadmium(II) and mercury(I) ions on the electronic structure of cinnamic acid (phenylacrylic acid) was studied. In this research many miscellaneous analytical methods, which complement one another, were used: infrared (FT-IR), Raman (FT-Raman), nuclear magnetic resonance ( 1H, 13C NMR) and quantum mechanical calculations. The spectroscopic studies provide some knowledge on the distribution of the electronic charge in molecule, the delocalization energy of π-electrons and the reactivity of metal complexes. In the series of Zn(II) → Cd(II) → Hg(I) cinnamates: (1) systematic shifts of several bands in the experimental and theoretical IR and Raman spectra and (2) regular chemical shifts for protons 1H and 13C nuclei were observed.

Infrared and Raman spectra of N-acetyl- L-amino acid methylamides with aromatic side groups

NASA Astrophysics Data System (ADS)

Matsuura, Hiroatsu; Hasegawa, Kodo; Miyazawa, Tatsuo

Infrared and Raman spectra of N-acetyl- L-phenylalanine methylamide, N-acetyl- L-tyrosine methylamide and N-acetyl- L-tryptophan methylamide, as model compounds of aromatic amino acid residues in proteins, were measured in the solid state and in methanol solutions. Vibrational assignments of the spectra were made by utilizing the deuteration effect and by comparison with the spectra of related compounds which include toluene, p-cresol and 3-methylindole. The amide I, III and IV bands were strong in Raman scattering, but other characteristic amide bands were ill-defined. In the Raman spectra of methanol solutions, only the bands due to the aromatic side group vibrations were markedly observed, but those due to the peptide backbone vibrations were very weak, suggesting the coexistence of various molecular conformations in solution.

Accelerated Detection of Viral Particles by Combining AC Electric Field Effects and Micro-Raman Spectroscopy

PubMed Central

Tomkins, Matthew Robert; Liao, David Shiqi; Docoslis, Aristides

2015-01-01

A detection method that combines electric field-assisted virus capture on antibody-decorated surfaces with the “fingerprinting” capabilities of micro-Raman spectroscopy is demonstrated for the case of M13 virus in water. The proof-of-principle surface mapping of model bioparticles (protein coated polystyrene spheres) captured by an AC electric field between planar microelectrodes is presented with a methodology for analyzing the resulting spectra by comparing relative peak intensities. The same principle is applied to dielectrophoretically captured M13 phage particles whose presence is indirectly confirmed with micro-Raman spectroscopy using NeutrAvidin-Cy3 as a labeling molecule. It is concluded that the combination of electrokinetically driven virus sampling and micro-Raman based signal transduction provides a promising approach for time-efficient and in situ detection of viruses. PMID:25580902

Influence of wavelength-dependent-loss on dispersive wave in nonlinear optical fibers.

PubMed

Herrera, Rodrigo Acuna

2012-11-01

In this work, we study numerically the influence of wavelength-dependent loss on the generation of dispersive waves (DWs) in nonlinear fiber. This kind of loss can be obtained, for instance, by the acousto-optic effect in fiber optics. We show that this loss lowers DW frequency in an opposite way that the Raman effect does. Also, we see that the Raman effect does not change the DW frequency too much when wavelength-dependent loss is included. Finally, we show that the DW frequency is not practically affected by fiber length.

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.

Diagnostic tool for early detection of ovarian cancers using Raman spectroscopy

NASA Astrophysics Data System (ADS)

Lieber, Chad A.; Molpus, Kelly; Brader, Kevin; Mahadevan-Jansen, Anita

2000-05-01

With an overall survival rate of about 35 percent, ovarian cancer claims more than 13,000 women in the US each year. It is estimated that roughly 1 in 70 women will develop ovarian cancer. Current screening techniques are challenged due to cost-effectiveness, variable false-positive results, and the asymptomatic nature of the early stages of ovarian cancer. The predominant screening method for ovarian cancers is transvaginal sonography (TVS). TVS is fairly accomplished at ovarian cancer detection, however it is inefficient in distinguishing between benign and malignant masses. Accurate diagnosis of the ovarian tumor relies on exploratory laparotomy, thus increasing the cost and hazard of false- positive screening methods. Raman spectroscopy has been sued successfully as a diagnostic tool in several organ systems in vitro. These studies have shown that Raman spectroscopy can be used to provide diagnosis of subtle changes in tissue pathology with high accuracy. Based on this success, we have developed a Raman spectroscopic system for application in the ovary. Using this system, the Raman signatures of normal and various types of non-normal human ovarian tissues were characterized in vitro. Raman spectra are being analyzed, and empirical as well as multivariate discriminatory algorithms developed. Based on the result of this study, a strategy for in vivo trials will be planned.

Graphitic carbon nanospheres: A Raman spectroscopic investigation of thermal conductivity and morphological evolution by pulsed laser irradiation

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

Agarwal, Radhe; Sahoo, Satyaprakash, E-mail: satya504@gmail.com, E-mail: rkatiyar@hpcf.upr.edu; Chitturi, Venkateswara Rao

2015-12-07

Graphitic carbon nanospheres (GCNSs) were prepared by a unique acidic treatment of multi-walled nanotubes. Spherical morphology with a narrow size distribution was confirmed by transmission electron microscopy studies. The room temperature Raman spectra showed a clear signature of D- and G-peaks at around 1350 and 1591 cm{sup −1}, respectively. Temperature dependent Raman scattering measurements were performed to understand the phonon dynamics and first order temperature coefficients related to the D- and G-peaks. The temperature dependent Raman spectra in a range of 83–473 K were analysed, where the D-peak was observed to show a red-shift with increasing temperature. The relative intensity ratio ofmore » D- to G-peaks also showed a significant rise with increasing temperature. Such a temperature dependent behaviour can be attributed to lengthening of the C-C bond due to thermal expansion in material. The estimated value of the thermal conductivity of GCNSs ∼0.97 W m{sup −1} K{sup −1} was calculated using Raman spectroscopy. In addition, the effect of pulsed laser treatment on the GCNSs was demonstrated by analyzing the Raman spectra of post irradiated samples.« less

Recognizing different tissues in human fetal femur cartilage by label-free Raman microspectroscopy

NASA Astrophysics Data System (ADS)

Kunstar, Aliz; Leijten, Jeroen; van Leuveren, Stefan; Hilderink, Janneke; Otto, Cees; van Blitterswijk, Clemens A.; Karperien, Marcel; van Apeldoorn, Aart A.

2012-11-01

Traditionally, the composition of bone and cartilage is determined by standard histological methods. We used Raman microscopy, which provides a molecular "fingerprint" of the investigated sample, to detect differences between the zones in human fetal femur cartilage without the need for additional staining or labeling. Raman area scans were made from the (pre)articular cartilage, resting, proliferative, and hypertrophic zones of growth plate and endochondral bone within human fetal femora. Multivariate data analysis was performed on Raman spectral datasets to construct cluster images with corresponding cluster averages. Cluster analysis resulted in detection of individual chondrocyte spectra that could be separated from cartilage extracellular matrix (ECM) spectra and was verified by comparing cluster images with intensity-based Raman images for the deoxyribonucleic acid/ribonucleic acid (DNA/RNA) band. Specific dendrograms were created using Ward's clustering method, and principal component analysis (PCA) was performed with the separated and averaged Raman spectra of cells and ECM of all measured zones. Overall (dis)similarities between measured zones were effectively visualized on the dendrograms and main spectral differences were revealed by PCA allowing for label-free detection of individual cartilaginous zones and for label-free evaluation of proper cartilaginous matrix formation for future tissue engineering and clinical purposes.

Raman mapping of mannitol/lysozyme particles produced via spray drying and single droplet drying.

PubMed

Pajander, Jari Pekka; Matero, Sanni; Sloth, Jakob; Wan, Feng; Rantanen, Jukka; Yang, Mingshi

2015-06-01

This study aimed to investigate the effect of a model protein on the solid state of a commonly used bulk agent in spray-dried formulations. A series of lysozyme/mannitol formulations were spray-dried using a lab-scale spray dryer. Further, the surface temperature of drying droplet/particles was monitored using the DRYING KINETICS ANALYZER™ (DKA) with controllable drying conditions mimicking the spray-drying process to estimate the drying kinetics of the lysozyme/mannitol formulations. The mannitol polymorphism and the spatial distribution of lysozyme in the particles were examined using X-ray powder diffractometry (XRPD) and Raman microscopy. Partial Least Squares Discriminant Analysis was used for analyzing the Raman microscopy data. XRPD results indicated that a mixture of β-mannitol and α-mannitol was produced in the spray-drying process which was supported by the Raman analysis, whereas Raman analysis indicated that a mixture of α-mannitol and δ-mannitol was detected in the single particles from DKA. In addition Raman mapping indicated that the presence of lysozyme seemed to favor the appearance of α-mannitol in the particles from DKA evidenced by close proximity of lysozyme and mannitol in the particles. It suggested that the presence of lysozyme tend to induce metastable solid state forms upon the drying process.

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.

Spotting the differences in two-dimensional materials - the Raman scattering perspective.

PubMed

Zhang, Shishu; Zhang, Na; Zhao, Yan; Cheng, Ting; Li, Xiaobo; Feng, Rui; Xu, Hua; Liu, Zhirong; Zhang, Jin; Tong, Lianming

2018-05-08

Two-dimensional (2D) layered materials have attracted tremendous attention and led to a prosperous development in both fundamental investigation and device applications in various fields, such as nanoelectronics, flexible devices, sustainable energy and catalysts. The precise characterization of the structure and properties of 2D materials is in urgent need. Raman scattering spectroscopy is one of the most popular characterization tools that is convenient, rapid and non-invasive. It provides information on both the lattice structure from the frequency of phonon modes and the electronic band structure through the intensity due to electronic resonance Raman scattering. Although a few morphological characterization tools can image 2D materials with atomic resolution, Raman scattering measurements are more tolerant to the conditions of sample preparation such as the substrate and less technically demanding, and have been one of the routine tools for the characterization of 2D materials. In this review, we focus on the characterization of 2D materials using Raman scattering spectroscopy, in particular, the revealing of differences from primitive 2D materials, such as defects, doping effects, van der Waals heterostructures and the interaction with molecules. The characteristic Raman features of such differences and the corresponding interpretation will be discussed. We hope that this review will be useful for wide research communities of materials, physics, chemistry and engineering.

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.

Analysis of low active-pharmaceutical-ingredient signal drugs based on thin layer chromatography and surface-enhanced Raman spectroscopy.

PubMed

Li, Xiao; Chen, Hui; Zhu, Qingxia; Liu, Yan; Lu, Feng

2016-11-30

Active pharmaceutical ingredients (API) embedded in the excipients of the formula can usually be unravelled by normal Raman spectroscopy (NRS). However, more and more drugs with low API content and/or low Raman scattering coefficient were insensitive to NRS analysis, which was for the first time defined as Low API-Signal Drugs (LASIDs) in this paper. The NRS spectra of these LASIDs were similar to their dominant excipients' profiles, such as lactose, starch, microcrystalline cellulose (MCC), etc., and were classified into three types as such. 21 out of 100 kinds of drugs were screened as LASIDs and characterized further by Raman microscopic mapping. Accordingly, we proposed a tailored solution to the qualitation and quantitation problem of these LASIDs, using surface-enhanced Raman spectroscopic (SERS) detection on the thin layer chromatographic (TLC) plate both in situ and after-separation. Experimental conditions and parameters including TLC support matrix, SERS substrate, detection mode, similarity threshold, internal standard, etc., were optimized. All LASIDs were satisfactorily identified and the quantitation results agreed well with those of high performance liquid chromatography (HPLC). For some structural analogues of LASIDs, although they presented highly similar SERS spectra and were tough to distinguish even with Raman microscopic mapping, they could be successfully discriminated from each other by coupling SERS (with portable Raman spectrometer) with TLC. These results demonstrated that the proposed solution could be employed to detect the LASIDs with high accuracy and cost-effectiveness. Copyright © 2016 Elsevier B.V. All rights reserved.

Ultrasensitive Raman sensor based on a highly scattering porous structure

NASA Astrophysics Data System (ADS)

Yakovlev, V. V.

2010-02-01

Analytical methods capable of in situ monitoring of water quality have been in high demand for environmental safety, the identification of minute impurities and fundamental understanding of potential risks of these molecular species. Raman spectroscopy, which provides 'fingerprint' information about molecular species in the excitation volume, is a powerful tool for in vivo diagnostics. However, due to a relatively weak Raman signal (~ 1 out of 1014 incident photons produces the useful signal) there is a need to significantly (by many orders of magnitude) enhance this signal, to raise the detection sensitivity of this technique. Traditionally, surface enhanced Raman spectroscopy is employed to dramatically increase the local field intensity and substantially improve the efficiency of Raman scattering. However, the above enhancement occurs only in "hot spots", which represent only a small percent of the total surface are of the substrate. Plasmonic nanostructures are also found to be hard to manufacture in large quantities with the desired degree of reproducibility and to be unable to handle high laser power. We propose and experimentally demonstrate a new type of approach for ultrasensitive Raman sensing. It is based on manufacturing a random porous structure of high-index material, such as GaP, and use the effect of light localization to help improving the detection sensitivity of such sensor. The desired structure was manufactured using electrochemical etching of GaP wafers. The observed Raman signal amplitudes are favorably compared to the best known plasmonic substrates.

Temperature and Salinity Effects on Quantitative Raman Spectroscopic Analysis of Dissolved Volatiles Concentration in Geofluids

NASA Astrophysics Data System (ADS)

Wu, X.; Lu, W.

2017-12-01

The concentration detection of the volatiles such as CH4 and CO2 in the hydrothermal systems and fluid inclusions is critical for understanding the fluxes of volatiles from mantle to crust and atmosphere. In-situ Raman spectroscopy has been developed successfully in laboratory, fluid inclusions and submarine environment because of its non-destructive and non-contact advantages. For improving the ability of detecting different species quantitatively by in-situ Raman spectroscopy in the extreme environment, such as the hydrothermal system and fluid inclusion, we studied the temperature- and salinity-dependence of Raman scattering cross section (RSCS) of the water OH stretching band at temperatures from 20 to 300 oC under 30 MPa. This is important because the water is often used as internal standard in the Raman quantitative application. Based on our previous study of NaCl-H2O system, we made further investigation on the CaCl2-H2O system. Our results revealed that the cation shows negligible effect on the RSCS of water OH stretching band, while the cations seems to have more obvious different effect on the structure of water within high temperatures. Besides the NaCl-CH4-H2O system, we also take the CO2-H2O system into account. Further conclusion can be made that the variation of the Raman quantitative factor (QF) (both PAR/mCH4 and PAR/mCO2) with the temperature and salinity is mainly caused by the temperature- and Cl- concentration-dependence of the relative RSCS of the water OH stretching band. If the Raman quantitative factor at ambient condition still being used, the RSCS of the water OH stretching band would induce about 47%, 34% and 29% error for the determined concentration of dissolved CH4 or CO2 (in mol/kg·H2O) by in-situ Raman spectroscopy for 0 m Cl-, 3 m Cl- and 5 m Cl- aqueous system when the temperature increases from 20 to 300 oC, respectively. Considering the wide range of the temperature and salinity in hydrothermal systems and fluid inclusions, the following equation can be used to calculate the relative QF at different temperatures and salinity referencing to the 0 m Cl- aqueous solution at 20 oC: QF(T, salinity)/QF(20 oC, 0 m Cl-)=k(T-20 oC)+b, where a=-0.0035× mCl-1/2+0.00168, b=-0.03× mCl-+1;

Enhancing Raman signals through electromagnetic hot zones induced by magnetic dipole resonance of metal-free nanoparticles

NASA Astrophysics Data System (ADS)

Tseng, Yi-Chuan; Lee, Yang-Chun; Chang, Sih-Wei; Lin, Tzu-Yao; Ma, Dai-Liang; Lin, Bo-Cheng; Chen, Hsuen-Li

2017-11-01

In this study, we found that the large area of electromagnetic field hot zone induced through magnetic dipole resonance of metal-free structures can greatly enhance Raman scattering signals. The magnetic resonant nanocavities, based on high-refractive-index silicon nanoparticles (SiNPs), were designed to resonate at the wavelength of the excitation laser of the Raman system. The well-dispersed SiNPs that were not closely packed displayed significant magnetic dipole resonance and gave a Raman enhancement per unit volume of 59 347. The hot zones of intense electric field were generated not only within the nonmetallic NPs but also around them, even within the underlying substrate. We observed experimentally that gallium nitride (GaN) and silicon carbide (SiC) surfaces presenting very few SiNPs (coverage: <0.3%) could display significantly enhanced (>50%) Raman signals. In contrast, the Raman signals of the underlying substrates were not enhanced by gold nanoparticles (AuNPs), even though these NPs displayed a localized surface plasmon resonance (LSPR) phenomenon. A comparison of the areas of the electric field hot zones (E 2 > 10) generated by SiNPs undergoing magnetic dipole resonance with the electric field hot spots (E 2 > 10) generated by AuNPs undergoing LSPR revealed that the former was approximately 70 times that of the latter. More noteworthily, the electromagnetic field hot zone generated from the SiNP is able to extend into the surrounding and underlying media. Relative to metallic NPs undergoing LSPR, these nonmetallic NPs displaying magnetic dipole resonance were more effective at enhancing the Raman scattering signals from analytes that were underlying, or even far away from, them. This application of magnetic dipole resonance in metal-free structures appears to have great potential for use in developing next-generation techniques for Raman enhancement.

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.

Raman spectroscopy of graphene-based materials and its applications in related devices.

PubMed

Wu, Jiang-Bin; Lin, Miao-Ling; Cong, Xin; Liu, He-Nan; Tan, Ping-Heng

2018-03-05

Graphene-based materials exhibit remarkable electronic, optical, and mechanical properties, which has resulted in both high scientific interest and huge potential for a variety of applications. Furthermore, the family of graphene-based materials is growing because of developments in preparation methods. Raman spectroscopy is a versatile tool to identify and characterize the chemical and physical properties of these materials, both at the laboratory and mass-production scale. This technique is so important that most of the papers published concerning these materials contain at least one Raman spectrum. Thus, here, we systematically review the developments in Raman spectroscopy of graphene-based materials from both fundamental research and practical (i.e., device applications) perspectives. We describe the essential Raman scattering processes of the entire first- and second-order modes in intrinsic graphene. Furthermore, the shear, layer-breathing, G and 2D modes of multilayer graphene with different stacking orders are discussed. Techniques to determine the number of graphene layers, to probe resonance Raman spectra of monolayer and multilayer graphenes and to obtain Raman images of graphene-based materials are also presented. The extensive capabilities of Raman spectroscopy for the investigation of the fundamental properties of graphene under external perturbations are described, which have also been extended to other graphene-based materials, such as graphene quantum dots, carbon dots, graphene oxide, nanoribbons, chemical vapor deposition-grown and SiC epitaxially grown graphene flakes, composites, and graphene-based van der Waals heterostructures. These fundamental properties have been used to probe the states, effects, and mechanisms of graphene materials present in the related heterostructures and devices. We hope that this review will be beneficial in all the aspects of graphene investigations, from basic research to material synthesis and device applications.

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.

Effect of the crushing process on Raman analyses: consequences for the Mars 2018 mission

NASA Astrophysics Data System (ADS)

Foucher, Frédéric; Westall, Frances; Bost, Nicolas; Rull, Fernando; Lopez-Reyes, Guillermo; Rüßmann, Philipp

2012-07-01

The payload of the 2018 Mars mission will comprise a Raman spectrometer as part of its instrument suite. Analyses with this instrument will be made on crushed samples. The crushing process will cause loss of important structural context and could change the physical properties of the studied materials resulting in misinterpretation of the data. We therefore investigated the influence of granulometry on the Raman spectrum of various minerals and rocks using laboratory equipment and the RLS Raman instrument being developed for the Pasteur payload of the ExoMars mission. The aim was to determine what influence the crushing process could have on the correct identification of rocks and minerals and the detection of possible traces of life. Whatever the sample type, our study shows that the crushing process leads to a strong increase in the background level and to a decrease in the signal/noise ratio. Moreover, for certain minerals, the Raman spectra can be significantly modified: the peaks are shifted and broadened and new peaks can appear. Since mineral identification using Raman spectroscopy is made by comparison with database spectra, this kind of change could lead to misinterpretation of the spectra and thus must be taken into account during the in situ investigation. However, the results obtained with the ExoMars instrument showed that, probably due to its irradiance and resolution characteristics, these effects are relatively limited and most of the time not observed with the RLS instrument. Finally, the loss of texture associated with the crushing process is shown to complicate identification of rocks with subsequent consequences for the eventual detection and interpretation of past traces of life. But, on the other hand, it is shown that the mixing of the components in the powder could facilitate the detection of minor phases.

Review structure of silk by raman spectromicroscopy: from the spinning glands to the fibers.

PubMed

Lefèvre, Thierry; Paquet-Mercier, François; Rioux-Dubé, Jean-François; Pézolet, Michel

2012-06-01

Raman spectroscopy has long been proved to be a useful tool to study the conformation of protein-based materials such as silk. Thanks to recent developments, linearly polarized Raman spectromicroscopy has appeared very efficient to characterize the molecular structure of native single silk fibers and spinning dopes because it can provide information relative to the protein secondary structure, molecular orientation, and amino acid composition. This review will describe recent advances in the study of the structure of silk by Raman spectromicroscopy. A particular emphasis is put on the spider dragline and silkworm cocoon threads, other fibers spun by orb-weaving spiders, the spinning dope contained in their silk glands and the effect of mechanical deformation. Taken together, the results of the literature show that Raman spectromicroscopy is particularly efficient to investigate all aspects of silk structure and production. The data provided can lead to a better understanding of the structure of the silk dope, transformations occurring during the spinning process, and structure and mechanical properties of native fibers. Copyright © 2011 Wiley Periodicals, Inc.

Influences of bicarbonate on processes of enamel subsurface remineralization and demineralization: assessment using micro-Raman spectroscopy and transverse microradiography.

PubMed

Kuramochi, Erika; Iizuka, Junko; Mukai, Yoshiharu

2016-12-01

In the present study, we investigated, using micro-Raman spectroscopy (Raman) and transverse microradiography, the influence of bicarbonate [sodium hydrogen carbonate (NaHCO 3 )] on the effects of carbonate ions in the mineral phase during demineralization (acid resistance test) of subsurface lesions. Baseline lesions were created by demineralizing bovine enamel, and specimens were then exposed to remineralization solutions containing 0, 5, or 50 mM bicarbonate. Acid resistance tests were performed on remineralized and sound enamel specimens. Raman spectra showed that carbonate and phosphate were incorporated into both surface layers and lesion bodies during remineralization in the presence of bicarbonate. Moreover, the presence of bicarbonate did not affect the rates of remineralization, although the average mineral profiles of remineralized enamel differed from those of sound enamel after acid resistance tests. Raman analyses enabled close evaluation of site-specific characteristics of carbonate and phosphate in subsurface lesions. In conclusion, incorporation of carbonate and phosphate ions into enamel subsurface lesions during remineralization does not affect the magnitude of remineralization or acid resistance. © 2016 Eur J Oral Sci.

Resonance Raman spectra of bacteriorhodopsin's primary photoproduct: evidence for a distorted 13-cis retinal chromophore.

PubMed Central

Braiman, M; Mathies, R

1982-01-01

We have obtained the resonance Raman spectrum of bacteriorhodopsin's primary photoproduct K with a novel low-temperature spinning sample technique. Purple membrane at 77 K is illuminated with spatially separated actinic (pump) and probe laser beams. The 514-nm pump beam produces a photostationary steady-state mixture of bacteriorhodopsin and K. This mixture is then rotated through the red (676 nm) probe beam, which selectively enhances the Raman scattering from K. The essential advantage of our successive pump-and-probe technique is that it prevents the fluorescence excited by the pump beam from masking the red probe Raman scattering. K exhibits strong Raman lines at 1516, 1294, 1194, 1012, 957, and 811 cm-1. The effects of C15 deuteration on K's fingerprint lines correlate well with those seen in 13-cis model compounds, indicating that K has a 13-cis chromophore. However, the presence of unusually strong "low-wavenumber" lines at 811 and 957 cm-1, attributable to hydrogen out-of-plane wags, indicates that the protein holds the chromophore in a distorted conformation after trans leads to cis isomerization. PMID:6281770

Near-field nano-Raman imaging of Si device structures

NASA Astrophysics Data System (ADS)

Atesang, Jacob; Geer, Robert

2005-05-01

Apertureless-based, near-field Raman imaging holds the potential for nanoscale stress metrology in emerging Si devices. Preliminary application of near-field Raman imaging on Si device structures has demonstrated the potential for stress measurements. However, detailed investigations have not been published regarding the effect of tip radius on observed near-field enhancement. Such investigations are important to understand the fundamental limits regarding the signal-to-noise ratio of the measurement and the spatial resolution that can potentially be achieved before wide application to semiconductor metrology can be considered. Investigations are presented into near-field enhancement of Raman scattering from Si device structures using a modified near-field optical microscope (NSOM). The nano-Raman system utilizes an off-axis (45°) backscattering NSOM geometry with free-space collection optics. The spectroscopic configuration utilizes a single-bounce spectrometer incorporating a holographic notch filter assembly utilized as a secondary beam-splitter for an apertureless backscattering collection geometry. Near-field enhancement is observed for both Al- and Ag-coated probes. An inverse square power-law relationship is observed between near-field enhancement factor and tip radius.

Raman and Brillouin scattering studies of bulk 2H-WSe2

NASA Astrophysics Data System (ADS)

Akintola, K.; Andrews, G. T.; Curnoe, S. H.; Koehler, M. R.; Keppens, V.

2015-10-01

Raman and Brillouin spectroscopy were used to probe optic and acoustic phonons in bulk 2H-WSe2. Raman spectra collected under different polarization conditions allowed assignment of spectral peaks to various first- and second-order processes. In contrast to some previous studies, a Raman peak at  ˜259 cm-1was found not to be due to the A1g mode but to a second-order process involving phonons at either the M or K point of the Brillouin zone. Resonance effects due to excitons were also observed in the Raman spectra. Brillouin spectra of 2H-WSe2 contain a single peak doublet arising from a Rayleigh surface mode propagating with a velocity of 1340+/- 20 m s-1. This value is comparable to that estimated from Density Functional Theory calculations and also to those for the transition metal diselenides 2H-TaSe2 and 2H-NbSe2. Unlike these two materials, however, peaks arising from scattering via the elasto-optic mechanism were not observed in Brillouin spectra of WSe2 despite its lower opacity.

[Analysis of pigments from Rhodotorula glutinis by Raman spectroscopy and thin layer chromatography].

PubMed

Yuan, Yu-feng; Tao, Zhan-hua; Wang, Xue; Li, Yong-qing; Liu, Jun-xian

2012-03-01

The pigments from Rhodotorula glutinis were separated by using thin layer chromatography, and the result showed that Rhodotorula glutinis cells could synthesize at least three kinds of pigments, which were beta-carotene, torulene, and torularhodin. The Raman spectra based on the three pigments were acquired, and original spectra were preprocessed by background elimination, baseline correction, and three-point-smoothing, then the averaged spectra from different pigments were investigated, and the result indicated that Raman shift which represents C-C bond was different, and the wave number of beta-carotene demonstrated the largest deviation, finally torulene and torularhodin in Rhodotorula glutinis had more content than beta-carotene. Quantitative analysis of Raman peak height ratio revealed that peak height ratio of pigments showed little difference, which could be used as parameters for further research on living cells, providing reference content of pigments. The above results suggest that Raman spectroscopy combined with thin layer chromatography can be applied to analyze pigments from Rhodotorula glutinis, provides abundant information about pigments, and serves as an effective method to study pigments.

Determination of composition and structure of spongy bone tissue in human head of femur by Raman spectral mapping.

PubMed

Kozielski, M; Buchwald, T; Szybowicz, M; Błaszczak, Z; Piotrowski, A; Ciesielczyk, B

2011-07-01

Biomechanical properties of bone depend on the composition and organization of collagen fibers. In this study, Raman microspectroscopy was employed to determine the content of mineral and organic constituents and orientation of collagen fibers in spongy bone in the human head of femur at the microstructural level. Changes in composition and structure of trabecula were illustrated using Raman spectral mapping. The polarized Raman spectra permit separate analysis of local variations in orientation and composition. The ratios of ν₂PO₄³⁻/Amide III, ν₄PO₄³⁻/Amide III and ν₁CO₃²⁻/ν₂PO₄³⁻ are used to describe relative amounts of spongy bone components. The ν₁PO₄³⁻/Amide I ratio is quite susceptible to orientation effect and brings information on collagen fibers orientation. The results presented illustrate the versatility of the Raman method in the study of bone tissue. The study permits better understanding of bone physiology and evaluation of the biomechanical properties of bone.

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

Nave, S.E.

Recent advances in fiber optics, diode lasers, CCD detectors, dielectric and holographic optical filters, grating spectrometers, and chemometric data analysis have greatly simplified Raman spectroscopy. In order to make a rugged fiber optic Raman probe for solids/slurries like these at Savannah River, we have designed a probe that eliminates as many optical elements and surfaces as possible. The diffuse reflectance probe tip is modified for Raman scattering by installing thin dielectric in-line filters. Effects of each filter are shown for the NaNO{sub 3} Raman spectrum. By using a diode laser excitation at 780 nm, fluorescence is greatly reduced, and excellentmore » spectra may be obtained from organic solids. At SRS, fiber optic Raman probes are being developed for in situ chemical mapping of radioactive waste storage tanks. Radiation darkening of silica fiber optics is negligible beyond 700 nm. Corrosion resistance is being evaluated. Analysis of process gas (off-gas from SRS processes) is investigated in some detail: hydrogen in nitrogen with NO{sub 2} interference. Other applications and the advantages of the method are pointed out briefly.« less

Temperature dependence Infrared and Raman studies of III-V/II-VI core-shell nanostructures

NASA Astrophysics Data System (ADS)

Manciu, Felicia S.; McCombe, Bruce D.; Lucey, Derrick

2005-03-01

The temperature dependence (8 K < T < 300 K) of optical phonon modes confined in InP/II-VI core-shell nanostructures have been investigated by far-infrared (FIR) and Raman scattering spectroscopies. The core-shell nanostructures were fabricated by colloidal chemistry and characterized by transmission electron microscopy and X-ray diffraction prior to being embedded in a polycrystalline CsI matrix for the present studies. The FIR measurements of InP/ZnSe sample exhibits three absorption features, one clearly due to the Froelich mode of the InP cores, and the others related to modes associated with the shell layer and its coupling to the matrix. Strong mixing of the characteristic vibrations of each constituent material was observed for InP/ZnS sample. Raman scattering (457.9 nm excitation) features were determined without polarization selection in the backscattering geometry. Interesting T-dependent resonant Raman effect of the surface optical phonon modes has been discovered in InP/ZnSe sample. Reasonable agreement is obtained between the Raman and FIR results, as well as with theoretical calculations.

The Inherent Visible Light Signature of an Intense Underwater Ultraviolet Light Source Due to Combined Raman and Fluorescence Effects

DTIC Science & Technology

2000-01-01

Humans cannot see ultraviolet light. The blue-sensitive cones in the retina would respond weakly to ultraviolet wavelengths if exposed to them, but...545, 1992. 3. C. S. Yentsch, and D. A. Phinney, " Autofluorescence and Raman scattering in the marine underwater environment," Ocean Optics X, SPIE

The effect of substrate on electric field enhancement of Tip-enhanced Raman spectroscopy (TERS)

NASA Astrophysics Data System (ADS)

Bahreini, Maryam

2018-01-01

The characterization of materials down to a few-molecule level is a key challenge in nanotechnology. Raman spectroscopy is a powerful method that provides chemical information via nondestructive vibrational fingerprinting. Unfortunately, this method suffers from signal weakness which prevents the study of small quantities. Tip-enhanced Raman spectroscopy (TERS) which combines the chemical sensitivity of Raman spectroscopy (RS) with high spatial resolution of scanning probe microscopy (SPM), provides chemical images of surfaces at the nanometer scale. In this method, irradiation of an SPM tip by a focused laser beam results in enhancement of local electric field via two reasons of localized surface plasmon resonance and lightning rod effect. This enhancement leads to the enhancement in Raman intensity from the sample surface in the vicinity of tip. In all TERS measurements, samples should be located on a substrate. In this paper, the dependence of the electric field enhancement to the substrate has been investigated. In simulations, three-dimensional finite-difference time-domain (3D-FDTD) method is used for numerical solution of Maxwell's equations. Our results show that the electric field enhancement is weak for the tip alone case. Introducing a substrate provides further electric field enhancement via near field electromagnetic dipole-dipole coupling between the tip and substrate. Since the side-illumination geometry is used for laser irradiation, the vertical component of the incident field plays a dominant role in the electric field enhancement. Therefore, the coupling effect between the tip and the substrate is the key contribution to the enhancement. For the case of silicon tip and the gold substrate, the electric field enhancement is improved considerably. There is an optimal tip size for TERS because of the competing effects of the radiation damping and the surface scattering of the tip. The results show the substrate as an effective tool for the improvement of the TERS detection sensitivity.

Mapping the absolute magnetic field and evaluating the quadratic Zeeman-effect-induced systematic error in an atom interferometer gravimeter

NASA Astrophysics Data System (ADS)

Hu, Qing-Qing; Freier, Christian; Leykauf, Bastian; Schkolnik, Vladimir; Yang, Jun; Krutzik, Markus; Peters, Achim

2017-09-01

Precisely evaluating the systematic error induced by the quadratic Zeeman effect is important for developing atom interferometer gravimeters aiming at an accuracy in the μ Gal regime (1 μ Gal =10-8m /s2 ≈10-9g ). This paper reports on the experimental investigation of Raman spectroscopy-based magnetic field measurements and the evaluation of the systematic error in the gravimetric atom interferometer (GAIN) due to quadratic Zeeman effect. We discuss Raman duration and frequency step-size-dependent magnetic field measurement uncertainty, present vector light shift and tensor light shift induced magnetic field measurement offset, and map the absolute magnetic field inside the interferometer chamber of GAIN with an uncertainty of 0.72 nT and a spatial resolution of 12.8 mm. We evaluate the quadratic Zeeman-effect-induced gravity measurement error in GAIN as 2.04 μ Gal . The methods shown in this paper are important for precisely mapping the absolute magnetic field in vacuum and reducing the quadratic Zeeman-effect-induced systematic error in Raman transition-based precision measurements, such as atomic interferometer gravimeters.

Intricate Resonant Raman Response in Anisotropic ReS2.

PubMed

McCreary, Amber; Simpson, Jeffrey R; Wang, Yuanxi; Rhodes, Daniel; Fujisawa, Kazunori; Balicas, Luis; Dubey, Madan; Crespi, Vincent H; Terrones, Mauricio; Hight Walker, Angela R

2017-10-11

The strong in-plane anisotropy of rhenium disulfide (ReS 2 ) offers an additional physical parameter that can be tuned for advanced applications such as logic circuits, thin-film polarizers, and polarization-sensitive photodetectors. ReS 2 also presents advantages for optoelectronics, as it is both a direct-gap semiconductor for few-layer thicknesses (unlike MoS 2 or WS 2 ) and stable in air (unlike black phosphorus). Raman spectroscopy is one of the most powerful characterization techniques to nondestructively and sensitively probe the fundamental photophysics of a 2D material. Here, we perform a thorough study of the resonant Raman response of the 18 first-order phonons in ReS 2 at various layer thicknesses and crystal orientations. Remarkably, we discover that, as opposed to a general increase in intensity of all of the Raman modes at excitonic transitions, each of the 18 modes behave differently relative to each other as a function of laser excitation, layer thickness, and orientation in a manner that highlights the importance of electron-phonon coupling in ReS 2 . In addition, we correct an unrecognized error in the calculation of the optical interference enhancement of the Raman signal of transition metal dichalcogenides on SiO 2 /Si substrates that has propagated through various reports. For ReS 2 , this correction is critical to properly assessing the resonant Raman behavior. We also implemented a perturbation approach to calculate frequency-dependent Raman intensities based on first-principles and demonstrate that, despite the neglect of excitonic effects, useful trends in the Raman intensities of monolayer and bulk ReS 2 at different laser energies can be accurately captured. Finally, the phonon dispersion calculated from first-principles is used to address the possible origins of unexplained peaks observed in the Raman spectra, such as infrared-active modes, defects, and second-order processes.

Formation Regularities of Plasmonic Silver Nanostructures on Porous Silicon for Effective Surface-Enhanced Raman Scattering

NASA Astrophysics Data System (ADS)

Bandarenka, Hanna V.; Girel, Kseniya V.; Bondarenko, Vitaly P.; Khodasevich, Inna A.; Panarin, Andrei Yu.; Terekhov, Sergei N.

2016-05-01

Plasmonic nanostructures demonstrating an activity in the surface-enhanced Raman scattering (SERS) spectroscopy have been fabricated by an immersion deposition of silver nanoparticles from silver salt solution on mesoporous silicon (meso-PS). The SERS signal intensity has been found to follow the periodical repacking of the silver nanoparticles, which grow according to the Volmer-Weber mechanism. The ratio of silver salt concentration and immersion time substantially manages the SERS intensity. It has been established that optimal conditions of nanostructured silver layers formation for a maximal Raman enhancement can be chosen taking into account a special parameter called effective time: a product of the silver salt concentration on the immersion deposition time. The detection limit for porphyrin molecules CuTMPyP4 adsorbed on the silvered PS has been evaluated as 10-11 M.

Mitigation of stimulated Raman scattering in high power fiber lasers using transmission gratings

NASA Astrophysics Data System (ADS)

Heck, Maximilian; Bock, Victor; Krämer, Ria G.; Richter, Daniel; Goebel, Thorsten A.; Matzdorf, Christian; Liem, Andreas; Schreiber, Thomas; Tünnermann, Andreas; Nolte, Stefan

2018-02-01

The average output power of fiber lasers have been scaled deep into the kW regime within the recent years. However a further scaling is limited due to nonlinear effects like stimulated Raman scattering (SRS). Using the special characteristics of femtosecond laser pulse written transmission fiber gratings, it is possible to realize a notch filter that mitigates efficiently this negative effect by coupling the Raman wavelength from the core into the cladding of the fiber. To the best of our knowledge, we realized for the first time highly efficient gratings in large mode area (LMA) fibers with cladding diameters up to 400 μm. The resonances show strong attenuation at design wavelength and simultaneously low out of band losses. A high power fiber amplifier with an implemented passive fiber grating is shown and its performance is carefully investigated.

Label-free imaging of fatty acid content within yeast samples

NASA Astrophysics Data System (ADS)

Garrett, N.; Moger, J.

2013-02-01

Fungi have been found to be an underlying cause of 70% of all plant and animal extinctions caused by infectious diseases. Fungal infections are a growing problem affecting global health, food production and ecosystems. Lipid metabolism is a promising target for antifungal drugs and since effective treatment of fungal infections requires a better understanding of the effects of antifungal agents at the cellular level, new techniques are needed to investigate this problem. Recent advances in nonlinear microscopy allow chemically-specific contrast to be obtained non-invasively from intrinsic chemical bonds within live samples using advanced spectroscopy techniques probing Raman-active resonances. We present preliminary data using Stimulated Raman Scattering (SRS) microscopy as a means to visualise lipid droplets within individual living fungi by probing Raman resonances of the CH stretching region between 2825cm-1 and 3030cm-1.

The Raman and SERS spectra of indigo and indigo-Ag2 complex: DFT calculation and comparison with experiment.

PubMed

Ricci, Marilena; Lofrumento, Cristiana; Becucci, Maurizio; Castellucci, Emilio M

2018-01-05

Using time-dependent density functional theory in conjunction with B3LYP functional and LANL2DZ/6-31+g(d,p) basis sets, static and pre-resonance Raman spectra of the indigo-Ag 2 complex have been calculated. Structure optimization, excitation energies and pre-resonance Raman spectra of the indigo molecule have been obtained at the same level of theory. The available experimental Raman spectra at 1064, 785 and 514nm and the SERS spectra at 785 and 514nm have been well reproduced by the calculation. Experimental SERS spectra are confronted with the calculated pre-resonance Raman spectra obtained for the indigo-Ag 2 complex. The Raman activities calculated under the infinite lifetime approximation show a strong dependence upon the proximity to the energy and the oscillator strength of the excitation electronic transition. The comparison of the integrated EFs for indigo and indigo-Ag 2 calculated Raman spectra, gave some hints as to the enhancement mechanisms acting for the different excitation wavelengths. Whereas for excitation at a wavelength corresponding to 785nm, the enhancement mechanism for the Raman spectrum of the metal complex seems the chemical one, the strong increment (ten times) of the integrated EF of the Raman spectra of the complex in the case of 514nm excitation, suggests the onset of other enhancement mechanisms. Assuming that intra-cluster transitions with high oscillator strength can be thought of as to mimic surface plasmons excitations, we suggest the onset of the electromagnetic mechanisms (EM) as the origin of the Raman spectrum enhancement. Nevertheless, other enhancement effects cannot be ruled out, as a new molecular transition gains strength in the proximity of the excitation wavelength, as a consequence of the symmetry lowering of the molecule in the complex. A large variation across vibrational modes, by a factor of at least 10 4 , was found for the EFs. This large variation in the EFs can indicate that B-term Herzberg-Teller scattering, due to metal and/or charge transfer states, can feed intensity to the inactive (in the molecule) and/or non totally symmetric modes. Copyright © 2017 Elsevier B.V. All rights reserved.

Rational design of Raman-labeled nanoparticles for a dual-modality, light scattering immunoassay on a polystyrene substrate.

PubMed

Israelsen, Nathan D; Wooley, Donald; Hanson, Cynthia; Vargis, Elizabeth

2016-01-01

Surface-enhanced Raman scattering (SERS) is a powerful light scattering technique that can be used for sensitive immunoassay development and cell labeling. A major obstacle to using SERS is the complexity of fabricating SERS probes since they require nanoscale characterization and optical uniformity. The light scattering response of SERS probes may also be modulated by the substrate used for SERS analysis. A typical SERS substrate such as quartz can be expensive. Polystyrene is a cheaper substrate option but can decrease the SERS response due to interfering Raman emission peaks and high background fluorescence. The goal of this research is to develop an optimized process for fabricating Raman-labeled nanoparticles for a SERS-based immunoassay on a polystyrene substrate. We have developed a method for fabricating SERS nanoparticle probes for use in a light scattering immunoassay on a polystyrene substrate. The light scattering profile of both spherical gold nanoparticle and gold nanorod SERS probes were characterized using Raman spectroscopy and optical absorbance spectroscopy. The effects of substrate interference and autofluorescence were reduced by selecting a Raman reporter with a strong light scattering response in a spectral region where interfering substrate emission peaks are minimized. Both spherical gold nanoparticles and gold nanorods SERS probes used in the immunoassay were detected at labeling concentrations in the low pM range. This analytical sensitivity falls within the typical dynamic range for direct labeling of cell-surface biomarkers using SERS probes. SERS nanoparticle probes were fabricated to produce a strong light scattering signal despite substrate interference. The optical extinction and inelastic light scattering of these probes was detected by optical absorbance spectroscopy and Raman spectroscopy, respectively. This immunoassay demonstrates the feasibility of analyzing strongly enhanced Raman signals on polystyrene, which is an inexpensive yet non-ideal Raman substrate. The assay sensitivity, which is in the low pM range, suggests that these SERS probe particles could be used for Raman labeling of cell or tissue samples in a polystyrene tissue culture plate. With continued development, this approach could be used for direct labeling of multiple cell surface biomarkers on strongly interfering substrate platforms.

The Raman and SERS spectra of indigo and indigo-Ag2 complex: DFT calculation and comparison with experiment

NASA Astrophysics Data System (ADS)

Ricci, Marilena; Lofrumento, Cristiana; Becucci, Maurizio; Castellucci, Emilio M.

2018-01-01

Using time-dependent density functional theory in conjunction with B3LYP functional and LANL2DZ/6-31+g(d,p) basis sets, static and pre-resonance Raman spectra of the indigo-Ag2 complex have been calculated. Structure optimization, excitation energies and pre-resonance Raman spectra of the indigo molecule have been obtained at the same level of theory. The available experimental Raman spectra at 1064, 785 and 514 nm and the SERS spectra at 785 and 514 nm have been well reproduced by the calculation. Experimental SERS spectra are confronted with the calculated pre-resonance Raman spectra obtained for the indigo-Ag2 complex. The Raman activities calculated under the infinite lifetime approximation show a strong dependence upon the proximity to the energy and the oscillator strength of the excitation electronic transition. The comparison of the integrated EFs for indigo and indigo-Ag2 calculated Raman spectra, gave some hints as to the enhancement mechanisms acting for the different excitation wavelengths. Whereas for excitation at a wavelength corresponding to 785 nm, the enhancement mechanism for the Raman spectrum of the metal complex seems the chemical one, the strong increment (ten times) of the integrated EF of the Raman spectra of the complex in the case of 514 nm excitation, suggests the onset of other enhancement mechanisms. Assuming that intra-cluster transitions with high oscillator strength can be thought of as to mimic surface plasmons excitations, we suggest the onset of the electromagnetic mechanisms (EM) as the origin of the Raman spectrum enhancement. Nevertheless, other enhancement effects cannot be ruled out, as a new molecular transition gains strength in the proximity of the excitation wavelength, as a consequence of the symmetry lowering of the molecule in the complex. A large variation across vibrational modes, by a factor of at least 104, was found for the EFs. This large variation in the EFs can indicate that B-term Herzberg-Teller scattering, due to metal and/or charge transfer states, can feed intensity to the inactive (in the molecule) and/or non totally symmetric modes.

Time-resolved remote Raman study of minerals under supercritical CO2 and high temperatures relevant to Venus exploration.

PubMed

Sharma, Shiv K; Misra, Anupam K; Clegg, Samuel M; Barefield, James E; Wiens, Roger C; Acosta, Tayro

2010-07-13

We report time-resolved (TR) remote Raman spectra of minerals under supercritical CO(2) (approx. 95 atm pressure and 423 K) and under atmospheric pressure and high temperature up to 1003 K at distances of 1.5 and 9 m, respectively. The TR Raman spectra of hydrous and anhydrous sulphates, carbonate and silicate minerals (e.g. talc, olivine, pyroxenes and feldspars) under supercritical CO(2) (approx. 95 atm pressure and 423 K) clearly show the well-defined Raman fingerprints of each mineral along with the Fermi resonance doublet of CO(2). Besides the CO(2) doublet and the effect of the viewing window, the main differences in the Raman spectra under Venus conditions are the phase transitions, the dehydration and decarbonation of various minerals, along with a slight shift in the peak positions and an increase in line-widths. The dehydration of melanterite (FeSO(4).7H(2)O) at 423 K under approximately 95 atm CO(2) is detected by the presence of the Raman fingerprints of rozenite (FeSO(4).4H(2)O) in the spectrum. Similarly, the high-temperature Raman spectra under ambient pressure of gypsum (CaSO(4).2H(2)O) and talc (Mg(3)Si(4)O(10)(OH)(2)) indicate that gypsum dehydrates at 518 K, but talc remains stable up to 1003 K. Partial dissociation of dolomite (CaMg(CO(3))(2)) is observed at 973 K. The TR remote Raman spectra of olivine, alpha-spodumene (LiAlSi(2)O(6)) and clino-enstatite (MgSiO(3)) pyroxenes and of albite (NaAlSi(3)O(8)) and microcline (KAlSi(3)O(8)) feldspars at high temperatures also show that the Raman lines remain sharp and well defined in the high-temperature spectra. The results of this study show that TR remote Raman spectroscopy could be a potential tool for exploring the surface mineralogy of Venus during both daytime and nighttime at short and long distances.

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

A spectroscopic and computational study of Al(III) complexes in sodium cryolite melts: ionic composition in a wide range of cryolite ratios.

PubMed

Nazmutdinov, Renat R; Zinkicheva, Tamara T; Vassiliev, Sergey Yu; Glukhov, Dmitri V; Tsirlina, Galina A; Probst, Michael

2010-04-01

The structure of sodium cryolite melts was studied using Raman spectroscopy and quantum chemical calculations performed at the density functional theory level. The existence of bridged forms in the melts was argued first from the analysis of experimental Raman spectra. In the quantum chemical modelling emphasis was put on the construction of potential energy surfaces describing the formation/dissociation of certain complex species. Effects of the ionic environment were found to play a crucial role in the energetics of model processes. The structure of the simplest possible polymeric forms involving two Al centres linked through F atoms ("dimers") was thoroughly investigated. The calculated equilibrium constants and model Raman spectra yield additional evidence in favour of the dimers. This agrees with a self-consistent analysis of a series of Raman spectra for a wide range of the melt composition. Copyright 2010. Published by Elsevier B.V.

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.

Detection of Explosives Using Differential Laser-Induced Perturbation Spectroscopy with a Raman-based Probe.

PubMed

Oztekin, Erman K; Burton, Dallas J; Hahn, David W

2016-04-01

Explosives detection is carried out with a novel spectral analysis technique referred to as differential laser-induced perturbation spectroscopy (DLIPS) on thin films of TNT, RDX, HMX, and PETN. The utility of Raman spectroscopy for detection of explosives is enhanced by inducing deep ultraviolet laser perturbation on molecular structures in combination with a differential Raman sensing scheme. Principal components analysis (PCA) is used to quantify the DLIPS method as benchmarked against a traditional Raman scattering probe, and the related photo-induced effects on the molecular structure of the targeted explosives are discussed in detail. Finally, unique detection is observed with TNT samples deposited on commonly available background substrates of nylon and polyester. Overall, the data support DLIPS as a noninvasive method that is promising for screening explosives in real-world environments and backgrounds. © The Author(s) 2016.

Hyperspectral depth-profiling with deep Raman spectroscopy for detecting chemicals in building materials.

PubMed

Cho, Youngho; Song, Si Won; Sung, Jiha; Jeong, Young-Su; Park, Chan Ryang; Kim, Hyung Min

2017-09-25

Toxic chemicals inside building materials have long-term harmful effects on human bodies. To prevent secondary damage caused by the evaporation of latent chemicals, it is necessary to detect the chemicals inside building materials at an early stage. Deep Raman spectroscopy is a potential candidate for on-site detection because it can provide molecular information about subsurface components. However, it is very difficult to spectrally distinguish the Raman signal of the internal chemicals from the background signal of the surrounding materials and to acquire the geometric information of chemicals. In this study, we developed hyperspectral wide-depth spatially offset Raman spectroscopy coupled with a data processing algorithm to identify toxic chemicals, such as chemical warfare agent (CWA) simulants in building materials. Furthermore, the spatial distribution of the chemicals and the thickness of the building material were also measured from one-dimensional (1D) spectral variation.

Identification of strained black phosphorous by Raman spectroscopy

NASA Astrophysics Data System (ADS)

Wan, Jiawei; Guo, Junhong; Hu, Fangren

2017-04-01

Phosphorene has a very high hole mobility and can be a tuned band structure, and has become an ideal material for electronic devices. For this new type of two-dimensional material, in the applied strain, black phosphorus (BP) can be changed into an indirect band gap and metallic materials from the direct band gap semiconductor material, which greatly affect its inherent physical characteristics. How to identify strained microstructure changes becomes an important problem. The calculated Raman spectra disclose that the A{}{{g}}2 mode and B{}2{{g}} mode will split and the Raman spectra appear, while the A{}{{g}}1 mode is shifted to low-frequency region. The deformation induced by strain will effectively change the Raman mode position and intensity, this can be used to identify phosphorus changes. Project supported by the National Science Foundation of China (Nos. 61505085, 61574080, 61274127) and the Innovation Project of Jiangsu Graduate Student, China (No. SJLX15_0379).

Single-Shot Rotational Raman Thermometry for Turbulent Flames Using a Low-Resolution Bandwidth Technique

NASA Technical Reports Server (NTRS)

Kojima, Jun; Nguyen, Quang-Viet

2007-01-01

An alternative optical thermometry technique that utilizes the low-resolution (order 10(exp 1)/cm) pure-rotational spontaneous Raman scattering of air is developed to aid single-shot multiscalar measurements in turbulent combustion studies. Temperature measurements are realized by correlating the measured envelope bandwidth of the pure-rotational manifold of the N2/O2 spectrum with a theoretical prediction of a species-weighted bandwidth. By coupling this thermometry technique with conventional vibrational Raman scattering for species determination, we demonstrate quantitative spatially resolved, single-shot measurements of the temperature and fuel/oxidizer concentrations in a high-pressure turbulent Cf4-air flame. Our technique provides not only an effective means of validating other temperature measurement methods, but also serves as a secondary thermometry technique in cases where the anti-Stokes vibrational N2 Raman signals are too low for a conventional vibrational temperature analysis.

Effect of concentration and pH on the surface-enhanced Raman scattering of captopril on nano-colloidal silver surface

NASA Astrophysics Data System (ADS)

Gao, Junxiang; Gu, Huaimin; Liu, Fangfang; Dong, Xiao; Xie, Min; Hu, Yongjun

2011-07-01

In this report, Raman and surface-enhanced Raman scattering (SERS) spectra of captopril are studied in detail. Herein, the Raman bands are assigned by the density functional theory (DFT) calculations and potential energy distributions (PED) based on internal coordinates of the molecule, which are found to be in good agree with the experimental values. Furthermore, the concentration and pH dependence of the SERS intensity of the molecule is discussed. By analyzing the intensities variation of SERS bands of the different concentrations of captopril solution, it can be concluded that the molecules orientation adsorbed on the silver nanoparticles surface change with the change of the concentrations. The variation of SERS spectra of captopril with the change of pH suggests that the interaction among the adsorbates with Ag cluster depend on the protonated state of the adsorbate and the aggregation of silver nanoparticles.

Highly sensitive surface-enhanced Raman scattering substrate made from superaligned carbon nanotubes.

PubMed

Sun, Yinghui; Liu, Kai; Miao, Jiao; Wang, Zheyao; Tian, Baozhong; Zhang, Lina; Li, Qunqing; Fan, Shoushan; Jiang, Kaili

2010-05-12

Surface-enhanced Raman scattering (SERS) has attracted wide attention because it can enhance normally weak Raman signal by several orders of magnitude and facilitate the sensitive detection of molecules. Conventional SERS substrates are constructed by placing metal nanoparticles on a planar surface. Here we show that, if the planar surface was substituted by a unique nanoporous surface, the enhancement effect can be dramatically improved. The nanoporous surface can be easily fabricated in batches and at low costs by cross stacking superaligned carbon nanotube films. The as-prepared transparent and freestanding SERS substrate is capable of detecting ambient trinitrotoluene vapor, showing much higher Raman enhancement than ordinary planar substrates because of the extremely large surface area and the unique zero-dimensional at one-dimensional nanostructure. These results not only provide a new approach to ultrasensitive SERS substrates, but also are helpful for improving the fundamental understanding of SERS phenomena.

Measuring changes in chemistry, composition, and molecular structure within hair fibers by infrared and Raman spectroscopic imaging.

PubMed

Zhang, Guojin; Senak, Laurence; Moore, David J

2011-05-01

Spatially resolved infrared (IR) and Raman images are acquired from human hair cross sections or intact hair fibers. The full informational content of these spectra are spatially correlated to hair chemistry, anatomy, and structural organization through univariate and multivariate data analysis. Specific IR and Raman images from untreated human hair describing the spatial dependence of lipid and protein distribution, protein secondary structure, lipid chain conformational order, and distribution of disulfide cross-links in hair protein are presented in this study. Factor analysis of the image plane acquired with IR microscopy in hair sections, permits delineation of specific micro-regions within the hair. These data indicate that both IR and Raman imaging of molecular structural changes in a specific region of hair will prove to be valuable tools in the understanding of hair structure, physiology, and the effect of various stresses upon its integrity.

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

Parkin, William M.; Balan, Adrian; Liang, Liangbo

Here, we report how the presence of electron-beam-induced sulfur vacancies affects first-order Raman modes and correlate the effects with the evolution of the in situ transmission-electron microscopy (TEM) two-terminal conductivity of monolayer MoS 2 under electron irradiation. We observe a redshift in the E Raman peak and a less pronounced blueshift in the A' 1 peak with increasing electron dose. Using energy-dispersive X-ray spectroscopy (EDS), we show that irradiation causes partial removal of sulfur and correlate the dependence of the Raman peak shifts with S vacancy density (a few %), which is confirmed by first-principles density functional theory calculations. Inmore » situ device current measurements show exponential decrease in channel current upon irradiation. Our analysis demonstrates that the observed frequency shifts are intrinsic properties of the defective systems and that Raman spectroscopy can be used as a quantitative diagnostic tool to characterize MoS 2-based transport channels.« less

Dynamics of magnetic-field-induced clustering in ionic ferrofluids from Raman scattering

NASA Astrophysics Data System (ADS)

Heinrich, D.; Goñi, A. R.; Thomsen, C.

2007-03-01

Using Raman spectroscopy, the authors have investigated the aggregation/disgregation of magnetic nanoparticles in dense ionic ferrofluids (IFF) into clusters due to the action of an inhomogeneous external magnetic field. Evidence for changes in particle density and/or effective cluster size were obtained from the variation of the Raman intensity in a time window from 10sto10min for magnetic fields up to 350mT and at a temperature of 28°C. Clustering sets in already at very low fields (>15mT) and the IFF samples exhibit a clear hysteresis in the Raman spectra after releasing the magnetic field, which lasts for many hours at room temperature. The authors determined the characteristic times of the two competing processes, that of field-induced cluster formation and, at room temperature, that of thermal-activated dissociation, to range from 100to150s.

Trigonal LaF3: a novel SRS-active crystal

NASA Astrophysics Data System (ADS)

Kaminskii, A. A.; Lux, O.; Hanuza, J.; Rhee, H.; Eichler, H. J.; Zhang, J.; Tang, D.; Shen, D.; Yoneda, H.; Shirakawa, A.

2014-12-01

Trigonal fluoride LaF3, widely known as a host crystal for Ln3+-lasants, was found to be an attractive many-phonon Raman material and a subject for the investigation of different χ(3)-nonlinear optical effects. We present the manifestation of photon-phonon interactions related to stimulated Raman scattering (SRS) and Raman-induced four-wave mixing (RFWM) processes, initiated by picosecond exсitation at room temperature. Sesqui-octave-spanning Stokes and anti-Stokes frequency comb generation as well as many-step cascaded and cross-cascaded up-conversion χ(3)-nonlinear processes have been observed. The recorded spectral lines originated by SRS and RFWM are identified and attributed to the three observed SRS-promoting phonon modes. The lower limit of the steady-state Raman gain coefficient for near-IR first Stokes generation was estimated. Moreover, a brief review of known Ln3+ : LaF3 laser crystals and SRS-active fluorides is given.

Raman spectroscopic study of the photoprotection of extremophilic microbes against ultraviolet radiation

NASA Astrophysics Data System (ADS)

Edwards, H. G. M.; Moeller, R.; Jorge Villar, S. E.; Horneck, G.; Stackebrandt, E.

2006-12-01

Extremophiles use a range of pigments for protection against low-wavelength radiation in exposed terrestrial habitats and photoaccessory materials are synthesized for the effective harnessing of photosynthetically active radiation. Raman spectroscopy has been demonstrated to be a useful probe for information on the survival strategies employed by extremophilic bacteria through the identification of key biomolecular signatures of the suite of protective chemicals synthesized by the organisms in stressed environments. Raman spectroscopic analyses of Bacillus spp. spores, Bacillus atrophaeus (DSM 675: deep red) and Bacillus subtilis (DSM 5611: light grey and DSM 7264: dark grey), Deinococcus radiodurans (pink) and Natronomonas pharaonis (red), of visually different pigmentation showed the presence of different carotenoids and other protectant biomolecules, which assist microorganisms against UVA radiation. The implications for the survival of extremophilic microbes in extraterrestrial habitats and for the detection of the protectant biomolecules by remote, robotic Raman spectroscopic instrumentation in an astrobiological search for life context are discussed.

Analysis of albumin Raman scattering in visible and near-infrared ranges

NASA Astrophysics Data System (ADS)

Lykina, Anastasia A.; Artemyev, Dmitry N.

2018-04-01

In this work the analysis of the shape and intensity of albumin Raman signals in visible and near-IR ranges was carried out. The experimental setup using lasers from the visible region first of all excites the fluorescence of the albumin solution, the main contribution to which is produced by sodium chloride, which is a component of the tested sample. At the same time, lasers from the near-infrared range excited the Raman signal of albumin most effectively. It was found that the highest ratio of Raman scattering to autofluorescence intensities in the detected signal was obtained using a laser with a wavelength of 1064 nm. To determine the albumin solution concentration by type of spectrum, a regression approach with the projection to latent structures method was applied. The lowest predicted error of albumin concentration of 2-3 g/l was obtained by using the near-infrared range lasers.

Raman spectroscopy of blood serum for Alzheimer's disease diagnostics: specificity relative to other types of dementia

PubMed Central

Ryzhikova, Elena; Kazakov, Oleksandr; Halamkova, Lenka; Celmins, Dzintra; Malone, Paula; Molho, Eric; Zimmerman, Earl A.; Lednev, Igor K.

2015-01-01

The key moment for efficiently and accurately diagnosing dementia occurs during the early stages. This is particularly true for Alzheimer's disease (AD). In this proof-of-concept study, we applied near infrared (NIR) Raman microspectroscopy of blood serum together with advanced multivariate statistics for the selective identification of AD. We analyzed data from 20 AD patients, 18 patients with other neurodegenerative dementias (OD) and 10 healthy control (HC) subjects. NIR Raman microspectroscopy differentiated patients with more than 95% sensitivity and specificity. We demonstrated the high discriminative power of artificial neural network (ANN) classification models, thus revealing the high potential of this developed methodology for the differential diagnosis of AD. Raman spectroscopic, blood-based tests may aid clinical assessments for the effective and accurate differential diagnosis of AD, decrease the labor, time and cost of diagnosis, and be useful for screening patient populations for AD development and progression. PMID:25256347

Raman-Suppressing Coupling for Optical Parametric Oscillator

NASA Technical Reports Server (NTRS)

Savchenkov, Anatoliy; Maleki, Lute; Matsko, Andrey; Rubiola, Enrico

2007-01-01

A Raman-scattering-suppressing input/ output coupling scheme has been devised for a whispering-gallery-mode optical resonator that is used as a four-wave-mixing device to effect an all-optical parametric oscillator. Raman scattering is undesired in such a device because (1) it is a nonlinear process that competes with the desired nonlinear four-wave conversion process involved in optical parametric oscillation and (2) as such, it reduces the power of the desired oscillation and contributes to output noise. The essence of the present input/output coupling scheme is to reduce output loading of the desired resonator modes while increasing output loading of the undesired ones.

A reexamination of the effects of adsorbates on the Raman spectrum of gibbsite.

USGS Publications Warehouse

Cunningham, K.W.; Goldberg, M.C.

1983-01-01

Previous workers have attributed substantial changes in the Raman intensities of the OH stretching bands in solid, powdered gibbsite of surface area 10 m2/g to surface interactions with the adsorbates 093Ca2+,HxPO43x- and SiO2.xH2O. These changes apparently resulted from an unsatisfactory Raman measurement procedure as a re-examination using an internal intensity standard (Na2C2O4 crystals) with gibbsite of surface area 39 m2/g showed no significant changes in the low-frequency band-height ratios of gibbsite and adsorbates.-D.J.M.

Optical phonon modes in rhombohedral boron monosulfide under high pressure

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

Cherednichenko, Kirill A.; IMPMC, UPMC Sorbonne Universités, CNRS UMR 7590, 75005 Paris; LSPM–CNRS, Université Paris Nord, 93430 Villetaneuse

2015-05-14

Raman spectra of rhombohedral boron monosulfide (r-BS) were measured under pressures up to 34 GPa at room temperature. No pressure-induced structural phase transition was observed, while strong pressure shift of Raman bands towards higher wavenumbers has been revealed. IR spectroscopy as a complementary technique has been used in order to completely describe the phonon modes of r-BS. All experimentally observed bands have been compared with theoretically calculated ones and modes assignment has been performed. r-BS enriched by {sup 10}B isotope was synthesized, and the effect of boron isotopic substitution on Raman spectra was observed and analyzed.

Discrimination of Medicine Radix Astragali from Different Geographic Origins Using Multiple Spectroscopies Combined with Data Fusion Methods

NASA Astrophysics Data System (ADS)

Wang, Hai-Yan; Song, Chao; Sha, Min; Liu, Jun; Li, Li-Ping; Zhang, Zheng-Yong

2018-05-01

Raman spectra and ultraviolet-visible absorption spectra of four different geographic origins of Radix Astragali were collected. These data were analyzed using kernel principal component analysis combined with sparse representation classification. The results showed that the recognition rate reached 70.44% using Raman spectra for data input and 90.34% using ultraviolet-visible absorption spectra for data input. A new fusion method based on Raman combined with ultraviolet-visible data was investigated and the recognition rate was increased to 96.43%. The experimental results suggested that the proposed data fusion method effectively improved the utilization rate of the original data.

Measuring skin penetration by confocal Raman microscopy (CRM): correlation to results from conventional experiments

NASA Astrophysics Data System (ADS)

Lunter, Dominique; Daniels, Rolf

2016-03-01

Confocal Raman microscopy has become an advancing technique in the characterization of drug transport into the skin. In this study the skin penetration of a local anesthetic from a semisolid preparation was investigated. Furthermore, the effect of the chemical enhancers propylene glycol and POE-23-lauryl ether on its penetration was investigated. The results show that confocal Raman microscopy may provide detailed information on the penetration of APIs into the skin and may elucidate their distribution within the skin with high resolution. The results of the CRM analysis are fully in line with those of conventional permeation and penetration experiments.

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.

Efficient Surface Enhanced Raman Scattering substrates from femtosecond laser based fabrication

NASA Astrophysics Data System (ADS)

Parmar, Vinod; Kanaujia, Pawan K.; Bommali, Ravi Kumar; Vijaya Prakash, G.

2017-10-01

A fast and simple femtosecond laser based methodology for efficient Surface Enhanced Raman Scattering (SERS) substrate fabrication has been proposed. Both nano scaffold silicon (black silicon) and gold nanoparticles (Au-NP) are fabricated by femtosecond laser based technique for mass production. Nano rough silicon scaffold enables large electromagnetic fields for the localized surface plasmons from decorated metallic nanoparticles. Thus giant enhancement (approximately in the order of 104) of Raman signal arises from the mixed effects of electron-photon-phonon coupling, even at nanomolar concentrations of test organic species (Rhodamine 6G). Proposed process demonstrates the low-cost and label-less application ability from these large-area SERS substrates.

Effect of solution concentration on the structured order and optical properties of short-chain polyene biomolecules

NASA Astrophysics Data System (ADS)

Ouyang, Shunli; Sun, Chenglin; Zhou, Mi; Li, Dongfei; Wang, Weiwei; Qu, Guannan; Li, Zuowei; Gao, Shuqin; Yang, Jiange

2010-09-01

We have measured the Raman spectra and UV-Vis absorption spectra of linear polyene biomolecules (β-carotene and lycopene) in CS2 at low concentrations (10-6-10-10 mol/L). With decreasing concentration, all the carbon-carbon vibrations form a coherent mode in ordered β-carotene and lycopene due to extended π-conjugation that gives strong electron-phonon coupling, which leads to an anomalous experimental phenomenon. We observed an extremely high Raman scattering cross section( RSCS) and the Raman activities in β-carotene and lycopene are characterized by intensive overtones and combinations. Further, the UV-Vis absorption bands become narrower.

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

Chow, Kam Kong; Zeng, Haishan, E-mail: hzeng@bccrc.ca; Short, Michael

Purpose: Breath analysis has a potential prospect to benefit the medical field based on its perceived advantages to become a point-of-care, easy to use, and cost-effective technology. Early studies done by mass spectrometry show that volatile organic compounds from human breath can represent certain disease states of our bodies, such as lung cancer, and revealed the potential of breath analysis. But mass spectrometry is costly and has slow-turnaround time. The authors’ goal is to develop a more portable and cost effective device based on Raman spectroscopy and hollow core-photonic crystal fiber (HC-PCF) for breath analysis. Methods: Raman scattering is amore » photon-molecular interaction based on the kinetic modes of an analyte which offers unique fingerprint type signals that allow molecular identification. HC-PCF is a novel light guide which allows light to be confined in a hollow core and it can be filled with a gaseous sample. Raman signals generated by the gaseous sample (i.e., human breath) can be guided and collected effectively for spectral analysis. Results: A Raman-cell based on HC-PCF in the near infrared wavelength range was developed and tested in a single pass forward-scattering mode for different gaseous samples. Raman spectra were obtained successfully from reference gases (hydrogen, oxygen, carbon dioxide gases), ambient air, and a human breath sample. The calculated minimum detectable concentration of this system was ∼15 parts per million by volume, determined by measuring the carbon dioxide concentration in ambient air via the characteristic Raman peaks at 1286 and 1388 cm{sup −1}. Conclusions: The results of this study were compared to a previous study using HC-PCF to trap industrial gases and backward-scatter 514.5 nm light from them. The authors found that the method presented in this paper has an advantage to enhance the signal-to-noise ratio (SNR). This SNR advantage, coupled with the better transmission of HC-PCF in the near-IR than in the visible wavelengths led to an estimated seven times improvement in the detection sensitivity. The authors’ prototype device also demonstrated a 100-fold improvement over a recently reported detection limit of a reflective capillary fiber-based Raman cell for breath analysis. Continued development is underway to increase the detection sensitivity further to reach practical clinical applications.« less

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

Intensity dependence of non-linear kinetic behaviour of stimulated Raman scattering in fusion relevant plasmas

NASA Astrophysics Data System (ADS)

Mašek, Martin; Rohlena, Karel

2015-05-01

Influence of kinetic effects on 3-wave interaction was examined within the frame of stimulated Raman backward scattering (SRBS) in a rarefied laser corona. The plasma is supposed to be weakly collisional with a negligible density gradient. The model is centred on the physical situation of shock ignition at a large scale direct drive compression experiments. The modelling uses a 1D geometry in a Maxwell-Vlasov model. The method used is a truncated Fourier-Hermite expansion numerically stabilized by a model collisional term with a realistic value of the collision frequency. In parallel, besides the linear theory of SRBS, a coupled mode 3-wave equation system (laser driving wave, Raman back-scattered wave and the daughter forward scattered plasma wave) is solved to demonstrate the correspondence between the full kinetic model and 3-wave interaction with no electron kinetics involved to identify the differences between both the solutions arising due to the electron kinetic effects. We concentrated mainly on the Raman reflectivity, which is one of the important parameters controlling the efficiency of the shock ignition scheme. It was found that the onset of the kinetic effects has a distinct intensity threshold, above which the Raman reflectivity may go down due to the electron kinetics. In addition, we were trying to identify the most important features of the electron phase space behaviour, such as particle trapping in potential minima of the generated plasma wave and its consequences for the 3-wave interaction. The role of the trapped electrons seems to be crucial for a deformation of the plasma wave dispersion curve, as indicated in some earlier work.

Performance-Enhancing Methods for Au Film over Nanosphere Surface-Enhanced Raman Scattering Substrate and Melamine Detection Application

PubMed Central

Wang, Jun Feng; Wu, Xue Zhong; Xiao, Rui; Dong, Pei Tao; Wang, Chao Guang

2014-01-01

A new high-performance surface-enhanced Raman scattering (SERS) substrate with extremely high SERS activity was produced. This SERS substrate combines the advantages of Au film over nanosphere (AuFON) substrate and Ag nanoparticles (AgNPs). A three order enhancement of SERS was observed when Rhodamine 6G (R6G) was used as a probe molecule to compare the SERS effects of the new substrate and commonly used AuFON substrate. These new SERS substrates can detect R6G down to 1 nM. The new substrate was also utilized to detect melamine, and the limit of detection (LOD) is 1 ppb. A linear relationship was also observed between the SERS intensity at Raman peak 682 cm−1 and the logarithm of melamine concentrations ranging from 10 ppm to 1 ppb. This ultrasensitive SERS substrate is a promising tool for detecting trace chemical molecules because of its simple and effective fabrication procedure, high sensitivity and high reproducibility of the SERS effect. PMID:24886913

Performance-enhancing methods for Au film over nanosphere surface-enhanced Raman scattering substrate and melamine detection application.

PubMed

Wang, Jun Feng; Wu, Xue Zhong; Xiao, Rui; Dong, Pei Tao; Wang, Chao Guang

2014-01-01

A new high-performance surface-enhanced Raman scattering (SERS) substrate with extremely high SERS activity was produced. This SERS substrate combines the advantages of Au film over nanosphere (AuFON) substrate and Ag nanoparticles (AgNPs). A three order enhancement of SERS was observed when Rhodamine 6G (R6G) was used as a probe molecule to compare the SERS effects of the new substrate and commonly used AuFON substrate. These new SERS substrates can detect R6G down to 1 nM. The new substrate was also utilized to detect melamine, and the limit of detection (LOD) is 1 ppb. A linear relationship was also observed between the SERS intensity at Raman peak 682 cm(-1) and the logarithm of melamine concentrations ranging from 10 ppm to 1 ppb. This ultrasensitive SERS substrate is a promising tool for detecting trace chemical molecules because of its simple and effective fabrication procedure, high sensitivity and high reproducibility of the SERS effect.

Raman Microscopic Characterization of Proton-Irradiated Polycrystalline Diamond Films

NASA Technical Reports Server (NTRS)

Newton, R. L.; Davidson, J. L.; Lance, M. J.

2004-01-01

The microstructural effects of irradiating polycrystalline diamond films with proton dosages ranging from 10(exp 15) to 10(exp 17) H(+) per square centimeter was examined. Scanning Electron Microscopy and Raman microscopy were used to examine the changes in the diamond crystalline lattice as a function of depth. Results indicate that the diamond lattice is retained, even at maximum irradiation levels.

Color and surface chemistry changes of extracted wood flour after heating at 120 °C

Treesearch

Yao Chen; Mandla A. Tshabalala; Jianmin Gao; Nicole M. Stark

2013-01-01

To investigate the effect of heat on color and surface chemistry of wood flour (WF), unextracted, extracted and delignified samples of commercial WF were heated at 120 °C for 24 h and analyzed by colorimetry, diffuse reflectance visible (DRV), attenuated total reflectance Fourier transform infrared (ATR-FTIR) and Fourier transform Raman (FT-Raman) spectroscopies....

Micro-Raman spectroscopy as a tool for the characterization of silicon carbide in power semiconductor material processing

NASA Astrophysics Data System (ADS)

De Biasio, M.; Kraft, M.; Schultz, M.; Goller, B.; Sternig, D.; Esteve, R.; Roesner, M.

2017-05-01

Silicon carbide (SiC) is a wide band-gap semi-conductor material that is used increasingly for high voltage power devices, since it has a higher breakdown field strength and better thermal conductivity than silicon. However, in particular its hardness makes wafer processing difficult and many standard semi-conductor processes have to be specially adapted. We measure the effects of (i) mechanical processing (i.e. grinding of the backside) and (ii) chemical and thermal processing (i.e. doping and annealing), using confocal microscopy to measure the surface roughness of ground wafers and micro-Raman spectroscopy to measure the stresses induced in the wafers by grinding. 4H-SiC wafers with different dopings were studied before and after annealing, using depth-resolved micro-Raman spectroscopy to observe how doping and annealing affect: i.) the damage and stresses induced on the crystalline structure of the samples and ii.) the concentration of free electrical carriers. Our results show that mechanical, chemical and thermal processing techniques have effects on this semiconductor material that can be observed and characterized using confocal microscopy and high resolution micro Raman spectroscopy.

Raman spectroscopy of isotopically pure ({sup 12}C, {sup 13}C) and isotopically mixed ({sup 12.5}C) diamond single crystals at ultrahigh pressures

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

Enkovich, P. V., E-mail: enkovich@hppi.troitsk.ru; Brazhkin, V. V.; Lyapin, S. G.

The Raman scattering by isotopically pure {sup 12}C and {sup 13}C diamond single crystals and by isotopically mixed {sup 12.5}C diamond single crystals is studied at a high accuracy. The studies are performed over a wide pressure range up to 73 GPa using helium as a hydrostatic pressure-transferring medium. It is found that the quantum effects, which determine the difference between the ratio of the Raman scattering frequencies in the {sup 12}C and {sup 13}C diamonds and the classical ratio (1.0408), increase to 30 GPa and then decrease. Thus, inversion in the sign of the quantum contribution to the physicalmore » properties of diamond during compression is detected. Our data suggest that the maximum possible difference between the bulk moduli of the {sup 12}C and {sup 13}C diamonds is 0.15%. The investigation of the isotopically mixed {sup 12.5}C diamond shows that the effective mass, which determines the Raman frequency, decreases during compression from 12.38 au at normal pressure to 12.33 au at 73 GPa.« less

PdSe 2: Pentagonal Two-Dimensional Layers with High Air Stability for Electronics

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

Oyedele, Akinola D.; Yang, Shize; Liang, Liangbo

Most studied two-dimensional (2D) materials exhibit isotropic behavior due to high lattice symmetry; however, lower-symmetry 2D materials such as phosphorene and other elemental 2D materials exhibit very interesting anisotropic properties. In this work, we report the atomic structure, electronic properties, and vibrational modes of few-layered PdSe 2, exfoliated from bulk crystals, a pentagonal 2D layered noble transition metal dichalcogenide with a puckered morphology that is air-stable. Micro-absorption optical spectroscopy and first-principles calculations reveal a wide band gap variation in this material from ~0 (bulk) to ~1.3 eV (monolayer). The Raman active vibrational modes of PdSe 2 were identified using polarizedmore » Raman spectroscopy, and the strong interlayer interaction was revealed from the large thickness-dependent Raman peak shifts, agreeing with first-principles Raman simulations. Field-effect transistors made from the few-layer PdSe 2 display tunable ambipolar charge carrier conduction with a high electron apparent field-effect mobility of ~158 cm 2V -1s -1, indicating the promise of this anisotropic, air-stable, pentagonal 2D material for 2D electronics.« less

PdSe 2: Pentagonal Two-Dimensional Layers with High Air Stability for Electronics

DOE PAGES

Oyedele, Akinola D.; Yang, Shize; Liang, Liangbo; ...

2017-09-05

Most studied two-dimensional (2D) materials exhibit isotropic behavior due to high lattice symmetry; however, lower-symmetry 2D materials such as phosphorene and other elemental 2D materials exhibit very interesting anisotropic properties. In this work, we report the atomic structure, electronic properties, and vibrational modes of few-layered PdSe 2, exfoliated from bulk crystals, a pentagonal 2D layered noble transition metal dichalcogenide with a puckered morphology that is air-stable. Micro-absorption optical spectroscopy and first-principles calculations reveal a wide band gap variation in this material from ~0 (bulk) to ~1.3 eV (monolayer). The Raman active vibrational modes of PdSe 2 were identified using polarizedmore » Raman spectroscopy, and the strong interlayer interaction was revealed from the large thickness-dependent Raman peak shifts, agreeing with first-principles Raman simulations. Field-effect transistors made from the few-layer PdSe 2 display tunable ambipolar charge carrier conduction with a high electron apparent field-effect mobility of ~158 cm 2V -1s -1, indicating the promise of this anisotropic, air-stable, pentagonal 2D material for 2D electronics.« less

Novel Method for Differentiating Histological Types of Gastric Adenocarcinoma by Using Confocal Raman Microspectroscopy

PubMed Central

Hsu, Chih-Wei; Huang, Chia-Chi; Sheu, Jeng-Horng; Lin, Chia-Wen; Lin, Lien-Fu; Jin, Jong-Shiaw; Chau, Lai-Kwan; Chen, Wenlung

2016-01-01

Gastric adenocarcinoma, a single heterogeneous disease with multiple epidemiological and histopathological characteristics, accounts for approximately 10% of cancers worldwide. It is categorized into four histological types: papillary adenocarcinoma (PAC), tubular adenocarcinoma (TAC), mucinous adenocarcinoma (MAC), and signet ring cell adenocarcinoma (SRC). Effective differentiation of the four types of adenocarcinoma will greatly improve the treatment of gastric adenocarcinoma to increase its five-year survival rate. We reported here the differentiation of the four histological types of gastric adenocarcinoma from the molecularly structural viewpoint of confocal Raman microspectroscopy. In total, 79 patients underwent laparoscopic or open radical gastrectomy during 2008–2011: 21 for signet ring cell carcinoma, 21 for tubular adenocarcinoma, 14 for papillary adenocarcinoma, 6 for mucinous carcinoma, and 17 for normal gastric mucosas obtained from patients underwent operation for other benign lesions. Clinical data were retrospectively reviewed from medical charts, and Raman data were processed and analyzed by using principal component analysis (PCA) and linear discriminant analysis (LDA). Two-dimensional plots of PCA and LDA clearly demonstrated that the four histological types of gastric adenocarcinoma could be differentiated, and confocal Raman microspectroscopy provides potentially a rapid and effective method for differentiating SRC and MAC from TAC or PAC. PMID:27472385

Differentiating gastrointestinal stromal tumors from gastric adenocarcinomas and normal mucosae using confocal Raman microspectroscopy

NASA Astrophysics Data System (ADS)

Hsu, Chih-Wei; Huang, Chia-Chi; Sheu, Jeng-Horng; Lin, Chia-Wen; Lin, Lien-Fu; Jin, Jong-Shiaw; Chen, Wenlung

2016-07-01

Gastrointestinal stromal tumors (GISTs) are the most common mesenchymal neoplasms of the gastrointestinal tract, and gastric adenocarcinomas are a common cancer worldwide. To differentiate GISTs from adenocarcinomas is important because the surgical processes for both are different; the former excises the tumor with negative margins, while the latter requires radical gastrectomy with lymph node dissection. Endoscopy with biopsy is used to distinguish GISTs from adenocarcinomas; however, it may cause tumor bleeding in GISTs. We reported here the confocal Raman microspectroscopy as an effective tool to differentiate GISTs, adenocarcinomas, and normal mucosae. Of 119 patients enrolled in this study, 102 patients underwent gastrectomy (40 GISTs and 62 adenocarcinomas), and 17 patients with benign lesions were obtained as normal mucosae. Raman signals were integrated for 100 s for each spot on the specimen, and 5 to 10 spots, depending on the sample size, were chosen for each specimen. There were significant differences among those tissues as evidenced by different Raman signal responding to phospholipids and protein structures. The spectral data were further processed and analyzed by using principal component analysis. A two-dimensional plot demonstrated that GISTs, adenocarcinomas, and normal gastric mucosae could be effectively differentiated from each other.

Explosive detection technology

NASA Astrophysics Data System (ADS)

Doremus, Steven; Crownover, Robin

2017-05-01

The continuing proliferation of improvised explosive devices is an omnipresent threat to civilians and members of military and law enforcement around the world. The ability to accurately and quickly detect explosive materials from a distance would be an extremely valuable tool for mitigating the risk posed by these devices. A variety of techniques exist that are capable of accurately identifying explosive compounds, but an effective standoff technique is still yet to be realized. Most of the methods being investigated to fill this gap in capabilities are laser based. Raman spectroscopy is one such technique that has been demonstrated to be effective at a distance. Spatially Offset Raman Spectroscopy (SORS) is a technique capable of identifying chemical compounds inside of containers, which could be used to detect hidden explosive devices. Coherent Anti-Stokes Raman Spectroscopy (CARS) utilized a coherent pair of lasers to excite a sample, greatly increasing the response of sample while decreasing the strength of the lasers being used, which significantly improves the eye safety issue that typically hinders laser-based detection methods. Time-gating techniques are also being developed to improve the data collection from Raman techniques, which are often hindered fluorescence of the test sample in addition to atmospheric, substrate, and contaminant responses. Ultraviolet based techniques have also shown significant promise by greatly improved signal strength from excitation of resonance in many explosive compounds. Raman spectroscopy, which identifies compounds based on their molecular response, can be coupled with Laser Induced Breakdown Spectroscopy (LIBS) capable of characterizing the sample's atomic composition using a single laser.

Application of imaging spectrometer in gas analysis by Raman scattering

NASA Astrophysics Data System (ADS)

Zuo, Duluo; Yu, Anlan; Li, Zhe; Wang, Xingbing; Xiong, Youhui

2015-09-01

Spontaneous Raman scattering is an effective technique in gas analysis, but the detection of minor constituents is difficult because of the low signal level and the usually existed background. Imaging spectrometer can provide highly spatial resolved spectra, so it should be much easier to pick up Raman signal of minor constituents from the Raman/fluorescence background of the sample cell and transporting optics compared with the widely used fiber-coupled spectrometers. For this reason, an imaging spectrometer was constructed from transmitting volume phase holographic grating, camera lenses and CCD detector. When it was used to analyze the gas sample in metal-lined capillary, which is a sample cell believed with great enhancement of Raman signal, the background was compressed obviously. When it was used to analyze the gas in a sample cell including a parabolic reflector, only weak background signal was observed, as the wide separation between the collecting zone (the focus point of the parabolic surface) and the wall of sample cell benefitted to the analysis by imaging spectrometer. By using the last sample cell, the signal from CO2 in ambient air was able to be found by an exposure time about 20 sec, and limits of detection for H2, CO2 and CO were estimated as 60 ppm, 100 ppm and 300 ppm respectively by the results of a longer exposure time. These results show that an imaging spectrometer paired with a well-arranged sample cell will lower the detecting limit effectively.

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.

Using Raman Spectroscopy in Studying the Effect of Propylene Glycol, Oleic Acid, and Their Combination on the Rat Skin.

PubMed

Atef, Eman; Altuwaijri, Njoud

2018-01-01

The permeability enhancement effect of oleic acid (OA) and propylene glycol (PG) as well as their (1:1 v/v) combined mixture was studied using rat skin. The percutaneous drug administration is a challenge and an opportunity for drug delivery. To date, there is limited research that illustrates the mechanism of penetration enhancers and their combinations on the skin. This project aims to explore the skin diffusion and penetration enhancement of PG, OA, and a combination of PG-OA (1:1 v/v) on rat skin and to identify the potential synergistic effect of the two enhancers utilizing Raman spectroscopy. Dissected dorsal skin was treated with either PG or OA or their combination for predetermined time intervals after which the Raman spectra of the treated skin were collected with the enhancer. A spectrum of the wiped and the washed skin were also collected. The skin integrity was tested before and after exposure to PG. The skin histology proved that the skin integrity has been maintained during experiments and the results indicated that OA disrupted rat skin lipid as evident by changes in the lipid peak. The results also showed that PG and OA improved the diffusion of each other and created faster, yet reversible changes of the skin peaks. In conclusion, Raman spectroscopy is a potential tool for ex vivo skin diffusion studies. We also concluded that PG and OA have potential synergistic reversible effect on the skin.

Nonlinear silicon photonics

NASA Astrophysics Data System (ADS)

Tsia, Kevin K.; Jalali, Bahram

2010-05-01

An intriguing optical property of silicon is that it exhibits a large third-order optical nonlinearity, with orders-ofmagnitude larger than that of silica glass in the telecommunication band. This allows efficient nonlinear optical interaction at relatively low power levels in a small footprint. Indeed, we have witnessed a stunning progress in harnessing the Raman and Kerr effects in silicon as the mechanisms for enabling chip-scale optical amplification, lasing, and wavelength conversion - functions that until recently were perceived to be beyond the reach of silicon. With all the continuous efforts developing novel techniques, nonlinear silicon photonics is expected to be able to reach even beyond the prior achievements. Instead of providing a comprehensive overview of this field, this manuscript highlights a number of new branches of nonlinear silicon photonics, which have not been fully recognized in the past. In particular, they are two-photon photovoltaic effect, mid-wave infrared (MWIR) silicon photonics, broadband Raman effects, inverse Raman scattering, and periodically-poled silicon (PePSi). These novel effects and techniques could create a new paradigm for silicon photonics and extend its utility beyond the traditionally anticipated applications.

Microfluidics, Chromatography, and Atomic-Force Microscopy

NASA Technical Reports Server (NTRS)

Anderson, Mark

2008-01-01

A Raman-and-atomic-force microscope (RAFM) has been shown to be capable of performing several liquid-transfer and sensory functions essential for the operation of a microfluidic laboratory on a chip that would be used to perform rapid, sensitive chromatographic and spectro-chemical analyses of unprecedentedly small quantities of liquids. The most novel aspect of this development lies in the exploitation of capillary and shear effects at the atomic-force-microscope (AFM) tip to produce shear-driven flow of liquids along open microchannels of a microfluidic device. The RAFM can also be used to perform such functions as imaging liquids in microchannels; removing liquid samples from channels for very sensitive, tip-localized spectrochemical analyses; measuring a quantity of liquid adhering to the tip; and dip-pen deposition from a chromatographic device. A commercial Raman-spectroscopy system and a commercial AFM were integrated to make the RAFM so as to be able to perform simultaneous topographical AFM imaging and surface-enhanced Raman spectroscopy (SERS) at the AFM tip. The Raman-spectroscopy system includes a Raman microprobe attached to an optical microscope, the translation stage of which is modified to accommodate the AFM head. The Raman laser excitation beam, which is aimed at the AFM tip, has a wavelength of 785 nm and a diameter of about 5 m, and its power is adjustable up to 10 mW. The AFM is coated with gold to enable tip-localized SERS.

Flexible Microsphere-Embedded Film for Microsphere-Enhanced Raman Spectroscopy.

PubMed

Xing, Cheng; Yan, Yinzhou; Feng, Chao; Xu, Jiayu; Dong, Peng; Guan, Wei; Zeng, Yong; Zhao, Yan; Jiang, Yijian

2017-09-27

Dielectric microspheres with extraordinary microscale optical properties, such as photonic nanojets, optical whispering-gallery modes (WGMs), and directional antennas, have drawn interest in many research fields. Microsphere-enhanced Raman spectroscopy (MERS) is an alternative approach for enhanced Raman detection by dielectric microstructures. Unfortunately, fabrication of microsphere monolayer arrays is the major challenge of MERS for practical applications on various specimen surfaces. Here we report a microsphere-embedded film (MF) by immersing a highly refractive microsphere monolayer array in the poly(dimethylsiloxane) (PDMS) film as a flexible MERS sensing platform for one- to three-dimensional (1D to 3D) specimen surfaces. The directional antennas and wave-guided whispering-gallery modes (WG-WGMs) contribute to the majority of Raman enhancement by the MFs. Moreover, the MF can be coupled with surface-enhanced Raman spectroscopy (SERS) to provide an extra >10-fold enhancement. The limit of detection is therefore improved for sensing of crystal violet (CV) and Sudan I molecules in aqueous solutions at concentrations down to 10 -7 M. A hybrid dual-layer microsphere enhancer, constructed by depositing a MF onto a microsphere monolayer array, is also demonstrated, wherein the WG-WGMs become dominant and boost the enhancement ratio >50-fold. The present work opens up new opportunities for design of cost-effective and flexible MERS sensing platforms as individual or associated techniques toward practical applications in ultrasensitive Raman detection.

Raman spectroscopic investigation of the chemopreventive response of naringenin and its nanoparticles in DMBA-induced oral carcinogenesis

NASA Astrophysics Data System (ADS)

Krishnakumar, N.; Sulfikkarali, N. K.; Manoharan, S.; Venkatachalam, P.

2013-11-01

Raman spectroscopy is a vibrational spectroscopic technique that can be used to optically probe the biomolecular changes associated with tumor progression. The aim of the present study is to investigate the biomolecular changes in chemopreventive response of prepared naringenin-loaded nanoparticles (NARNPs) relative to efficacy of free naringenin (NAR) during 7,12-dimethyl benz(a)anthracene (DMBA)-induced oral carcinogenesis by Fourier Transform Raman (FT-Raman) spectroscopy. Oral squamous cell carcinoma (OSCC) was developed in the buccal pouch of golden Syrian hamsters by painting with 0.5% DMBA in liquid paraffin three times a week for 14 weeks. Raman spectra differed significantly between the control and tumor tissues, with tumors showing higher percentage signals for nucleic acids, phenylalanine and tryptophan and a lower in the percentage of phospholipids. Moreover, oral administration of free NAR and NARNPs significantly increased phospholipids and decreased the levels of tryptophan, phenylalanine and nucleic acid contents. On a comparative basis, NARNPs was found to have a more potent antitumor effect than free NAR in completely preventing the formation of squamous cell carcinoma and in improving the biochemical status to a normal range in DMBA-induced oral carcinogenesis. The present study further suggest that Raman spectroscopy could be a valuable tool for rapid and sensitive detection of specific biomolecular changes in response to chemopreventive agents.

Industrial Raman gas sensing for real-time system control

NASA Astrophysics Data System (ADS)

Buric, M.; Mullen, J.; Chorpening, B.; Woodruff, S.

2014-06-01

Opportunities exist to improve on-line process control in energy applications with a fast, non-destructive measurement of gas composition. Here, we demonstrate a Raman sensing system which is capable of reporting the concentrations of numerous species simultaneously with sub-percent accuracy and sampling times below one-second for process control applications in energy or chemical production. The sensor is based upon a hollow-core capillary waveguide with a 300 micron bore with reflective thin-film metal and dielectric linings. The effect of using such a waveguide in a Raman process is to integrate Raman photons along the length of the sample-filled waveguide, thus permitting the acquisition of very large Raman signals for low-density gases in a short time. The resultant integrated Raman signals can then be used for quick and accurate analysis of a gaseous mixture. The sensor is currently being tested for energy applications such as coal gasification, turbine control, well-head monitoring for exploration or production, and non-conventional gas utilization. In conjunction with an ongoing commercialization effort, the researchers have recently completed two prototype instruments suitable for hazardous area operation and testing. Here, we report pre-commercialization testing of those field prototypes for control applications in gasification or similar processes. Results will be discussed with respect to accuracy, calibration requirements, gas sampling techniques, and possible control strategies of industrial significance.

Ultra-sensitive molecular detection using surface-enhanced Raman scattering on periodic metal-dielectric nanostructures

NASA Astrophysics Data System (ADS)

Nien, Chun; Li, Yi-Hsuan; Su, Vin-Cent; Kuan, Chieh-Hsiung

2017-02-01

Surface-enhanced Raman scattering (SERS) is a powerful technique for trace chemical analysis and single molecule detection in the application of biochemical monitoring and food safety due to its ability to enhance the Raman scattering of molecules near the metallic surface or nanostructures. Here, we present a comprehensive study of the SERS enhancement by the periodically nanostructured surface, where the thin film of silver is deposited onto the surface, except the sidewall of posts, of 1-D lamellar gratings with varying pitch to forming metal-dielectric composite nanostructures. By enhancing the localized and surface-propagating mode in the vicinity of the concaves, the SERS signal can be improved by amplifying the intensity of electric field and increasing the optical path length of the incident light. Experimental investigations show that the enhancement factor can be manipulated by varying the polarization of incident light and the pitch size of gratings. To demonstrate the SERS effects of the proposed structures, thin layers of benzoic acid, which is commonly used as a food preservative, are deposited on the SERS substrates by spin-coating a solution of benzoic acid and dried at room temperature. A Confocal Raman microscope with a 532 nm laser source is used to illuminate light and measure the Raman spectrum of benzoic acid. We demonstrate the Raman signal of benzoic acid can be enhanced on the order of 102 on the SERS substrates.

Photoinduced oxygen dynamics in lyophilized hemoglobin

NASA Astrophysics Data System (ADS)

Nöllmann, M.; Etchegoin, P.

2000-12-01

Reversible laser induced deoxygenation in the lyophilized phase of hemoglobin is demonstrated by means of resonant Raman scattering, luminescence, and optical transmission. Specific Raman modes, which are both sensitive to the spin states of Fe(II) in the hemes and resonant in the visible, are monitored as a function of time to evaluate the effect of the illuminating laser. These modes act as in-situ markers of the oxygen content of the protein. The reversible photoinduced deoxygenation can be observed through both the Raman spin-markers and the optical transmission experiments. In the former, reversible changes in the intensities of specific Raman modes are observed, while in the latter, the oscillator strength of the two main absorptions of oxyhemoglobin in the visible are seen to vary accordingly. The luminescence in lyophilized hemoglobin is found to have at least two different contributions, (i) a resonant component with the Raman modes and; (ii) a nonresonant contribution, which increases at high input laser powers and eventually masks the Raman signals. The nonresonant contribution is the luminescence of the photoproduct achieved by thermal denaturation of the protein and remains standing as a permanent nonreversible damage in the illuminated spot. Semiempirical electronic calculations of the wavefunction and total energy of the iron porphyrin reveal the underlying physical origin of the laser induced deoxygenation process in the hemes and are also presented.

Resonance and Variable Temperature Raman Studies of Chloroperoxidase and Methemoglobin.

NASA Astrophysics Data System (ADS)

Remba, Ronald David

1980-12-01

Raman spectra of the heme proteins chloroperoxidase and methemoglobin, chemically and temperature modified, are obtained for laser excitation near the Soret absorption band. Numerous biochemical and physical results are obtained. The following observations for chloroperoxidase have been made. The scattered intensity for resonance (406.7 nm) excitation is at least twenty times that for near resonance (457.9 nm) excitation. In resonance only totally symmetric modes are enhanced. The positions of marker band I ((TURN) 1370 cm(' -1)) for both the native and reduced enzymes are lower than expected for high-spin heme proteins indicating a strongly electron donating axial ligand. From shifts in spin-sensitive Raman peaks as the temperature is lowered, a high-spin to low-spin transition of the heme iron is inferred. Raman spectra of chloroperoxidase liganded with small ions indicate that there is a second anion binding site near the heme. Photo-dissociation of CO from reduced chloroperoxidase is observed. The position of marker band I in the CO complex indicates that electron density is transferred from the heme onto the CO. The resonance Raman spectra of chloroperoxidase and cytochrome P-450 are nearly identical and are very different from those of horseradish peroxidase and cytochrome c. These results, particularly for the reduced enzymes, indicate that the heme sites in chloroperoxidase and P -450 are essentially the same. Raman spectra of a number of methemoglobins complexed with various small ions are obtained as a function of temperature in the region of spin-sensitive marker band (II) ((TURN) 1500 cm('-1)) for laser excitation near the Soret absorption band. For certain ligands, H(,2)O, N(,3)('-), OCN('-), OH('-) and SCN('-), the iron spin state changes from high spin to low spin with decreasing temperature. The relative spin concentrations are monitored by measuring the Raman intensity ratio, I(,h)/I(,1), of the high-spin and low -spin versions of marker band (II) as a function of temperature. This is the first study where the marker band technique is used to measure quantitatively spin transitions. For hydroxide and cyanate methemoglobin, log(I(,h)/I(,1)) varies linearly with 1/T, indicating a high-spin/low-spin thermal equilibrium. The data are analyzed to extract enthalpic and entropic changes. (DELTA)H values from Raman and static magnetic susceptibility techniques show good agreement. (DELTA)S values for horse hydroxide methemoglobin also agree. However, for cyanate methemoglobin, Raman and susceptibility (DELTA)S values differ substantially. Other evidence (ESR, optical, etc.) supports the Raman result. The discrepancy is probably due to the effects of freezing on the protein solution. Other methemoglobins show a discontinuity in the Raman intensity ratio at the freezing transition indicating a non-equilibrium situation where the freezing process drives the spin transition. Effects of freezing the protein solution on the spin transition are discussed. Both the high-spin and low-spin Raman frequencies are observed to remain constant (within (+OR-) 2 cm('-1)) when the temperature is varied. This is discussed in terms of core expansion and heme deformation. Experimental (DELTA)S values are much larger than the spin-only value. This is discussed in terms of a linear temperature dependence on the energy gap between the ('2)T(,2) ground state and the ('6)A(,1) first excited state. Variable temperature Raman data for carp azide methemoglobin with and without IHP indicate that the free energy for the spin transition decreases by 0.6 (+OR-) 0.3 kcal/mole when hemoglobin quaternary structure changes from R to T. Lack of any frequency shift in either the high-spin or low-spin Raman band upon addition of IHP is consistent with other evidence indicating no iron movement upon conversion of R to T quaternary forms.

Gap-mode enhancement on MoS2 probed by functionalized tip-enhanced Raman spectroscopy

NASA Astrophysics Data System (ADS)

Alajlan, Abdulrahman M.; Voronine, Dmitri V.; Sinyukov, Alexander M.; Zhang, Zhenrong; Sokolov, Alexei V.; Scully, Marlan O.

2016-09-01

Surface enhancement of molecular spectroscopic signals has been widely used for sensing and nanoscale imaging. Because of the weak electromagnetic enhancement of Raman signals on semiconductors, it is motivating but challenging to study the electromagnetic effect separately from the chemical effects. We report tip-enhanced Raman scattering measurements on Au and bulk MoS2 substrates using a metallic tip functionalized with copper phthalocyanine molecules and demonstrate similar gap-mode enhancement on both substrates. We compare the experimental results with theoretical calculations to confirm the gap-mode enhancement on MoS2 using a well-established electrostatic model. The functionalized tip approach allows for suppressing the background and is ideal for separating electromagnetic and chemical enhancement mechanisms on various substrates. Our results may find a wide range of applications in MoS2-based devices, sensors, and metal-free nanoscale bio-imaging.

Rare-earth metal halogenide encapsulation-induced modifications in Raman spectra of single-walled carbon nanotubes

NASA Astrophysics Data System (ADS)

Kharlamova, M. V.

2015-01-01

In the present work, a detailed Raman spectroscopy investigation on the single-walled carbon nanotubes (SWCNTs) filled with praseodymium chloride, terbium chloride and thulium chloride was performed. The salts were incorporated inside the SWCNTs by a capillary filling method using melts, and the high-resolution transmission electron microscopy data proved the high filling degree of the nanotube channels. A thorough analysis of the radial breathing mode and G-band of the Raman spectra of the pristine and filled SWCNTs showed that the encapsulated salts cause acceptor doping of the host nanotubes, and the doping efficiency depends on the compound. The incorporated thulium chloride has the strongest doping effect on the SWCNTs, whereas praseodymium chloride has the weakest effect. It was found that the encapsulated salts modify more significantly the electronic structure of metallic nanotubes than semiconducting SWCNTs.

The graphene phonon dispersion with C12 and C13 isotopes

NASA Astrophysics Data System (ADS)

Whiteway, Eric; Bernard, Simon; Yu, Victor; Austing, D. Guy; Hilke, Michael

2013-12-01

Using very uniform large scale chemical vapor deposition grown graphene transferred onto silicon, we were able to identify 15 distinct Raman lines associated with graphene monolayers. This was possible thanks to a combination of different carbon isotopes and different Raman laser energies and extensive averaging without increasing the laser power. This allowed us to obtain a detailed experimental phonon dispersion relation for many points in the Brillouin zone. We further identified a D+D' peak corresponding to a double phonon process involving both an inter- and intra-valley phonon. In order to both eliminate substrate effects and to probe large areas, we undertook to study Raman scattering for large scale chemical vapor deposition (CVD) grown graphene using two different isotopes (C12 and C13) so that we can effectively exclude and subtract the substrate contributions, since a heavier mass downshifts only the vibrational properties, while keeping all other properties the same.

Nonlinear Raman forward scattering of a short laser pulse in a collisional transversely magnetized plasma

NASA Astrophysics Data System (ADS)

Paknezhad, Alireza

2013-01-01

Nonlinear Raman forward scattering (NRFS) of an intense short laser pulse with a duration shorter than the plasma period through a homogenous collisional transversely magnetized plasma is investigated theoretically when ponderomotive, relativistic and collioninal nonlinearities are taken into account. The plasma is embedded in a uniform magnetic field perpendicular to both, the direction of propagation and electric vector of the radiation field. Nonlinear wave equation is set up and Fourier transformation method is used to solve the coupled equations describing NRFS instability. Finally, the growth rate of this instability is obtained. Thermal effects of plasma electrons and effect of the electron-ion collisions are examined. It is found that the growth rate of Raman forward scattering first decreases on increasing electron thermal velocity, minimizes at an optimum value, and then increases. Our results also show that the growth rate increases by increasing the electron-ion collisions.

Surface-enhanced Raman spectroscopy with Au-nanoparticle substrate fabricated by using femtosecond pulse

NASA Astrophysics Data System (ADS)

Zhang, Wending; Li, Cheng; Gao, Kun; Lu, Fanfan; Liu, Min; Li, Xin; Zhang, Lu; Mao, Dong; Gao, Feng; Huang, Ligang; Mei, Ting; Zhao, Jianlin

2018-05-01

Au-nanoparticle (Au-NP) substrates for surface-enhanced Raman spectroscopy (SERS) were fabricated by grid-like scanning a Au-film using a femtosecond pulse. The Au-NPs were directly deposited on the Au-film surface due to the scanning process. The experimentally obtained Au-NPs presented local surface plasmon resonance effect in the visible spectral range, as verified by finite difference time domain simulations and measured reflection spectrum. The SERS experiment using the Au-NP substrates exhibited high activity and excellent substrate reproducibility and stability, and a clearly present Raman spectra of target analytes, e.g. Rhodamine-6G, Rhodamine-B and Malachite green, with concentrations down to 10‑9 M. This work presents an effective approach to producing Au-NP SERS substrates with advantages in activity, reproducibility and stability, which could be used in a wide variety of practical applications for trace amount detection.

Assessing the effect of a high-fat diet on rodents' adipose tissue using Brillouin and Raman spectroscopy

NASA Astrophysics Data System (ADS)

Troyanova-Wood, Maria; Gobbell, Cassidy; Meng, Zhaokai; Yakovlev, Vladislav V.

2016-03-01

The purpose of this study is to evaluate the effect of a high-lipid diet on elasticity of adipose tissue. We employed dual Raman/Brillouin microspectroscopy to analyze brown and white adipose tissues obtained from adult rats. The rats were divided into two groups, one of which received a high-fat feed, while the other served as a control. We hypothesized that the changes in the elasticity of adipose tissues between the two groups can be successfully assessed using Brillouin spectroscopy. We found that the brown adipose tissue possessed a lesser Brillouin shift than the white adipose within each group and that the elastic modulus of both adipose tissues increases in the high-fat diet group. The Raman spectra provided supplementary chemical information and indicated an increase in the lipid-to-protein ratio in the brown adipose, but not in the white adipose.

Surface-enhanced Raman spectroscopy with Au-nanoparticle substrate fabricated by using femtosecond pulse.

PubMed

Zhang, Wending; Li, Cheng; Gao, Kun; Lu, Fanfan; Liu, Min; Li, Xin; Zhang, Lu; Mao, Dong; Gao, Feng; Huang, Ligang; Mei, Ting; Zhao, Jianlin

2018-05-18

Au-nanoparticle (Au-NP) substrates for surface-enhanced Raman spectroscopy (SERS) were fabricated by grid-like scanning a Au-film using a femtosecond pulse. The Au-NPs were directly deposited on the Au-film surface due to the scanning process. The experimentally obtained Au-NPs presented local surface plasmon resonance effect in the visible spectral range, as verified by finite difference time domain simulations and measured reflection spectrum. The SERS experiment using the Au-NP substrates exhibited high activity and excellent substrate reproducibility and stability, and a clearly present Raman spectra of target analytes, e.g. Rhodamine-6G, Rhodamine-B and Malachite green, with concentrations down to 10 -9 M. This work presents an effective approach to producing Au-NP SERS substrates with advantages in activity, reproducibility and stability, which could be used in a wide variety of practical applications for trace amount detection.

Dynamics of the time-resolved stimulated Raman scattering spectrum in presence of transient vibronic inversion of population on the example of optically excited trans-β-apo-8{sup ′}-carotenal

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

Kardaś, T. M., E-mail: kardas@chem.uw.edu.pl; Ratajska-Gadomska, B.; Gadomski, W.

2014-05-28

We have studied the effect of transient vibrational inversion of population in trans-β-apo-8{sup ′}-carotenal on the time-resolved femtosecond stimulated Raman scattering (TR-FSRS) signal. The experimental data are interpreted by applying a quantum mechanical approach, using the formalism of projection operators for constructing the theoretical model of TR-FSRS. Within this theoretical frame we explain the presence of transient Raman losses on the Stokes side of the TR-FSRS spectrum as the effect of vibrational inversion of population. In view of the obtained experimental and theoretical results, we conclude that the excited S{sub 2} electronic level of trans-β-apo-8{sup ′}-carotenal relaxes towards the S{submore » 0} ground state through a set of four vibrational sublevels of S{sub 1} state.« less

Raman Scattering in the Magnetized Semiconductor Plasma

NASA Astrophysics Data System (ADS)

Jankauskas, Zigmantas; Kvedaras, Vygaudas; Balevičius, Saulius

2005-04-01

Radio frequency (RF) magnetoplasmic waves known as helicons will propagate in solid-state plasmas when a strong magnetic field is applied. In our device the helicons were excited by RFs (the range 100-2000 MHz) much higher than the helicon generation frequency (the main peak at 20 MHz). The excitation of helicons in this case may be described by the effect similar to the Combination Scattering (Raman effect) when a part of the high RF wave energy that passes through the active material is absorbed and re-emitted by the magnetized solid-state plasma. It is expedient to call this experimental device a Helicon Maser (HRM) and the higher frequency e/m field - a pumping field. In full analogy with the usual Raman maser (or laser) the magnetized semiconductor sample plays the role of active material and the connecting cable - the role of high quality external resonator.

Raman Scattering in the Magnetized Semiconductor Plasma

NASA Astrophysics Data System (ADS)

Jankauskas, Zigmantas; Kvedaras, Vygaudas; Balevičius, Saulius

Radio frequency (RF) magnetoplasmic waves known as helicons will propagate in solid-state plasmas when a strong magnetic field is applied. In our device the helicons were excited by RFs (the range 100-2000 MHz) much higher than the helicon generation frequency (the main peak at 20 MHz). The excitation of helicons in this case may be described by the effect similar to the Combination Scattering (Raman effect) when a part of the high RF wave energy that passes through the active material is absorbed and re-emitted by the magnetized solid-state plasma. It is expedient to call this experimental device a Helicon Maser (HRM) and the higher frequency e/m field - a pumping field. In full analogy with the usual Raman maser (or laser) the magnetized semiconductor sample plays the role of active material and the connecting cable - the role of high quality external resonator.

Simultaneous measurement of temperature, stress, and electric field in GaN HEMTs with micro-Raman spectroscopy.

PubMed

Bagnall, Kevin R; Moore, Elizabeth A; Badescu, Stefan C; Zhang, Lenan; Wang, Evelyn N

2017-11-01

As semiconductor devices based on silicon reach their intrinsic material limits, compound semiconductors, such as gallium nitride (GaN), are gaining increasing interest for high performance, solid-state transistor applications. Unfortunately, higher voltage, current, and/or power levels in GaN high electron mobility transistors (HEMTs) often result in elevated device temperatures, degraded performance, and shorter lifetimes. Although micro-Raman spectroscopy has become one of the most popular techniques for measuring localized temperature rise in GaN HEMTs for reliability assessment, decoupling the effects of temperature, mechanical stress, and electric field on the optical phonon frequencies measured by micro-Raman spectroscopy is challenging. In this work, we demonstrate the simultaneous measurement of temperature rise, inverse piezoelectric stress, thermoelastic stress, and vertical electric field via micro-Raman spectroscopy from the shifts of the E 2 (high), A 1 longitudinal optical (LO), and E 2 (low) optical phonon frequencies in wurtzite GaN. We also validate experimentally that the pinched OFF state as the unpowered reference accurately measures the temperature rise by removing the effect of the vertical electric field on the Raman spectrum and that the vertical electric field is approximately the same whether the channel is open or closed. Our experimental results are in good quantitative agreement with a 3D electro-thermo-mechanical model of the HEMT we tested and indicate that the GaN buffer acts as a semi-insulating, p-type material due to the presence of deep acceptors in the lower half of the bandgap. This implementation of micro-Raman spectroscopy offers an exciting opportunity to simultaneously probe thermal, mechanical, and electrical phenomena in semiconductor devices under bias, providing unique insight into the complex physics that describes device behavior and reliability. Although GaN HEMTs have been specifically used in this study to demonstrate its viability, this technique is applicable to any solid-state material with a suitable Raman response and will likely enable new measurement capabilities in a wide variety of scientific and engineering applications.

Simultaneous measurement of temperature, stress, and electric field in GaN HEMTs with micro-Raman spectroscopy

NASA Astrophysics Data System (ADS)

Bagnall, Kevin R.; Moore, Elizabeth A.; Badescu, Stefan C.; Zhang, Lenan; Wang, Evelyn N.

2017-11-01

As semiconductor devices based on silicon reach their intrinsic material limits, compound semiconductors, such as gallium nitride (GaN), are gaining increasing interest for high performance, solid-state transistor applications. Unfortunately, higher voltage, current, and/or power levels in GaN high electron mobility transistors (HEMTs) often result in elevated device temperatures, degraded performance, and shorter lifetimes. Although micro-Raman spectroscopy has become one of the most popular techniques for measuring localized temperature rise in GaN HEMTs for reliability assessment, decoupling the effects of temperature, mechanical stress, and electric field on the optical phonon frequencies measured by micro-Raman spectroscopy is challenging. In this work, we demonstrate the simultaneous measurement of temperature rise, inverse piezoelectric stress, thermoelastic stress, and vertical electric field via micro-Raman spectroscopy from the shifts of the E2 (high), A1 longitudinal optical (LO), and E2 (low) optical phonon frequencies in wurtzite GaN. We also validate experimentally that the pinched OFF state as the unpowered reference accurately measures the temperature rise by removing the effect of the vertical electric field on the Raman spectrum and that the vertical electric field is approximately the same whether the channel is open or closed. Our experimental results are in good quantitative agreement with a 3D electro-thermo-mechanical model of the HEMT we tested and indicate that the GaN buffer acts as a semi-insulating, p-type material due to the presence of deep acceptors in the lower half of the bandgap. This implementation of micro-Raman spectroscopy offers an exciting opportunity to simultaneously probe thermal, mechanical, and electrical phenomena in semiconductor devices under bias, providing unique insight into the complex physics that describes device behavior and reliability. Although GaN HEMTs have been specifically used in this study to demonstrate its viability, this technique is applicable to any solid-state material with a suitable Raman response and will likely enable new measurement capabilities in a wide variety of scientific and engineering applications.

Water Raman normalization of airborne laser fluorosensor measurements - A computer model study

NASA Technical Reports Server (NTRS)

Poole, L. R.; Esaias, W. E.

1982-01-01

The technique for normalizing airborne lidar measurements of chlorophyll fluoresence by the water Raman scattering signal is investigated for laser-excitation wavelengths of 480 and 532 nm using a semianalytic Monte Carlo methodology (SALMON). The signal-integration depth for chlorophyll fluorescence Z(90,F), is found to be insensitive to excitation wavelength and ranges from a maximum of 4.5 m in clearest waters to less than 1 m at a chlorophyll concentration of 20 microgram/liter. For excitation at 532 nm, the signal-integration depth for Raman scattering, Z(90,R), is comparable to Z(90,F). For excitation at 480 nm, Z(90,R) is four times as large as Z(90,F) in clearest waters but nearly equivalent at chlorophyll concentrations greater than 2-3 microgram/liter. Absolute signal levels are stronger with excitation at 480 nm than with excitation at 532 nm, but this advantage must be weighed against potential ambiguities resulting from different integration depths for the fluorescence and Raman scattering signals in clearer waters. To the precision of the simulations, Raman normalization produces effectively linear response to chlorophyll concentration for both excitation wavelengths.

Goldindec: A Novel Algorithm for Raman Spectrum Baseline Correction

PubMed Central

Liu, Juntao; Sun, Jianyang; Huang, Xiuzhen; Li, Guojun; Liu, Binqiang

2016-01-01

Raman spectra have been widely used in biology, physics, and chemistry and have become an essential tool for the studies of macromolecules. Nevertheless, the raw Raman signal is often obscured by a broad background curve (or baseline) due to the intrinsic fluorescence of the organic molecules, which leads to unpredictable negative effects in quantitative analysis of Raman spectra. Therefore, it is essential to correct this baseline before analyzing raw Raman spectra. Polynomial fitting has proven to be the most convenient and simplest method and has high accuracy. In polynomial fitting, the cost function used and its parameters are crucial. This article proposes a novel iterative algorithm named Goldindec, freely available for noncommercial use as noted in text, with a new cost function that not only conquers the influence of great peaks but also solves the problem of low correction accuracy when there is a high peak number. Goldindec automatically generates parameters from the raw data rather than by empirical choice, as in previous methods. Comparisons with other algorithms on the benchmark data show that Goldindec has a higher accuracy and computational efficiency, and is hardly affected by great peaks, peak number, and wavenumber. PMID:26037638

DNA-Encoded Raman-Active Anisotropic Nanoparticles for microRNA Detection.

PubMed

Qi, Lin; Xiao, Mingshu; Wang, Xiwei; Wang, Cheng; Wang, Lihua; Song, Shiping; Qu, Xiangmeng; Li, Li; Shi, Jiye; Pei, Hao

2017-09-19

The development of highly sensitive and selective methods for the detection of microRNA (miRNA) has attracted tremendous attention because of its importance in fundamental biological studies and diagnostic applications. In this work, we develop DNA-encoded Raman-active anisotropic nanoparticles modified origami paper analytical devices (oPADs) for rapid, highly sensitive, and specific miRNA detection. The Raman-active anisotropic nanoparticles were prepared using 10-mer oligo-A, -T, -C, and -G to mediate the growth of Ag cubic seeds into Ag nanoparticles (AgNPs) with different morphologies. The resulting AgNPs were further encoded with DNA probes to serve as effective surface-enhanced Raman scattering (SERS) probes. The analytical device was then fabricated on a single piece of SERS probes loaded paper-based substrate and assembled based on the principles of origami. The addition of the target analyte amplifies the Raman signals on DNA-encoded AgNPs through a target-dependent, sequence specific DNA hybridization assembly. This simple and low-cost analytical device is generic and applicable to a variety of miRNAs, allowing detection sensitivity down to 1 pM and assay time within 15 min, and therefore holds promising applications in point-of-care diagnostics.

Detection of innersphere interactions between magnesium hydrate and the phosphate backbone of the HDV ribozyme using Raman crystallography.

PubMed

Gong, Bo; Chen, Yuanyuan; Christian, Eric L; Chen, Jui-Hui; Chase, Elaine; Chadalavada, Durga M; Yajima, Rieko; Golden, Barbara L; Bevilacqua, Philip C; Carey, Paul R

2008-07-30

A Raman microscope and Raman difference spectroscopy are used to detect the vibrational signature of RNA-bound magnesium hydrate in crystals of hepatitis delta virus (HDV) ribozyme and to follow the effects of magnesium hydrate binding to the nonbridging phosphate oxygens in the phosphodiester backbone. There is a correlation between the Raman intensity of the innersphere magnesium hydrate signature peak, near 322 cm-1, and the intensity of the PO2- symmetric stretch, near 1100 cm-1, perturbed by magnesium binding, demonstrating direct observation of -PO2-...Mg2+(H2O)x innersphere complexes. The complexes may be pentahydrates (x = 5) and tetrahydrates (x = 4). The assignment of the Raman feature near 322 cm-1 to a magnesium hydrate species is confirmed by isotope shifts observed in D2O and H218O that are semiquantitatively reproduced by calculations. The standardized intensity changes in the 1100 cm-1 PO2- feature seen upon magnesium hydrate binding indicates that there are approximately 5 innersphere Mg2+...-O2P contacts per HDV molecule when the crystal is exposed to a solution containing 20 mM magnesium.

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.

Low-frequency Raman scattering in a Xe hydrate.

PubMed

Adichtchev, S V; Belosludov, V R; Ildyakov, A V; Malinovsky, V K; Manakov, A Yu; Subbotin, O S; Surovtsev, N V

2013-09-12

The physics of gas hydrates are rich in interesting phenomena such as anomalies for thermal conductivity, self-preservation effects for decomposition, and others. Some of these phenomena are presumably attributed to the resonance interaction of the rattling motions of guest molecules or atoms with the lattice modes. This can be expected to induce some specific features in the low-frequency (THz) vibrational response. Here we present results for low-frequency Raman scattering in a Xe hydrate, supported by numerical calculations of vibrational density of states. A number of narrow lines, located in the range from 18 to 90 cm(-1), were found in the Raman spectrum. Numerical calculations confirm that these lines correspond to resonance modes of the Xe hydrate. Also, low-frequency Raman scattering was studied during gas hydrate decomposition, and two scenarios were observed. The first one is the direct decomposition of the Xe hydrate to water and gas. The second one is the hydrate decomposition to ice and gas with subsequent melting of ice. In the latter case, a transient low-frequency Raman band is observed, which is associated with low-frequency bands (e.g., boson peak) of disordered solids.

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 Imaging in Cell Membranes, Lipid-Rich Organelles, and Lipid Bilayers.

PubMed

Syed, Aleem; Smith, Emily A

2017-06-12

Raman-based optical imaging is a promising analytical tool for noninvasive, label-free chemical imaging of lipid bilayers and cellular membranes. Imaging using spontaneous Raman scattering suffers from a low intensity that hinders its use in some cellular applications. However, developments in coherent Raman imaging, surface-enhanced Raman imaging, and tip-enhanced Raman imaging have enabled video-rate imaging, excellent detection limits, and nanometer spatial resolution, respectively. After a brief introduction to these commonly used Raman imaging techniques for cell membrane studies, this review discusses selected applications of these modalities for chemical imaging of membrane proteins and lipids. Finally, recent developments in chemical tags for Raman imaging and their applications in the analysis of selected cell membrane components are summarized. Ongoing developments toward improving the temporal and spatial resolution of Raman imaging and small-molecule tags with strong Raman scattering cross sections continue to expand the utility of Raman imaging for diverse cell membrane studies.

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.

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.

Evolution of Instrumentation for Detection of the Raman Effect as Driven by Available Technologies and by Developing Applications

ERIC Educational Resources Information Center

Adar, Fran; Delhaye, Michel; DaSilva, Edouard

2007-01-01

The evolution of Raman instrumentation from the time of the initial report of the phenomenon in 1928 to 2006 is discussed. The first instruments were prism-based spectrographs using lenses for collimation and focusing and the 21st century instruments are also spectrographs, but they use CCD cameras. The Lippmann filter technology that appears to…

Study on the application of Raman spectroscopy on detecting water hardness.

PubMed

Yang, Chang-Hu; Shi, Xiang-Hua; Yuan, Jian-Hui

2014-05-01

Laser Raman spectrum method was used to study the hardness index of four water samples. The ratio of bending vibration peak intensity to stretching vibration peak intensity of these water samples was measured. The results showed that as the total hardness of water decreases, so does the ratio. This offers a possible new approach to water quality analysis that is both simple and effective.

DOE ASR Final Report on “Use of ARM Observations to Investigate the Role of Tropical Radiative Processes and Cloud Radiative Effects in Climate Simulations”

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

Fu, Qiang; Comstock, Jennifer

The overall objective of this ASR funded project is to investigate the role of cloud radiative effects, especially those associated with tropical thin cirrus clouds in the tropical tropopause layer, by analyzing the ARM observations combined with numerical models. In particular, we have processed and analyzed the observations from the Raman lidar at the ARM SGP and TWP sites. In the tenure of the project (8/15/2013 – 8/14/2016 and with a no-cost extension to 8/14/2017), we have been concentrating on (i) developing an automated feature detection scheme of clouds and aerosols for the ARM Raman lidar; (ii) developing an automatedmore » retrieval of cloud and aerosol extinctions for the ARM Raman lidar; (iii) investigating cloud radiative effects based on the observations on the simulated temperatures in the tropical tropopause layer using a radiative-convective model; and (iv) examining the effect of changes of atmospheric composition on the tropical lower-stratospheric temperatures. In addition, we have examined the biases in the CALIPSO-inferred aerosol direct radiative effects using ground-based Raman lidars at the ARM SGP and TWP sites, and estimated the impact of lidar detection sensitivity on assessing global aerosol direct radiative effects. We have also investigated the diurnal cycle of clouds and precipitation at the ARM site using the cloud radar observations along with simulations from the multiscale modeling framework. The main results of our research efforts are reported in the six referred journal publications that acknowledge the DOE Grant DE-SC0010557.« less

In vivo Raman spectroscopy for biochemical monitoring of the human cervix throughout pregnancy.

PubMed

O'Brien, Christine M; Vargis, Elizabeth; Rudin, Amy; Slaughter, James C; Thomas, Giju; Newton, J Michael; Reese, Jeff; Bennett, Kelly A; Mahadevan-Jansen, Anita

2018-05-01

The cervix must undergo significant biochemical remodeling to allow for successful parturition. This process is not fully understood, especially in instances of spontaneous preterm birth. In vivo Raman spectroscopy is an optical technique that can be used to investigate the biochemical composition of tissue longitudinally and noninvasively in human beings, and has been utilized to measure physiology and disease states in a variety of medical applications. The purpose of this study is to measure in vivo Raman spectra of the cervix throughout pregnancy in women, and to identify biochemical markers that change with the preparation for delivery and postpartum repair. In all, 68 healthy pregnant women were recruited. Raman spectra were measured from the cervix of each patient monthly in the first and second trimesters, weekly in the third trimester, and at the 6-week postpartum visit. Raman spectra were measured using an in vivo Raman system with an optical fiber probe to excite the tissue with 785 nm light. A spectral model was developed to highlight spectral regions that undergo the most changes throughout pregnancy, which were subsequently used for identifying Raman peaks for further analysis. These peaks were analyzed longitudinally to determine if they underwent significant changes over the course of pregnancy (P < .05). Finally, 6 individual components that comprise key biochemical constituents of the human cervix were measured to extract their contributions in spectral changes throughout pregnancy using a linear combination method. Patient factors including body mass index and parity were included as variables in these analyses. Raman peaks indicative of extracellular matrix proteins (1248 and 1254 cm -1 ) significantly decreased (P < .05), while peaks corresponding to blood (1233 and 1563 cm -1 ) significantly increased (P < .0005) in a linear manner throughout pregnancy. In the postpartum cervix, significant increases in peaks corresponding to actin (1003, 1339, and 1657 cm -1 ) and cholesterol (1447 cm -1 ) were observed when compared to late gestation, while signatures from blood significantly decreased. Postpartum actin signals were significantly higher than early pregnancy, whereas extracellular matrix proteins and water signals were significantly lower than early weeks of gestation. Parity had a significant effect on blood and extracellular matrix protein signals, with nulliparous patients having significant increases in blood signals throughout pregnancy, and higher extracellular matrix protein signals in early pregnancy compared to patients with prior pregnancies. Body mass index significantly affected actin signal contribution, with low body mass index patients showing decreasing actin contribution throughout pregnancy and high body mass index patients demonstrating increasing actin signals. Raman spectroscopy was successfully used to biochemically monitor cervical remodeling in pregnant women during prenatal visits. This foundational study has demonstrated sensitivity to known biochemical dynamics that occur during cervical remodeling, and identified patient variables that have significant effects on Raman spectra throughout pregnancy. Raman spectroscopy has the potential to improve our understanding of cervical maturation, and be used as a noninvasive preterm birth risk assessment tool to reduce the incidence, morbidity, and mortality caused by preterm birth. Copyright © 2018. Published by Elsevier Inc.

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 from the inverse piezoelectric effect in wurtzite GaN, which has been predicted theoretically in zinc blende gallium arsenide (GaAs).« less

Test of Equivalence Principle at 10(-8) Level by a Dual-Species Double-Diffraction Raman Atom Interferometer.

PubMed

Zhou, Lin; Long, Shitong; Tang, Biao; Chen, Xi; Gao, Fen; Peng, Wencui; Duan, Weitao; Zhong, Jiaqi; Xiong, Zongyuan; Wang, Jin; Zhang, Yuanzhong; Zhan, Mingsheng

2015-07-03

We report an improved test of the weak equivalence principle by using a simultaneous 85Rb-87Rb dual-species atom interferometer. We propose and implement a four-wave double-diffraction Raman transition scheme for the interferometer, and demonstrate its ability in suppressing common-mode phase noise of Raman lasers after their frequencies and intensity ratios are optimized. The statistical uncertainty of the experimental data for Eötvös parameter η is 0.8×10(-8) at 3200 s. With various systematic errors corrected, the final value is η=(2.8±3.0)×10(-8). The major uncertainty is attributed to the Coriolis effect.

Analysis of human hair by Raman microspectroscopy

NASA Astrophysics Data System (ADS)

Plascencia-Castro, A. S.; Cordova-Fraga, T.; Piña-Ruiz, A. L.; Hernández-Rayas, A.; Bernal, J. J.

2017-04-01

Raman microspectroscopy is an optical compound identification technique, which is widely used nowadays for different field applications. A crucial part of this technique is the focus given to the sample in the microscope because it depends on which part of the sample it will analyze. In this work, the effects of irradiating a natural hair samples, obtained from women aged 18 to 55, with a monochromatic light of the Raman spectrometer in two different focus is presented. Two different spectra were obtained with a peak in common. Depending on the information wanted, how the sample is focused plays a crucial role, either way the spectra is information-rich and may be used for biomedical applications.

Impact of Graphene-Metal Interfaces on the Raman and Transport Properties of Graphene Devices

NASA Astrophysics Data System (ADS)

Hsu, Allen; Hofmann, Mario; Fang, Wenjing; Kimg, Ki Kang; Kong, Jing; Palacios, Tomas

2012-02-01

Graphene is an amazing nano-material with many exciting properties and applications. However, due to its low dimensionality, the performance of this material is mainly limited by interfaces and surface properties. One of these interfaces, important for graphene field effect transistors and catalysts supported on graphene membranes, is that between the graphene and a metal layer. In this study, we experimentally examine the impact of various metals on graphene through Raman and Transmission Electron Microscopy. We find that strong graphene-metal interactions have significant impacts on the phonon structure in graphene. Furthermore, we observe changes in our Raman spectra relating to the crystallographic orientation between a metal and graphene.

Interaction of proflavine with DNA studied by colloid surface enhanced resonance Raman spectroscopy

NASA Astrophysics Data System (ADS)

Koglin, E.; Séquaris, J.-M.

1986-03-01

The interaction of the mutagenic highly fluourescing proflavine (3,6-diaminoacridine: PF) dye with calf thymus DNA has been studied by Surface Enhanced Resonance Raman Scattering (SERRS). Since the Ag-colloids almost completely quenche the strong fluorescence it is possible to obtain excellent vibrational spectra in a wide frequency range providing valuable information about the intercalation. The intercalation does not affect the vibrational frequencies of the proflavine dye. On the other hand, intensity changes are observed in some of the ring- and NH 2-modes of proflavine upon intercalation. This Raman hypochromism is characteristic for ring stacking interactions and in the SERRS spetroscopy for an additional effects of the dye orientation to the surface.

Influence of nonlinear detuning at plasma wavebreaking threshold on backward Raman compression of non-relativistic laser pulses

NASA Astrophysics Data System (ADS)

Balakin, A. A.; Fraiman, G. M.; Jia, Q.; Fisch, N. J.

2018-06-01

Taking into account the nonlinear dispersion of the plasma wave, the fluid equations for the three-wave (Raman) interaction in plasmas are derived. It is found that, in some parameter regimes, the nonlinear detuning resulting from the plasma wave dispersion during Raman compression limits the plasma wave amplitude to noticeably below the generally recognized wavebreaking threshold. Particle-in-cell simulations confirm the theoretical estimates. For weakly nonlinear dispersion, the detuning effect can be counteracted by pump chirping or, equivalently, by upshifting slightly the pump frequency, so that the frequency-upshifted pump interacts with the seed at the point where the plasma wave enters the nonlinear stage.

Research study of the treatment efficacy of staphylococcia in the palatine tonsils by using Raman-scattering spectroscopy method

NASA Astrophysics Data System (ADS)

Timchenko, E. V.; Timchenko, P. E.; Asadova, A. A.; Ityaksov, Yu. D.; Tyumchenkova, A. S.

2017-08-01

Analysis of effectiveness of the staphylococcal infections treatment in the tonsils is carried out using Raman spectroscopy method. Spectral changes were established in the treatment of palatine tonsils with the antibiotic Amoksiklav. It was shown that when the antibiotic dosage is 500mg / 10ml, the lines disappear at wave numbers 735 cm-1 and 783 cm-1, 986 cm-1, and 1633 cm-1, corresponding to adenine, cytosine, proteins, and amide I, which indicates the effectiveness of treatment.

Comparison of time-gated surface-enhanced Raman spectroscopy (TG-SERS) and classical SERS based monitoring of Escherichia coli cultivation samples.

PubMed

Kögler, Martin; Paul, Andrea; Anane, Emmanuel; Birkholz, Mario; Bunker, Alex; Viitala, Tapani; Maiwald, Michael; Junne, Stefan; Neubauer, Peter

2018-06-08

The application of Raman spectroscopy as a monitoring technique for bioprocesses is severely limited by a large background signal originating from fluorescing compounds in the culture media. Here we compare time-gated Raman (TG-Raman)-, continuous wave NIR-process Raman (NIR-Raman) and continuous wave micro-Raman (micro-Raman) approaches in combination with surface enhanced Raman spectroscopy (SERS) for their potential to overcome this limit. For that purpose, we monitored metabolite concentrations of Escherichia coli bioreactor cultivations in cell-free supernatant samples. We investigated concentration transients of glucose, acetate, AMP and cAMP at alternating substrate availability, from deficiency to excess. Raman and SERS signals were compared to off-line metabolite analysis of carbohydrates, carboxylic acids and nucleotides. Results demonstrate that SERS, in almost all cases, led to a higher number of identifiable signals and better resolved spectra. Spectra derived from the TG-Raman were comparable to those of micro-Raman resulting in well-discernable Raman peaks, which allowed for the identification of a higher number of compounds. In contrast, NIR-Raman provided a superior performance for the quantitative evaluation of analytes, both with and without SERS nanoparticles when using multivariate data analysis. This article is protected by copyright. All rights reserved. © 2018 American Institute of Chemical Engineers.

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 labels will allow in situ detection of metabolically-targeted active community members on complex natural substrates providing a crucial link between microbial activity and environmental context.

High pressure studies on group VI metal hexacarbonyl molecular solids

NASA Astrophysics Data System (ADS)

Garimella, Subrahmanyam Venkata

Group VI metal hexacarbonyls, M(CO)6 (M = Cr, Mo and W), are of extreme importance as catalysts in industry and also of fundamental interest due to the established charge transfer mechanism between the carbon monoxide and the metal. They condense to molecular solids at ambient conditions retaining the octahedral (Oh) symmetry of gas phase and have been extensively investigated by previous workers to understand their fundamental chemical bonding and possible industrial applications. However little is known about their behavior at high pressures which is the focus of this dissertation. Metal hexacarbonyls were subjected to high pressures in Diamond-Anvil cells to understand the pressure effect on chemical bonding using Raman scattering in situ. The high-pressure results on each of the three metal hexacarbonyls are presented and are followed by a critical analysis of the entire family. The Raman study was conducted at pressures up to 45 GPa and X-ray up to 58 GPa. This is followed by a discussion on infra red spectra in conjunction with Raman and X-ray analysis to provide a rationale for polymerization. Finally the probable synthesis of extremely reactive species under high-pressures and as identified via Raman is discussed. The high-pressure Raman scattering, up to 30 GPa, demonstrated the absence of pi-backbonding. The disappearance of parental Raman spectra for (M = Cr, Mo and W) at 29.6, 23.3 and 22.2 GPa respectively was attributed to the total collapse of the Oh symmetry. This collapse under high-pressure lead to metal-mediated polymeric phase characterized by Raman active delta(OCO) feature, originating from intermolecular vibrational coupling in the parent sample. Further increase in pressures up to 45 GPa, did not affect this feature. The pressure quenched Raman spectra, revealed various chemical groups non-characteristic of the parent sample and adsorption of CO in addition to the characteristic delta(OCO) feature. The thus recorded Raman, complemented with the far and mid-infrared pressure quenched spectra, reveal the formation of novel metal-mediated polymers. The X-ray diffraction on W(CO)6 up to 58 GPa revealed the generation of amorphous polymeric pattern which was retained back to ambient conditions.

Screening and staging for non-small cell lung cancer by serum laser Raman spectroscopy.

PubMed

Wang, Hong; Zhang, Shaohong; Wan, Limei; Sun, Hong; Tan, Jie; Su, Qiucheng

2018-08-05

Lung cancer is the leading cause of cancer-related death worldwide. Current clinical screening methods to detect lung cancer are expensive and associated with many complications. Raman spectroscopy is a spectroscopic technique that offers a convenient method to gain molecular information about biological samples. In this study, we measured the serum Raman spectral intensity of healthy volunteers and patients with different stages of non-small cell lung cancer. The purpose of this study was to evaluate the application of serum laser Raman spectroscopy as a low cost alternative method in the screening and staging of non-small cell lung cancer (NSCLC). The Raman spectra of the sera of peripheral venous blood were measured with a LabRAM HR 800 confocal Micro Raman spectrometer for individuals from five groups including 14 healthy volunteers (control group), 23 patients with stage I NSCLC (stage I group), 24 patients with stage II NSCLC (stage II group), 19 patients with stage III NSCLC (stage III group), 11 patients with stage IV NSCLC (stage IV group). Each serum sample was measured 3 times at different spots and the average spectra represented the signal of Raman spectra in each case. The Raman spectrum signal data of the five groups were statistically analyzed by analysis of variance (ANOVA), principal component analysis (PCA), linear discriminant analysis (LDA), and cross-validation. Raman spectral intensity was sequentially reduced in serum samples from control group, stage I group, stage II group and stage III/IV group. The strongest peak intensity was observed in the control group, and the weakest one was found in the stage III/IV group at bands of 848 cm -1 , 999 cm -1 , 1152 cm -1 , 1446 cm -1 and 1658 cm -1 (P < 0.05). Linear discriminant analysis showed that the sensitivity to identify healthy people, stage I, stage II, and stage III/IV NSCLC was 86%, 65%, 75%, and 87%, respectively; the specificity was 95%, 94%, 88%, and 93%, respectively; and the overall accuracy rate was 92% (71/77). The laser Raman spectroscopy can effectively identify patients with stage I, stage II or stage III/IV Non-Small Cell Lung cancer using patient serum samples. Copyright © 2018 Elsevier B.V. All rights reserved.

Design of SERS nanoprobes for Raman imaging: materials, critical factors and architectures.

PubMed

Li, Mingwang; Qiu, Yuanyuan; Fan, Chenchen; Cui, Kai; Zhang, Yongming; Xiao, Zeyu

2018-05-01

Raman imaging yields high specificity and sensitivity when compared to other imaging modalities, mainly due to its fingerprint signature. However, intrinsic Raman signals are weak, thus limiting medical applications of Raman imaging. By adsorbing Raman molecules onto specific nanostructures such as noble metals, Raman signals can be significantly enhanced, termed surface-enhanced Raman scattering (SERS). Recent years have witnessed great interest in the development of SERS nanoprobes for Raman imaging. Rationally designed SERS nanoprobes have greatly enhanced Raman signals by several orders of magnitude, thus showing great potential for biomedical applications. In this review we elaborate on recent progress in design strategies with emphasis on material properties, modifying factors, and structural parameters.

The Raman Laser Spectrometer for the ExoMars Rover Mission to Mars

NASA Astrophysics Data System (ADS)

Rull, Fernando; Maurice, Sylvestre; Hutchinson, Ian; Moral, Andoni; Perez, Carlos; Diaz, Carlos; Colombo, Maria; Belenguer, Tomas; Lopez-Reyes, Guillermo; Sansano, Antonio; Forni, Olivier; Parot, Yann; Striebig, Nicolas; Woodward, Simon; Howe, Chris; Tarcea, Nicolau; Rodriguez, Pablo; Seoane, Laura; Santiago, Amaia; Rodriguez-Prieto, Jose A.; Medina, Jesús; Gallego, Paloma; Canchal, Rosario; Santamaría, Pilar; Ramos, Gonzalo; Vago, Jorge L.; RLS Team

2017-07-01

The Raman Laser Spectrometer (RLS) on board the ESA/Roscosmos ExoMars 2020 mission will provide precise identification of the mineral phases and the possibility to detect organics on the Red Planet. The RLS will work on the powdered samples prepared inside the Pasteur analytical suite and collected on the surface and subsurface by a drill system. Raman spectroscopy is a well-known analytical technique based on the inelastic scattering by matter of incident monochromatic light (the Raman effect) that has many applications in laboratory and industry, yet to be used in space applications. Raman spectrometers will be included in two Mars rovers scheduled to be launched in 2020. The Raman instrument for ExoMars 2020 consists of three main units: (1) a transmission spectrograph coupled to a CCD detector; (2) an electronics box, including the excitation laser that controls the instrument functions; and (3) an optical head with an autofocus mechanism illuminating and collecting the scattered light from the spot under investigation. The optical head is connected to the excitation laser and the spectrometer by optical fibers. The instrument also has two targets positioned inside the rover analytical laboratory for onboard Raman spectral calibration. The aim of this article was to present a detailed description of the RLS instrument, including its operation on Mars. To verify RLS operation before launch and to prepare science scenarios for the mission, a simulator of the sample analysis chain has been developed by the team. The results obtained are also discussed. Finally, the potential of the Raman instrument for use in field conditions is addressed. By using a ruggedized prototype, also developed by our team, a wide range of terrestrial analog sites across the world have been studied. These investigations allowed preparing a large collection of real, in situ spectra of samples from different geological processes and periods of Earth evolution. On this basis, we are working to develop models for interpreting analog processes on Mars during the mission.

Exploiting LBL-assembled Au nanoparticles to enhance Raman signals for point-of-care testing of osteoporosis with excreta sample

NASA Astrophysics Data System (ADS)

Sun, Jian F.; Liu, Xuan; Guo, Zhi R.; Dong, Jian; Huang, Yawen; Zhang, Jie; Jin, Hui; Gu, Ning

2017-02-01

Due to the intrinsic lack of specific biomarkers, there is an increasing demand for degenerative diseases to develop a testing method independent upon the targeting biomolecules. In this paper, we proposed a novel idea for this issue which was to analyze the characteristic information of metabolites with Raman spectrum. First, we achieved the fabrication of stable, uniform and reproducible substrate to enhance the Raman signals, which is crucial to the following analysis of information. This idea was confirmed with the osteoporosis-modeled mice. Furthermore, the testing results with clinical samples also preliminarily exhibited the feasibility of this strategy. The substrate to enhance Raman signal was fabricated by the layer-by-layer assembly of Au nanoparticles. The osteoporosis modeling was made by bilateral ovariectomy. Ten female mice were randomly divided into two groups. The urine and dejecta samples of mice were collected every week. Clinic urine samples were collected from patients with osteoporosis while the controlled samples were from the young students in our university. The LBL-assembled substrate of Au nanoparticles was uniform, stable and reproducible to significantly enhance the Raman signals from tiny amount of samples. With a simple data processing technique, the Raman signal-based method can effectively reflect the development of osteoporosis by comparison with micro-CT characterization. Moreover, the Raman signal from samples of clinic patients also showed the obvious difference with that of the control. Raman spectrum may be a good tool to convey the pathological information of metabolites in molecular level. Our results manifested that the information-based testing is possibly feasible and promising. Our strategy utilizes the characteristic information rather than the biological recognition to test the diseases which are difficult to find specific biomarkers. This will be greatly beneficial to the prevention and diagnosis of degenerative diseases. Also, we believe the combination of big bio-data and characteristic recognition will change the current paradigm of medical diagnosis essentially.

Raman-based system for DNA sequencing-mapping and other separations

DOEpatents

Vo-Dinh, Tuan

1994-01-01

DNA sequencing and mapping are performed by using a Raman spectrometer with a surface enhanced Raman scattering (SERS) substrate to enhance the Raman signal. A SERS label is attached to a DNA fragment and then analyzed with the Raman spectrometer to identify the DNA fragment according to characteristics of the Raman spectrum generated.

Identification of Multiple Water-Iodide Species in Concentrated NaI Solutions Based on the Raman Bending Vibration of Water.

PubMed

Besemer, Matthieu; Bloemenkamp, Rob; Ariese, Freek; van Manen, Henk-Jan

2016-02-11

The influence of aqueous electrolytes on the water bending vibration was studied with Raman spectroscopy. For all salts investigated (NaI, NaBr, NaCl, and NaSCN), we observed a nonlinear intensity increase of the water bending vibration with increasing concentration. Different lasers and a tunable frequency-doubled optical parametric oscillator system were used to achieve excitation wavelengths between 785 and 374 nm. Focusing on NaI solutions, the relative enhancement of the water bending vibration was found to increase strongly with excitation photon energy, in line with a preresonance effect from the iodide-water charge-transfer transition. We used multivariate curve resolution (MCR) to decompose the measured Raman spectra of NaI solutions into three interconverting spectral components assigned to bulk water and water molecules interacting with one (X···H-O-H···O) and two (X···H-O-H···X) iodide ions (X = I(-)). The Raman spectrum of solid sodium iodide dihydrate supports the assignment of the latter. Using the MCR results, relative Raman scattering cross sections of 4.0 ± 0.6 and 14.0 ± 0.1 were calculated for the mono- and di-iodide species, respectively (compared to that of bulk water set to unity). In addition, it was found that at relatively low concentrations each iodide ion affects the Raman spectrum of roughly 22 surrounding water molecules, indicating that the influence of iodide extends beyond the first solvation shell. Our results demonstrate that the Raman bending vibration of water is a sensitive probe, providing new insights into anion solvation in aqueous environments.

Feasibility of Raman spectroscopy in vitro after 5-ALA-based fluorescence diagnosis in the bladder

NASA Astrophysics Data System (ADS)

Grimbergen, M. C. M.; van Swol, C. F. P.; van Moorselaar, R. J. A.; Mahadevan-Jansen, A.,; Stone, N.

2006-02-01

Photodynamic diagnosis (PDD) has become popular in bladder cancer detection. Several studies have however shown an increased false positive biopsies rate under PDD guidance compared to conventional cystoscopy. Raman spectroscopy is an optical technique that utilizes molecular specific, inelastic scattering of light photons to interrogate biological tissues, which can successfully differentiate epithelial neoplasia from normal tissue and inflammations in vitro. This investigation was performed to show the feasibility of NIR Raman spectroscopy in vitro on biopsies obtained under guidance of 5-ALA induced PPIX fluorescence imaging. Raman spectra of a PPIX solution was measured to obtain a characteristic signature for the photosensitzer without contributions from tissue constituents. Biopsies were obtained from patients with known bladder cancer instilled with 50ml, 5mg 5-ALA two hours prior to trans-urethral resection of tumor (TURT). Additional biopsies were obtained at a fluorescent and non-fluorescent area, snap-frozen in liquid nitrogen and stored at -80 °C. Each biopsy was thawed before measurements (10sec integration time) with a confocal Raman system (Renishaw Gloucestershire, UK). The 830 nm excitation (300mW) source is focused on the tissue by a 20X ultra-long-working-distance objective. Differences in fluorescence background between the two groups were removed by means of a special developed fluorescence subtraction algorithm. Raman spectra from ALA biopsies showed different fluorescence background which can be effectively removed by a fluorescence subtraction algorithm. This investigation shows that the interaction of the ALA induced PPIX with Raman spectroscopy in bladder samples. Combination of these techniques in-vivo may lead to a viable method of optical biopsies in bladder cancer detection.

Density functional theory study on Herzberg-Teller contribution in Raman scattering from 4-aminothiophenol-metal complex and metal-4-aminothiophenol-metal junction

NASA Astrophysics Data System (ADS)

Liu, Shasha; Zhao, Xiuming; Li, Yuanzuo; Zhao, Xiaohong; Chen, Maodu

2009-06-01

Density functional theory (DFT) and time-dependent DFT calculations have been performed to investigate the Raman scattering spectra of metal-molecule complex and metal-molecule-metal junction architectures interconnected with 4-aminothiophenol (PATP) molecule. The simulated profiles of normal Raman scattering (NRS) spectra for the two complexes (Ag2-PATP and PATP-Au2) and the two junctions (Ag2-PATP-Au2 and Au2-PATP-Ag2) are similar to each other, but exhibit obviously different Raman intensities. Due to the lager static polarizabilities of the two junctions, which directly influence the ground state chemical enhancement in NRS spectra, the calculated normal Raman intensities of them are stronger than those of two complexes by the factor of 102. We calculate preresonance Raman scattering (RRS) spectra with incident light at 1064 nm, which is much lower than the S1 electronic transition energy of complexes and junctions. Ag2-PATP-Au2 and Au2-PATP-Ag2 junctions yield higher Raman intensities than those of Ag2-PATP and PATP-Au2 complexes, especially for b2 modes. This effect is mainly attributed to charge transfer (CT) between the metal gap and the PAPT molecule which results in the occurrence of CT resonance enhancement. The calculated pre-RRS spectra strongly depend on the electronic transition state produced by new structures. With excitation at 514.5 nm, the calculated pre-RRS spectra of two complexes and two junctions are stronger than those of with excitation at 1064 nm. A charge difference densities methodology has been used to visually describe chemical enhancement mechanism of RRS spectrum. This methodology aims at visualizing intermolecular CT which provides direct evidence of the Herzberg-Teller mechanism.

Use of in situ and confocal Raman spectroscopy to study the nature and distribution of carotenoids in brown patinas from a deteriorated wall painting in Marcus Lucretius House (Pompeii).

PubMed

Maguregui, M; Knuutinen, U; Trebolazabala, J; Morillas, H; Castro, K; Martinez-Arkarazo, I; Madariaga, J M

2012-02-01

Colonisation of wall paintings by microorganisms and other organisms is a well-known problematic phenomenon. Besides taxonomic identification of the biodeteriogen, it is essential to evaluate the consequences of the colonisation, e.g., unsightly coloured patinas. This work proposes new methodology for characterisation of the nature of the main carotenoids and their distribution in brown stains or patinas of a deteriorated wall painting on the north wall of the atrium of Marcus Lucretius House (Pompeii, Italy). Characterisation of the brown patinas and surrounding areas (plaster and polychromy) from the wall painting started with in situ screening using, mainly, a portable Raman instrument with a handheld FTIR (DRIFTS sampling interface) in order to select the sampling areas suitable for further analysis in the laboratory. Two wall painting fragments were then analysed in the laboratory in two steps. First, microscopic observations (SEM and phase-contrast microscopy) were used to determine whether biodeteriogens were present in the samples. In a second step, confocal Raman microscopy (785 and 514 nm excitation lasers) was used to characterise the main biogenic compounds of the brown stains. Because of the resonance Raman effect (514 nm excitation laser), it was possible to obtain reliable Raman features to assign not only the nature of the main biogenic pigments (carotenoids) present in the stains, but also their spatial conformation. Moreover, Raman confocal applications, for example, Raman imaging and depth profiling were also used in a first attempt to determine the distribution of biosynthesised carotenoids in the stains, and to determine the thickness of the brown patinas.

Niobium pentoxide: a promising surface-enhanced Raman scattering active semiconductor substrate

NASA Astrophysics Data System (ADS)

Shan, Yufeng; Zheng, Zhihui; Liu, Jianjun; Yang, Yong; Li, Zhiyuan; Huang, Zhengren; Jiang, Dongliang

2017-03-01

Surface-enhanced Raman scattering technique, as a powerful tool to identify the molecular species, has been severely restricted to the noble metals. The surface-enhanced Raman scattering substrates based on semiconductors would overcome the shortcomings of metal substrates and promote development of surface-enhanced Raman scattering technique in surface science, spectroscopy, and biomedicine studies. However, the detection sensitivity and enhancement effects of semiconductor substrates are suffering from their weak activities. In this work, a semiconductor based on Nb2O5 is reported as a new candidate for highly sensitive surface-enhanced Raman scattering detection of dye molecules. The largest enhancement factor value greater than 107 was observed with the laser excitation at 633 and 780 nm for methylene blue detection. As far as literature review shows, this is in the rank of the highest sensitivity among semiconductor materials; even comparable to the metal nanostructure substrates with "hot spots". The impressive surface-enhanced Raman scattering activities can be attributed to the chemical enhancement dominated by the photo-induced charge transfer, as well as the electromagnetic enhancement, which have been supported by the density-functional-theory and finite element method calculation results. The chemisorption of dye on Nb2O5 creates a new highest occupied molecular orbital and lowest unoccupied molecular orbital contributed by both fragments in the molecule-Nb2O5 system, which makes the charge transfer more feasible with longer excitation wavelength. In addition, the electromagnetic enhancement mechanism also accounts for two orders of magnitude enhancement in the overall enhancement factor value. This work has revealed Nb2O5 nanoparticles as a new semiconductor surface-enhanced Raman scattering substrate that is able to replace noble metals and shows great potentials applied in the fields of biology related.

Circularly polarized Raman study on diamond structure crystals

NASA Astrophysics Data System (ADS)

Lee, Je-Ho; Kim, Sera; Seong, Maeng-Je

2018-01-01

Circularly polarized Raman and/or photoluminescence (PL) analyses have recently been very important in studying physical properties of many layered materials that were either mechanically exfoliated or grown by chemical-vapor-deposition (CVD) on silicon substrates. Since silicon Raman signal is always accompanied by the circularly polarized Raman and/or PL signal from the layered materials, observation of proper circularly polarized Raman selection rules on silicon substrates would be extremely good indicator that the circularly polarized Raman and/or PL measurements on the layered materials were done properly. We have performed circularly polarized Raman measurements on silicon substrates and compared the results with the Raman intensities calculated by using Raman tensors of the diamond crystal structure. Our experimental results were in excellent agreement with the calculation. Similar circularly polarized Raman analysis done on germanium substrate also showed good agreement.

Characterization of Raman Scattering in Solid Samples with Different Particle Sizes and Elucidation on the Trends of Particle Size-Dependent Intensity Variations in Relation to Changes in the Sizes of Laser Illumination and Detection Area.

PubMed

Duy, Pham K; Chun, Seulah; Chung, Hoeil

2017-11-21

We have systematically characterized Raman scatterings in solid samples with different particle sizes and investigated subsequent trends of particle size-induced intensity variations. For this purpose, both lactose powders and pellets composed of five different particle sizes were prepared. Uniquely in this study, three spectral acquisition schemes with different sizes of laser illuminations and detection windows were employed for the evaluation, since it was expected that the experimental configuration would be another factor potentially influencing the intensity of the lactose peak, along with the particle size itself. In both samples, the distribution of Raman photons became broader with the increase in particle size, as the mean free path of laser photons, the average photon travel distance between consecutive scattering locations, became longer under this situation. When the particle size was the same, the Raman photon distribution was narrower in the pellets since the individual particles were more densely packed in a given volume (the shorter mean free path). When the size of the detection window was small, the number of photons reaching the detector decreased as the photon distribution was larger. Meanwhile, a large-window detector was able to collect the widely distributed Raman photons more effectively; therefore, the trends of intensity change with the variation in particle size were dissimilar depending on the employed spectral acquisition schemes. Overall, the Monte Carlo simulation was effective at probing the photon distribution inside the samples and helped to support the experimental observations.

Comparing dried and liquid blood serum samples of depressed patients: An analysis by Raman and infrared spectroscopy methods.

PubMed

Depciuch, J; Parlinska-Wojtan, M

2018-02-20

Depression is a serious mental illness. To study the mechanism of depression and search for new, more effective therapies, animal models are often used. Unfortunately, none of the available models reflects all the symptoms of depression. Therefore researchers are looking for new tools to diagnose depression. Unfortunately, the nowadays-available depression diagnosis methods are only psychological tests. However, it is known, that the amount of phospholipids, proteins and lipids decreases during depression. Raman and FTIR (Fourier Transform Infra Red) spectroscopies provide information on the chemical compounds in the measured sample e.g. blood serum. These spectroscopic techniques may thus become reliable and accurate tools for evaluating changes in the amount of phospholipids and proteins in depression disease. In this study differences between dried and liquid blood serum samples of healthy and depressed individuals measured by Raman (range 0-3000cm -1 ) and FTIR (Fourier Transform Infrared) (range 900-3000cm -1 ) spectroscopy were evaluated. The resulting spectra and accurate analysis led to the conclusion that an appropriate measurement of the background and the elimination of peaks from water had the greatest impact on the reliability of the results. Furthermore, after detailed studies of FTIR and Raman spectra of dried and liquid blood serum samples, including a complete analysis of peaks after Kramers-Kröning (KK) transformation, it was found that the sample preparation did not affect the results obtained by Raman spectroscopy. In FTIR measurements only a minimal effect on peak intensity was observed. Copyright © 2017 Elsevier B.V. All rights reserved.

Raman study of the shear elastic modulus of iron and iron-nickel alloys at varying P-T conditions: implication for the iron core conditions

NASA Astrophysics Data System (ADS)

Goncharov, A.; Struzhkin, V.

2003-04-01

The knowledge of high-pressure properties of iron and iron-rich alloys are crucial for understanding of the Earth interior, because iron is the major constitute element of the Earth core. Raman spectroscopy has been used recently [1,2] for the shear elastic modulus C44 determination in Fe at compression levels approaching the core boundary. We studied iron-rich alloys of Ni (0 to 20 % Ni) up to 150 GPa, and also at varying temperatures (78-400 K). We find substantial decrease of the Raman hcp-phonon frequency compared to the pure iron, and also considerable anharmonic temperature effects. We argue that the strong anharmonicity of the E2g mode the vicinity of α to ɛ transition can be one of the reasons of the discrepancy between theoretical [3,4] and experimental Raman frequencies and the shear elastic modulus C44. Theoretical calculations do not take into the account the anharmonic effects explicitly, so that the calculated Raman frequency is higher than the experimental one, which is strongly renormalized as a consequence of a Fermi damping. The E2g mode becomes less anharmonic at high pressures (>80 GPa), and theory and experiment are indeed in a much better agreement. [1] S. Merkel et al., Science 288, 1626 (2000). [2] H. Olijnyk, A.P. Jephcoat, K. Refson, Europhys. Lett. 53, 504 (2001). [3] G. Steinle-Neumann, L. Stixrude, and R.E. Cohen, Phys. Rev. B 60, 791 (1999). [4] L. Vocadlo, personal communication.

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.

Conversion of ultrashort laser pulses to wavelengths above 3 mm in tapered germanate fibres

NASA Astrophysics Data System (ADS)

Anashkina, E. A.; Andrianov, A. V.; Kim, A. V.

2015-05-01

Tapered germanate fibres are proposed for effective adiabatic conversion of Raman soliton pulses to the mid-IR region. A theoretical analysis demonstrates that, in fibres with anomalous group velocity dispersion decreasing along their length, wavelengths of up to 3.5 μm can be reached, which are unattainable in fibres with a constant core diameter at the same parameters of a 2-μm input signal. The analysis relies on a one-way wave equation that takes into account the combined effect of dispersion, Kerr and Raman nonlinearities, nonlinear dispersion and optical losses and the frequency dependence of the effective fundamental transverse mode size.

Remote Raman Efficiencies and Cross-Sections of Organic and Inorganic Chemicals.

PubMed

Acosta-Maeda, Tayro E; Misra, Anupam K; Porter, John N; Bates, David E; Sharma, Shiv K

2017-05-01

We determined Raman cross-sections of various organic liquids and inorganic polyatomic ions in aqueous solutions with a 532 nm pulsed laser using remote Raman systems developed at the University of Hawaii. Using a calibrated integrating sphere as a light source, we converted the intensity counts in the spectrum of the light from the integrating sphere measured with UH remote Raman instrument to spectral radiance. From these data, a response function of the remote Raman instrument was obtained. With the intensity-calibrated instrument, we collected remote Raman data from a standard 1 mm path length fused silica spectrophotometer cell filled with cyclohexane. The measured value of the differential Raman cross-section for the 801 cm -1 vibrational mode of cyclohexane is 4.55 × 10 -30 cm 2 sr -1 molecule -1 when excited by a 532 nm laser, in good agreement with the values reported in the literature. Using the measured cyclohexane Raman cross-section as a reference and relative Raman mode intensities of the various ions and organic liquids, we calculated the Raman cross-sections of the strongest Raman lines of nitrate, sulfate, carbonate, phosphate ions, and organic liquids by maintaining same experimental conditions for remote Raman detection. These relative Raman cross-section values will be useful for estimating detection capabilities of remote Raman systems for planetary exploration.

Raman spectroscopic study of synthetic pyrope-grossular garnets: structural implications

NASA Astrophysics Data System (ADS)

Du, Wei; Han, Baofu; Clark, Simon Martin; Wang, Yichuan; Liu, Xi

2018-02-01

A study of the effect of substitution of Mg and Ca in garnet solid solution (Grtss) was carried out using Raman spectroscopy to probe changes to the crystal lattice. The garnet solid solutions with composition changing along pyrope (Py; Mg3Al2Si3O12) and grossular (Gr; Ca3Al2Si3O12) binary were synthesized from glass at 6 GPa and 1400 °C and a second series of Grtss with composition Py40Gr60 were synthesized at 6 GPa but different temperatures from 1000 to 1400 °C. Raman mode assignments were made based on a comparison with the two end members pyrope and grossular, which show consistent result with literature study on single crystals data. The correlation between the Raman mode frequencies and compositional changes along the pyrope-grossular binary suggests a two-mode behavior for Mg and Ca cations in the garnet structure. The full widths at half-maximum of selected Raman modes increase on moving away from the end members and are about double the end-member values in the mid-position, where the frequencies closely linearly change with composition. The frequencies of the translational modes of the SiO4 tetrahedron (T(SiO4)) show large deviations from linearity indicating a strong kinematic coupling with the translational modes of the Ca and Mg cations. The anomalies in T(SiO4) are linked to mixing unit cell volume, suggesting that the nonlinear mixing volume behavior along the pyrope-grossular binary is related to the resistance of the Si-O bond to expansion and compression, which is caused by substitution of Mg and Ca cations in the dodecahedral sites. Annealing temperature also shows effect on Raman mode frequencies, but the main factor controlling the changes in mode frequencies along pyrope-grossular binary is composition.

Carotene location in processed food samples measured by cryo In-SEM Raman.

PubMed

Lopez-Sanchez, Patricia; Schumm, Stephan; Pudney, Paul D A; Hazekamp, Johan

2011-09-21

Cryo In-SEM Raman has been used for the first time to localise carotene compounds in a food matrix. Raman spectra of lycopene and β-carotene have been obtained from sampling oil droplets and plant cell structures visualised with cryo-SEM in tomato and carrot based emulsions containing 5% oil. It was possible to identify the carotenoids in both the oil droplets and the cell walls. Furthermore our results gave some indication that the carotenoids were in the non-crystalline state. It has been suggested that a higher amount of carotenes solubilised into the oil phase of the food matrix would lead to a higher bioaccessibility, thus understanding the effect of processing conditions on micronutrients distribution in a food matrix might help the design of plant based food products with a better nutritional quality. This shows improved structural characterisation of the cryo-SEM with the molecular sensitivity of Raman spectroscopy as a promising approach for complex biological problems.

SERS and DFT study of p-hydroxybenzoic acid adsorbed on colloidal silver particles.

PubMed

Chen, Y; Chen, S J; Li, S; Wei, J J

2015-10-16

In this study, normal Raman spectra of p—hydroxybenzoic acid (PHBA) powder and its surface—enhanced Raman scattering (SERS) spectra in silver colloidal solutions were measured under near infrared excitation conditions. In theoretical calculation, two models of PHBA adsorbed on the surfaces of silver nanoparticles were established. The Raman frequencies of these two models using density functional theory (DFT) method were calculated, and compared with the experimental results. It was found that the calculated Raman frequencies were in good agreement with experimental values, which indicates that there are two enhanced mechanism physical (electromagnetic, EM) enhancement and chemical (charge—transfer, CT) enhancement, in silver colloidal solutions regarding SERS effect. Furthermore, from high—quality SERS spectrum of PHBA obtained in silver colloids, we inferred that PHBA molecules in silver colloids adsorb onto the metal surfaces through carboxyl at a perpendicular orientation. The combination of SERS spectra and DFT calculation is thus useful for studies of the adsorption—orientation of a molecule on a metal colloid.

Experimental Detection of the Intrinsic Difference in Raman Optical Activity of a Photoreceptor Protein under Preresonance and Resonance Conditions.

PubMed

Haraguchi, Shojiro; Hara, Miwa; Shingae, Takahito; Kumauchi, Masato; Hoff, Wouter D; Unno, Masashi

2015-09-21

Raman optical activity (ROA) is an advanced technique capable of detecting structural deformations of light-absorbing molecules embedded in chromophoric proteins. Resonance Raman (RR) spectroscopy is widely used to enhance the band intensities. However, theoretical work has predicted that under resonance conditions the ROA spectrum resembles the shape of the RR spectrum. Herein, we use photoactive yellow protein (PYP) to measure the first experimental data on the effect of changing the excitation wavelength on the ROA spectra of a protein. We observe a close similarity between the shape of the RR spectrum and the resonance ROA spectrum of PYP. Furthermore, we experimentally verify the theoretical prediction concerning the ratio of the amplitudes of the ROA and Raman spectra. Our data demonstrate that selecting an appropriate excitation wavelength is a key factor for extracting structural information on a protein active site using ROA spectroscopy. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Quantitative tradeoffs between spatial, temporal, and thermometric resolution of nonresonant Raman thermometry for dynamic experiments.

PubMed

McGrane, Shawn D; Moore, David S; Goodwin, Peter M; Dattelbaum, Dana M

2014-01-01

The ratio of Stokes to anti-Stokes nonresonant spontaneous Raman can provide an in situ thermometer that is noncontact, independent of any material specific parameters or calibrations, can be multiplexed spatially with line imaging, and can be time resolved for dynamic measurements. However, spontaneous Raman cross sections are very small, and thermometric measurements are often limited by the amount of laser energy that can be applied without damaging the sample or changing its temperature appreciably. In this paper, we quantitatively detail the tradeoff space between spatial, temporal, and thermometric accuracy measurable with spontaneous Raman. Theoretical estimates are pinned to experimental measurements to form realistic expectations of the resolution tradeoffs appropriate to various experiments. We consider the effects of signal to noise, collection efficiency, laser heating, pulsed laser ablation, and blackbody emission as limiting factors, provide formulae to help choose optimal conditions and provide estimates relevant to planning experiments along with concrete examples for single-shot measurements.

Optical properties of nucleobase thin films as studied by attenuated total reflection and surface-enhanced Raman spectroscopy

NASA Astrophysics Data System (ADS)

Kim, MinSuk; Ham, Won Kyu; Kim, Wonyoung; Hwangbo, Chang Kwon; Choi, Eun Ha; Lee, Geon Joon

2018-04-01

Optical properties of nucleobase thin films were studied by attenuated total reflection (ATR) and surface-enhanced Raman spectroscopy (SERS). Adenine and guanine films were deposited on fused silica and silver at room temperature by thermal evaporation, and the normal dispersion of refractive indices of transparent adenine and guanine films in the visible and near-infrared regions were analyzed. The measured ATR spectra of adenine (guanine) films and numerical simulations by optical transfer matrix formalism demonstrate that the shift of surface plasmon resonance (SPR) wavelength is approximately linearly proportional to the adenine (guanine) film thickness, indicating that SPR can be used for quantitative measurements of biomaterials. The Raman spectra indicated that the adenine (guanine) films can be deposited by thermal evaporation. The adenine (guanine) films on silver exhibited Raman intensity enhancement as compared to those on glass, which was attributed to the SPR effect of silver platform and might play a role as a hot plate for SERS detection of biomaterials.

A rapid detection method of Escherichia coli by surface enhanced Raman scattering

NASA Astrophysics Data System (ADS)

Tao, Feifei; Peng, Yankun; Xu, Tianfeng

2015-05-01

Conventional microbiological detection and enumeration methods are time-consuming, labor-intensive, and giving retrospective information. The objectives of the present work are to study the capability of surface enhanced Raman scattering (SERS) to detect Escherichia coli (E. coli) using the presented silver colloidal substrate. The obtained results showed that the adaptive iteratively reweighed Penalized Least Squares (airPLS) algorithm could effectively remove the fluorescent background from original Raman spectra, and Raman characteristic peaks of 558, 682, 726, 1128, 1210 and 1328 cm-1 could be observed stably in the baseline corrected SERS spectra of all studied bacterial concentrations. The detection limit of SERS could be determined to be as low as 0.73 log CFU/ml for E. coli with the prepared silver colloidal substrate. The quantitative prediction results using the intensity values of characteristic peaks were not good, with the correlation coefficients of calibration set and cross validation set of 0.99 and 0.64, respectively.

Analysis of Raman lasing without inversion

NASA Astrophysics Data System (ADS)

Sheldon, Paul Martin

1999-12-01

Properties of lasing without inversion were studied analytically and numerically using Maple computer assisted algebra software. Gain for probe electromagnetic field without population inversion in detuned three level atomic schemes has been found. Matter density matrix dynamics and coherence is explored using Pauli matrices in 2-level systems and Gell-Mann matrices in 3-level systems. It is shown that extreme inversion produces no coherence and hence no lasing. Unitary transformation from the strict field-matter Hamiltonian to an effective two-photon Raman Hamiltonian for multilevel systems has been derived. Feynman diagrams inherent in the derivation show interesting physics. An additional picture change was achieved and showed cw gain possible. Properties of a Raman-like laser based on injection of 3- level coherently driven Λ-type atoms whose Hamiltonian contains the Raman Hamiltonian and microwave coupling the two bottom states have been studied in the limits of small and big photon numbers in the drive field. Another picture change removed the microwave coupler to all orders and simplified analysis. New possibilities of inversionless generation were found.

The spectroscopic (FT-IR, FT-Raman and 1H, 13C NMR) and theoretical studies of cinnamic acid and alkali metal cinnamates

NASA Astrophysics Data System (ADS)

Kalinowska, Monika; Świsłocka, Renata; Lewandowski, Włodzimierz

2007-05-01

The effect of alkali metals (Li → Na → K → Rb → Cs) on the electronic structure of cinnamic acid (phenylacrylic acid) was studied. In this research many miscellaneous analytical methods, which complement one another, were used: infrared (FT-IR), Raman (FT-Raman), nuclear magnetic resonance ( 1H, 13C NMR) and quantum mechanical calculations. The spectroscopic studies lead to conclusions concerning the distribution of the electronic charge in molecule, the delocalization energy of π-electrons and the reactivity of metal complexes. The change of metal along with the series: Li → Na → K → Rb → Cs caused: (1) the change of electronic charge distribution in cinnamate anion what is seen via the occurrence of the systematic shifts of several bands in the experimental and theoretical IR and Raman spectra of cinnamates, (2) systematic chemical shifts for protons 1H and 13C nuclei.

Raman spectroscopy of apatite irradiated with swift heavy ions with and without simultaneous exertion of high pressure

NASA Astrophysics Data System (ADS)

Liu, J.; Glasmacher, U. A.; Lang, M.; Trautmann, C.; Voss, K.-O.; Neumann, R.; Wagner, G. A.; Miletich, R.

2008-04-01

Durango apatite was irradiated with energetic U ions of 2.64 GeV and Kr ions of 2.1 GeV, with and without simultaneous exposure to a pressure of 10.5 GPa. Analysis by confocal Raman spectroscopy gives evidence of vibrational changes being marginal for fluences below 5×1011 ions/cm2 but becoming dominant when increasing the fluence to 8×1012 ions/cm2. Samples irradiated with U ions experience severe strain resulting in crystal cracking and finally breakage at high fluences. These radiation effects are directly linked to the formation of amorphous tracks and the fraction of amorphized material increasing with fluence. Raman spectroscopy of pressurized irradiated samples shows small shifts of the band positions with decreasing pressure but without a significant change of the Grüneisen parameter. Compared to irradiations at ambient conditions, the Raman spectra of apatite irradiated at 10.5 GPa exhibit fewer modifications, suggesting a higher radiation stability of the lattice by the pressure applied.

Raman characterization of a new Te-rich binary compound: CdTe2.

PubMed

Rousset, Jean; Rzepka, Edouard; Lincot, Daniel

2009-04-02

Structural characterization by Raman spectroscopy of CdTe thin films electrodeposited in acidic conditions is considered in this work. This study focuses on the evolution of material properties as a function of the applied potential and the film thickness, demonstrating the possibility to obtain a new Te-rich compound with a II/VI ratio of 1/2 under specific bath conditions. Raman measurements carried out on etched samples first allow the elimination of the assumption of a mixture of phases CdTe + Te and tend to confirm the formation of the CdTe(2) binary compound. The signature of this phase on the Raman spectrum is the increase of the LO band intensity compared to that obtained for the CdTe. The influence of the laser power is also considered. While no effect is observed on CdTe films, the increase of the incident irradiation power leads to the decomposition of the CdTe(2) compound into two more stable phases namely CdTe and Te.

Implementation of an Analytical Raman Scattering Correction for Satellite Ocean-Color Processing

NASA Technical Reports Server (NTRS)

McKinna, Lachlan I. W.; Werdell, P. Jeremy; Proctor, Christopher W.

2016-01-01

Raman scattering of photons by seawater molecules is an inelastic scattering process. This effect can contribute significantly to the water-leaving radiance signal observed by space-borne ocean-color spectroradiometers. If not accounted for during ocean-color processing, Raman scattering can cause biases in derived inherent optical properties (IOPs). Here we describe a Raman scattering correction (RSC) algorithm that has been integrated within NASA's standard ocean-color processing software. We tested the RSC with NASA's Generalized Inherent Optical Properties algorithm (GIOP). A comparison between derived IOPs and in situ data revealed that the magnitude of the derived backscattering coefficient and the phytoplankton absorption coefficient were reduced when the RSC was applied, whilst the absorption coefficient of colored dissolved and detrital matter remained unchanged. Importantly, our results show that the RSC did not degrade the retrieval skill of the GIOP. In addition, a timeseries study of oligotrophic waters near Bermuda showed that the RSC did not introduce unwanted temporal trends or artifacts into derived IOPs.

Application of infrared reflection and Raman spectroscopy for quantitative determination of fat in potato chips

NASA Astrophysics Data System (ADS)

Mazurek, Sylwester; Szostak, Roman; Kita, Agnieszka

2016-12-01

Potato chips are important products in the snack industry. The most significant parameter monitored during their quality control process is fat content. The Soxhlet method, which is applied for this purpose, is time consuming and expensive. We demonstrate that both infrared and Raman spectroscopy can effectively replace the extraction method. Raman, mid-infrared (MIR) and near-infrared (NIR) spectra of the homogenised laboratory-prepared chips were recorded. On the basis of obtained spectra, partial least squares (PLS) calibration models were constructed. They were characterised by the values of relative standard errors of prediction (RSEP) in the 1.0-1.9% range for both calibration and validation data sets. Using the developed models, six commercial products were successfully quantified with recovery in the 98.5-102.3% range against the AOAC extraction method. The proposed method for fat quantification in potato chips based on Raman spectroscopy can be easily adopted for on-line product analysis.

Forensic identification of blood in the presence of contaminations using Raman microspectroscopy coupled with advanced statistics: effect of sand, dust, and soil.

PubMed

Sikirzhytskaya, Aliaksandra; Sikirzhytski, Vitali; McLaughlin, Gregory; Lednev, Igor K

2013-09-01

Body fluid traces recovered at crime scenes are among the most common and important types of forensic evidence. However, the ability to characterize a biological stain at a crime scene nondestructively has not yet been demonstrated. Here, we expand the Raman spectroscopic approach for the identification of dry traces of pure body fluids to address the problem of heterogeneous contamination, which can impair the performance of conventional methods. The concept of multidimensional Raman signatures was utilized for the identification of blood in dry traces contaminated with sand, dust, and soil. Multiple Raman spectra were acquired from the samples via automatic scanning, and the contribution of blood was evaluated through the fitting quality using spectroscopic signature components. The spatial mapping technique allowed for detection of "hot spots" dominated by blood contribution. The proposed method has great potential for blood identification in highly contaminated samples. © 2013 American Academy of Forensic Sciences.

Raman scattering and attenuated-total-reflection studies of surface-plasmon polaritons

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

Kurosawa, K.; Pierce, R.M.; Ushioda, S.

1986-01-15

We have made in situ measurements of attenuated total reflection (ATR) and Raman scattering from a layered structure consisting of a glass prism, a thin silver film, an MgF2 spacer, and a liquid mixture whose refractive index is matched to that of MgF2. When the incident angle of the laser beam coincides with the ATR angle, the surface-plasmon polariton (SPP) of the silver film is excited resonantly and the Raman scattering intensity of the liquid shows a maximum. The same effect is observed at the frequency of the Stokes scattered light. By measuring the decrease of the Raman scattering intensitymore » of the liquid with increase of the thickness of the MgF2 spacer layer, we have determined the decay length (l/sub d/) of the SPP field into the liquid. The measured value of l/sub d/ = 1539 A agrees with the calculated value, 1534 A.« less

Bacterial detection using bacteriophages and gold nanorods by following time-dependent changes in Raman spectral signals.

PubMed

Moghtader, Farzaneh; Tomak, Aysel; Zareie, Hadi M; Piskin, Erhan

2018-03-27

This study attemps to develop bacterial detection strategies using bacteriophages and gold nanorods (GNRs) by Raman spectral analysis. Escherichia coli was selected as the target and its specific phage was used as the bioprobe. Target bacteria and phages were propagated/purified by traditional techniques. GNRs were synthesized by using hexadecyltrimethyl ammonium bromide (CTAB) as stabilizer. A two-step detection strategy was applied: Firstly, the target bacteria were interacted with GNRs in suspensions, and then they were dropped onto silica substrates for detection. It was possible to obtain clear surface-enchanced Raman spectroscopy (SERS) peaks of the target bacteria, even without using phages. In the second step, the phage nanoemulsions were droped onto the bacterial-GNRs complexes on those surfaces and time-dependent changes in the Raman spectra were monitored at different time intervals upto 40 min. These results demonstrated that how one can apply phages with plasmonic nanoparticles for detection of pathogenic bacteria very effectively in a quite simple test.

Raman-based system for DNA sequencing-mapping and other separations

DOEpatents

Vo-Dinh, T.

1994-04-26

DNA sequencing and mapping are performed by using a Raman spectrometer with a surface enhanced Raman scattering (SERS) substrate to enhance the Raman signal. A SERS label is attached to a DNA fragment and then analyzed with the Raman spectrometer to identify the DNA fragment according to characteristics of the Raman spectrum generated. 11 figures.

Classification and Visualization of Physical and Chemical Properties of Falsified Medicines with Handheld Raman Spectroscopy and X-Ray Computed Tomography.

PubMed

Kakio, Tomoko; Yoshida, Naoko; Macha, Susan; Moriguchi, Kazunobu; Hiroshima, Takashi; Ikeda, Yukihiro; Tsuboi, Hirohito; Kimura, Kazuko

2017-09-01

Analytical methods for the detection of substandard and falsified medical products (SFs) are important for public health and patient safety. Research to understand how the physical and chemical properties of SFs can be most effectively applied to distinguish the SFs from authentic products has not yet been investigated enough. Here, we investigated the usefulness of two analytical methods, handheld Raman spectroscopy (handheld Raman) and X-ray computed tomography (X-ray CT), for detecting SFs among oral solid antihypertensive pharmaceutical products containing candesartan cilexetil as an active pharmaceutical ingredient (API). X-ray CT visualized at least two different types of falsified tablets, one containing many cracks and voids and the other containing aggregates with high electron density, such as from the presence of the heavy elements. Generic products that purported to contain equivalent amounts of API to the authentic products were discriminated from the authentic products by the handheld Raman and the different physical structure on X-ray CT. Approach to investigate both the chemical and physical properties with handheld Raman and X-ray CT, respectively, promise the accurate discrimination of the SFs, even if their visual appearance is similar with authentic products. We present a decision tree for investigating the authenticity of samples purporting to be authentic commercial tablets. Our results indicate that the combination approach of visual observation, handheld Raman and X-ray CT is a powerful strategy for nondestructive discrimination of suspect samples.