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Sample records for in-situ raman imaging

  1. Image-guided Raman spectroscopic recovery of canine cortical bone contrast in situ

    PubMed Central

    Srinivasan, Subhadra; Schulmerich, Matthew; Cole, Jacqueline H.; Dooley, Kathryn A.; Kreider, Jaclynn M.; Pogue, Brian W.; Morris, Michael D.; Goldstein, Steven A.

    2009-01-01

    Raman scattering provides valuable biochemical and molecular markers for studying bone tissue composition with use in predicting fracture risk in osteoporosis. Raman tomography can image through a few centimeters of tissue but is limited by low spatial resolution. X-ray computed tomography (CT) imaging can provide high-resolution image-guidance of the Raman spectroscopic characterization, which enhances the quantitative recovery of the Raman signals, and this technique provides additional information to standard imaging methods. This hypothesis was tested in data measured from Teflon® tissue phantoms and from a canine limb. Image-guided Raman spectroscopy (IG-RS) of the canine limb using CT images of the tissue to guide the recovery recovered a contrast of 145:1 between the cortical bone and background. Considerably less contrast was found without the CT image to guide recovery. This study presents the first known IG-RS results from tissue and indicates that intrinsically high contrasts (on the order of a hundred fold) are available. PMID:18679495

  2. Raman Imaging

    NASA Astrophysics Data System (ADS)

    Stewart, Shona; Priore, Ryan J.; Nelson, Matthew P.; Treado, Patrick J.

    2012-07-01

    The past decade has seen an enormous increase in the number and breadth of imaging techniques developed for analysis in many industries, including pharmaceuticals, food, and especially biomedicine. Rather than accept single-dimensional forms of information, users now demand multidimensional assessment of samples. High specificity and the need for little or no sample preparation make Raman imaging a highly attractive analytical technique and provide motivation for continuing advances in its supporting technology and utilization. This review discusses the current tools employed in Raman imaging, the recent advances, and the major applications in this ever-growing analytical field.

  3. Raman imaging of extraterrestrial materials

    NASA Astrophysics Data System (ADS)

    Wang, Alian; Korotev, Randy L.; Jolliff, Bradley L.; Ling, Zongcheng

    2015-07-01

    Laser Raman Spectroscopy has been proposed and is under extensive development for surface exploration missions to planetary bodies of our Solar System. It reveals information on molecular structure and chemistry. The spatial distribution of molecular species in natural geological samples and planetary materials has significance for the geological processes by which they formed. Raman imaging is the best way to combine the molecular identification and characterization of geologic materials with their spatial distribution. This paper reports Raman imaging studies of five types of extraterrestrial materials and three terrestrial samples using a state-of-the-art Raman imaging system. The Raman spectral features of major, minor, and trace species in these samples, together with their spatial correlations revealed by these Raman imaging studies indicate the genetic relationships and the geological processes that these materials have been experienced. For robotic planetary surface exploration mission, a simple yet very useful molecular map of a sample can be generated by using line-scan or grid-scan of an in situ Raman system with tightly focused laser beam.

  4. Time-resolved Raman spectroscopy for in situ planetary mineralogy.

    PubMed

    Blacksberg, Jordana; Rossman, George R; Gleckler, Anthony

    2010-09-10

    Planetary mineralogy can be revealed through a variety of remote sensing and in situ investigations that precede any plans for eventual sample return. We briefly review those techniques and focus on the capabilities for on-surface in situ examination of Mars, Venus, the Moon, asteroids, and other bodies. Over the past decade, Raman spectroscopy has continued to develop as a prime candidate for the next generation of in situ planetary instruments, as it provides definitive structural and compositional information of minerals in their natural geological context. Traditional continuous-wave Raman spectroscopy using a green laser suffers from fluorescence interference, which can be large (sometimes saturating the detector), particularly in altered minerals, which are of the greatest geophysical interest. Taking advantage of the fact that fluorescence occurs at a later time than the instantaneous Raman signal, we have developed a time-resolved Raman spectrometer that uses a streak camera and pulsed miniature microchip laser to provide picosecond time resolution. Our ability to observe the complete time evolution of Raman and fluorescence spectra in minerals makes this technique ideal for exploration of diverse planetary environments, some of which are expected to contain strong, if not overwhelming, fluorescence signatures. We discuss performance capability and present time-resolved pulsed Raman spectra collected from several highly fluorescent and Mars-relevant minerals. In particular, we have found that conventional Raman spectra from fine grained clays, sulfates, and phosphates exhibited large fluorescent signatures, but high quality spectra could be obtained using our time-resolved approach.

  5. Imaging with Raman spectroscopy.

    PubMed

    Zhang, Yin; Hong, Hao; Cai, Weibo

    2010-09-01

    Raman spectroscopy, based on the inelastic scattering of a photon, has been widely used as an analytical tool in many research fields. Recently, Raman spectroscopy has also been explored for biomedical applications (e.g. cancer diagnosis) because it can provide detailed information on the chemical composition of cells and tissues. For imaging applications, several variations of Raman spectroscopy have been developed to enhance its sensitivity. This review article will provide a brief summary of Raman spectroscopy-based imaging, which includes the use of coherent anti-Stokes Raman spectroscopy (CARS, primarily used for imaging the C-H bond in lipids), surface-enhanced Raman spectroscopy (SERS, for which a variety of nanoparticles can be used as contrast agents), and single-walled carbon nanotubes (SWNTs, with its intrinsic Raman signal). The superb multiplexing capability of SERS-based Raman imaging can be extremely powerful in future research where different agents can be attached to different Raman tags to enable the interrogation of multiple biological events simultaneously in living subjects. The primary limitations of Raman imaging in humans are those also faced by other optical techniques, in particular limited tissue penetration. Over the last several years, Raman spectroscopy imaging has advanced significantly and many critical proof-of-principle experiments have been successfully carried out. It is expected that imaging with Raman Spectroscopy will continue to be a dynamic research field over the next decade.

  6. Raman spectroscopy for in-situ monitoring of electrode processes

    SciTech Connect

    Varma, R; Cook, G M; Yao, N P

    1982-04-01

    The theoretical and experimental applications of Raman spectroscopic techniques to the study of battery electrode processes are described. In particular, the potential of Raman spectroscopy as an in-situ analytical tool for the characterization of the structure and composition of electrode surface layers at electrode-electrolyte interfaces during electrolysis is examined. It is anticipated that this understanding of the battery electrode processes will be helpful in designing battery active material with improved performance. The applications of Raman spectroscopy to the in-situ study of electrode processes has been demonstrated in a few selected areas, including: (1) the anodic corrosion of lead in sulfuric acid and (2) the anodization and sulfation of tetrabasicleadsulfate in sulfuric acid. Preliminary results on the anodization of iron and on the electrochemical behavior of nickel positive-electrode active material in potassium hydroxide electrolytes are presented in the Appendix.

  7. The use of in situ near infrared imaging and Raman mapping to study the disproportionation of a drug HCl salt during dissolution.

    PubMed

    Wray, Patrick S; Sinclair, Wayne E; Jones, John W; Clarke, Graham S; Both, Douglas

    2015-09-30

    NIR imaging and Raman mapping of the dissolution of model pharmaceutical formulations containing the HCl salt of a developmental compound, were carried out using a custom designed flow through cell. The results of this work have shown that NIR imaging and Raman mapping are capable of monitoring the distribution of the components in a formulation during dissolution while also revealing any form changes which may occur in real time. The NIR and Raman data revealed that the drug underwent conversion to the free base when water was used as the dissolution medium. However, in 0.1M HCl this conversion was no longer seen as the medium was below the pHmax (the pH of saturation of both unionised and ionised species and above which the free base can form) of the drug. The data from both approaches broadly agreed demonstrating the applicability of these methods to studying and enhancing our understanding of the complex physical and chemical processes which occur during dissolution in real time.

  8. In Situ Detection of Antibiotic Amphotericin B Produced in Streptomyces nodosus Using Raman Microspectroscopy

    PubMed Central

    Miyaoka, Rimi; Hosokawa, Masahito; Ando, Masahiro; Mori, Tetsushi; Hamaguchi, Hiro-o; Takeyama, Haruko

    2014-01-01

    The study of spatial distribution of secondary metabolites within microbial cells facilitates the screening of candidate strains from marine environments for functional metabolites and allows for the subsequent assessment of the production of metabolites, such as antibiotics. This paper demonstrates the first application of Raman microspectroscopy for in situ detection of the antifungal antibiotic amphotericin B (AmB) produced by actinomycetes—Streptomyces nodosus. Raman spectra measured from hyphae of S. nodosus show the specific Raman bands, caused by resonance enhancement, corresponding to the polyene chain of AmB. In addition, Raman microspectroscopy enabled us to monitor the time-dependent change of AmB production corresponding to the growth of mycelia. The Raman images of S. nodosus reveal the heterogeneous distribution of AmB within the mycelia and individual hyphae. Moreover, the molecular association state of AmB in the mycelia was directly identified by observed Raman spectral shifts. These findings suggest that Raman microspectroscopy could be used for in situ monitoring of antibiotic production directly in marine microorganisms with a method that is non-destructive and does not require labeling. PMID:24828290

  9. Analysis of Surface Leaching Processes in Vitrified High-Level Nuclear Wastes Using In-Situ Raman Imaging and Atomistic Modeling - Final Report

    SciTech Connect

    Simmons, Joseph H.

    2001-04-24

    The in situ analysis of surface conditions of vitrified nuclear wastes can provide an important check of the burial status of radioactive objects without risk of radiation exposure. Raman spectroscopy was initially chosen as the most promising method for testing the surface conditions of glasses undergoing chemical corrosion, and was used extensively during the first year. However, it was determined that infrared reflection spectroscopy was better suited to this particular need and was used for the remaining two years to investigate the surface corrosion behavior of model silicate glasses for extension to nuclear waste glasses. The developed methodology is consistent with the known theory of optical propagation of dielectric media and uses the Kramers-Kronig formalism. The results show that it is possible to study the corrosion of glass by analyzing the glass surface using reflection fast Fourier infrared measurements and the newly developed ''dispersion analysis method.'' The data show how this analysis can be used to monitor the corrosion behavior of vitrified waste glasses over extended periods of storage.

  10. Water monitoring by optofluidic Raman spectroscopy for in situ applications.

    PubMed

    Persichetti, Gianluca; Bernini, Romeo

    2016-08-01

    The feasibility of water monitoring by Raman spectroscopy with a portable optofluidic system for in-situ applications has been successfully demonstrated. In the proposed approach, the sample under analysis is injected into a capillary nozzle in order to produce a liquid jet that acts as an optical waveguide. This jet waveguide provides an effective strategy to excite and collect the Raman signals arising from water contaminants due to the high refractive index difference between air and water. The proposed approach avoids any necessity of liquid container or flow cell and removes any background signal coming from the sample container commonly affects Raman measurements. Furthermore, this absence is a significant advantage for in situ measurements where fouling problems can be relevant and cleaning procedures are troublesome. The extreme simplicity and efficiency of the optical scheme adopted in our approach result in highly sensitive and rapid measurements that have been performed on different representative water pollutants. The experimental results demonstrate the high potentiality of our device in water quality monitoring and analysis. In particular, nitrate and sulfate are detected below the maximum contamination level allowed for drinking water, whereas a limit of detection of 40mg/l has been found for benzene. PMID:27216667

  11. Water monitoring by optofluidic Raman spectroscopy for in situ applications.

    PubMed

    Persichetti, Gianluca; Bernini, Romeo

    2016-08-01

    The feasibility of water monitoring by Raman spectroscopy with a portable optofluidic system for in-situ applications has been successfully demonstrated. In the proposed approach, the sample under analysis is injected into a capillary nozzle in order to produce a liquid jet that acts as an optical waveguide. This jet waveguide provides an effective strategy to excite and collect the Raman signals arising from water contaminants due to the high refractive index difference between air and water. The proposed approach avoids any necessity of liquid container or flow cell and removes any background signal coming from the sample container commonly affects Raman measurements. Furthermore, this absence is a significant advantage for in situ measurements where fouling problems can be relevant and cleaning procedures are troublesome. The extreme simplicity and efficiency of the optical scheme adopted in our approach result in highly sensitive and rapid measurements that have been performed on different representative water pollutants. The experimental results demonstrate the high potentiality of our device in water quality monitoring and analysis. In particular, nitrate and sulfate are detected below the maximum contamination level allowed for drinking water, whereas a limit of detection of 40mg/l has been found for benzene.

  12. In situ Raman spectroscopy study of oxidation of nanostructured carbons

    NASA Astrophysics Data System (ADS)

    Osswald, Sebastian

    The ability to synthesize carbon nanostructures, such as fullerenes, carbon nanotubes, nanodiamond, and mesoporous carbon; functionalize their surface; or assemble them into three-dimensional networks has opened new avenues for material design. Carbon nanostructures possess tunable optical, electrical or mechanical properties, making them ideal candidates for numerous applications ranging from composite structures and chemical sensors to electronic devices and medical implants. Unfortunately, current synthesis techniques typically lead to a mixture of different types of carbon rather than a particular nanostructure with defined size and properties. In order to fully exploit the great potential of carbon nanostructures, one needs to provide purification procedures that allow a selective separation of carbon nanostructures, and methods which enable a control of size and surface functionalization. Oxidation is a frequently used method for purification of carbon materials, but it can also damage or destroy the sample. In situ Raman spectroscopy during heating in a controlled environment allows a time-resolved investigation of the oxidation kinetics and can identify the changes in material structure and composition, thus helping to accurately determine optimal purification conditions. However, while carbon allotropes such as graphite and diamond show unique Raman signals and allow a fast and straightforward identification, the interpretation of Raman spectra recorded from nanostructures containing mixtures of sp, sp2 and sp3 bonded carbon is more complex and the origin of some peaks in Raman spectra of nanocarbons is not yet fully understood. In this study we applied in situ Raman spectroscopy to determine conditions for selective oxidation of carbon nanostructures, such as nanodiamond, nanotubes, carbide-derived carbon and carbon onions; accurately measure and control the crystal size; and improve the fundamental understanding of effects of temperature, quantum

  13. In situ solution-phase Raman spectroscopy under forced convection.

    PubMed

    Zhu, Huanfeng; Wu, Jun; Shi, Qingfang; Wang, Zhenghao; Scherson, Daniel A

    2007-11-01

    In situ Raman spectra of solution-phase electrogenerated species have been recorded in a channel-type electrochemical cell incorporating a flat optically transparent window placed parallel to the channel plane that contains the embedded working electrode. A microscope objective with its main axis (Z) aligned normal to the direction of flow was used to focus the excitation laser beam (lambda exc = 532 nm) in the solution and also to collect the Raman scattered light from species present therein. Judicious adjustment of the cell position along Z allowed the depth of focus to overlap the diffusion boundary layer to achieve maximum detection sensitivity. Measurements were performed using a Au working electrode in iron hexacyanoferrate(II), [Fe(CN)6]4-, and nitrite, NO2-, containing aqueous solutions as a function of the applied potential, E. Linear correlations were found between both the gain and the loss of the integrated Raman intensity, IR, of bands, attributed to [Fe(CN)6]3- and [Fe(CN)6]4-, respectively, recorded downstream from the edge of the working electrode, and the current measured at the Au electrode as a function of E. The same overall trend was found for the gain in the IR of the NO3- band in the nitrite solution. Also included in this work is a ray trace analysis of the optical system.

  14. Stimulated Raman photoacoustic imaging

    PubMed Central

    Yakovlev, Vladislav V.; Zhang, Hao F.; Noojin, Gary D.; Denton, Michael L.; Thomas, Robert J.; Scully, Marlan O.

    2010-01-01

    Achieving label-free, molecular-specific imaging with high spatial resolution in deep tissue is often considered the grand challenge of optical imaging. To accomplish this goal, significant optical scattering in tissues has to be overcome while achieving molecular specificity without resorting to extrinsic labeling. We demonstrate the feasibility of developing such an optical imaging modality by combining the molecularly specific stimulated Raman excitation with the photoacoustic detection. By employing two ultrashort excitation laser pulses, separated in frequency by the vibrational frequency of a targeted molecule, only the specific vibrational level of the target molecules in the illuminated tissue volume is excited. This targeted optical absorption generates ultrasonic waves (referred to as stimulated Raman photoacoustic waves) which are detected using a traditional ultrasonic transducer to form an image following the design of the established photoacoustic microscopy. PMID:21059930

  15. In situ dissolution analysis using coherent anti-Stokes Raman scattering (CARS) and hyperspectral CARS microscopy.

    PubMed

    Fussell, Andrew; Garbacik, Erik; Offerhaus, Herman; Kleinebudde, Peter; Strachan, Clare

    2013-11-01

    The solid-state form of an active pharmaceutical ingredient (API) in an oral dosage form plays an important role in determining the dissolution rate of the API. As the solid-state form can change during dissolution, there is a need to monitor the oral dosage form during dissolution testing. Coherent anti-Stokes Raman scattering (CARS) microscopy provides rapid, spectrally selective imaging to monitor the oral dosage form during dissolution. In this study, in situ CARS microscopy was combined with inline UV absorption spectroscopy to monitor the solid-state change in oral dosage forms containing theophylline anhydrate undergoing dissolution and to correlate the solid-state change with a change in dissolution rate. The results from in situ CARS microscopy showed that theophylline anhydrate converted to theophylline monohydrate during dissolution resulting in a reduction in the dissolution rate. The addition of methyl cellulose to the dissolution medium was found to delay the theophylline monohydrate growth and changed the morphology of the monohydrate. The net effect was an increased dissolution rate for theophylline anhydrate. Our results show that in situ CARS microscopy combined with inline UV absorption spectroscopy is capable of monitoring oral dosage forms undergoing dissolution and correlating changes in solid-state form with changes in dissolution rate. PMID:23994672

  16. Waterproofing in Arabidopsis: Following phenolics and lipids in situ by Confocal Raman Microscopy

    NASA Astrophysics Data System (ADS)

    Prats Mateu, Batirtze; Hauser, Marie-Theres; Heredia, Antonio; Gierlinger, Notburga

    2016-02-01

    Waterproofing of the aerial organs of plants imposed a big evolutionary step during the colonization of the terrestrial environment. The main plant polymers responsible of water repelling are lipids and lignin, which play also important roles in the protection against biotic/abiotic stresses, regulation of flux of gases and solutes and mechanical stability against negative pressure, among others. While the lipids, non-polymerized cuticular waxes together with the polymerized cutin, protect the outer surface, lignin is confined to the secondary cell wall within mechanical important tissues. In the present work a micro cross-section of the stem of Arabidopsis thaliana was used to track in situ the distribution of these non-carbohydrate polymers by Confocal Raman Microscopy. Raman hyperspectral imaging gives a molecular fingerprint of the native waterproofing tissues and cells with diffraction limited spatial resolution (~300 nm) at relatively high speed and without any tedious sample preparation. Lipids and lignified tissues as well as their effect on water content was directly visualized by integrating the 1299 cm-1, 1600 cm-1 and 3400 cm-1 band, respectively. For detailed insights into compositional changes of these polymers vertex component analysis was performed on selected sample positions. Changes have been elucidated in the composition of lignin within the lignified tissues and between interfascicular fibers and xylem vessels. Hydrophobising changes were revealed from the epidermal layer to the cuticle as well as a change in the aromatic composition within the cuticle of trichomes. To verify Raman signatures of different waterproofing polymers additionally Raman spectra of the cuticle and cutin monomer from tomato (Solanum lycopersicum) as well as aromatic model polymers (milled wood lignin and dehydrogenation polymer of coniferyl alcohol) and phenolic acids were acquired. Keywords: Arabidopsis thaliana, lignin, cutin, wax, Raman, cuticle, waterproofing

  17. Support Routines for In Situ Image Processing

    NASA Technical Reports Server (NTRS)

    Deen, Robert G.; Pariser, Oleg; Yeates, Matthew C.; Lee, Hyun H.; Lorre, Jean

    2013-01-01

    This software consists of a set of application programs that support ground-based image processing for in situ missions. These programs represent a collection of utility routines that perform miscellaneous functions in the context of the ground data system. Each one fulfills some specific need as determined via operational experience. The most unique aspect to these programs is that they are integrated into the large, in situ image processing system via the PIG (Planetary Image Geometry) library. They work directly with space in situ data, understanding the appropriate image meta-data fields and updating them properly. The programs themselves are completely multimission; all mission dependencies are handled by PIG. This suite of programs consists of: (1)marscahv: Generates a linearized, epi-polar aligned image given a stereo pair of images. These images are optimized for 1-D stereo correlations, (2) marscheckcm: Compares the camera model in an image label with one derived via kinematics modeling on the ground, (3) marschkovl: Checks the overlaps between a list of images in order to determine which might be stereo pairs. This is useful for non-traditional stereo images like long-baseline or those from an articulating arm camera, (4) marscoordtrans: Translates mosaic coordinates from one form into another, (5) marsdispcompare: Checks a Left Right stereo disparity image against a Right Left disparity image to ensure they are consistent with each other, (6) marsdispwarp: Takes one image of a stereo pair and warps it through a disparity map to create a synthetic opposite- eye image. For example, a right eye image could be transformed to look like it was taken from the left eye via this program, (7) marsfidfinder: Finds fiducial markers in an image by projecting their approximate location and then using correlation to locate the markers to subpixel accuracy. These fiducial markets are small targets attached to the spacecraft surface. This helps verify, or improve, the

  18. Waterproofing in Arabidopsis: Following Phenolics and Lipids In situ by Confocal Raman Microscopy.

    PubMed

    Prats Mateu, Batirtze; Hauser, Marie Theres; Heredia, Antonio; Gierlinger, Notburga

    2016-01-01

    Waterproofing of the aerial organs of plants imposed a big evolutionary step during the colonization of the terrestrial environment. The main plant polymers responsible of water repelling are lipids and lignin, which play also important roles in the protection against biotic/abiotic stresses, regulation of flux of gases and solutes, and mechanical stability against negative pressure, among others. While the lipids, non-polymerized cuticular waxes together with the polymerized cutin, protect the outer surface, lignin is confined to the secondary cell wall within mechanical important tissues. In the present work a micro cross-section of the stem of Arabidopsis thaliana was used to track in situ the distribution of these non-carbohydrate polymers by Confocal Raman Microscopy. Raman hyperspectral imaging gives a molecular fingerprint of the native waterproofing tissues and cells with diffraction limited spatial resolution (~300 nm) at relatively high speed and without any tedious sample preparation. Lipids and lignified tissues as well as their effect on water content was directly visualized by integrating the 1299, 1600, and 3400 cm(-1) band, respectively. For detailed insights into compositional changes of these polymers vertex component analysis was performed on selected sample positions. Changes have been elucidated in the composition of lignin within the lignified tissues and between interfascicular fibers and xylem vessels. Hydrophobizing changes were revealed from the epidermal layer to the cuticle as well as a change in the aromatic composition within the cuticle of trichomes. To verify Raman signatures of different waterproofing polymers additionally Raman spectra of the cuticle and cutin monomer from tomato (Solanum lycopersicum) as well as aromatic model polymers (milled wood lignin and dehydrogenation polymer of coniferyl alcohol) and phenolic acids were acquired. PMID:26973831

  19. Waterproofing in Arabidopsis: Following Phenolics and Lipids In situ by Confocal Raman Microscopy

    PubMed Central

    Prats Mateu, Batirtze; Hauser, Marie Theres; Heredia, Antonio; Gierlinger, Notburga

    2016-01-01

    Waterproofing of the aerial organs of plants imposed a big evolutionary step during the colonization of the terrestrial environment. The main plant polymers responsible of water repelling are lipids and lignin, which play also important roles in the protection against biotic/abiotic stresses, regulation of flux of gases and solutes, and mechanical stability against negative pressure, among others. While the lipids, non-polymerized cuticular waxes together with the polymerized cutin, protect the outer surface, lignin is confined to the secondary cell wall within mechanical important tissues. In the present work a micro cross-section of the stem of Arabidopsis thaliana was used to track in situ the distribution of these non-carbohydrate polymers by Confocal Raman Microscopy. Raman hyperspectral imaging gives a molecular fingerprint of the native waterproofing tissues and cells with diffraction limited spatial resolution (~300 nm) at relatively high speed and without any tedious sample preparation. Lipids and lignified tissues as well as their effect on water content was directly visualized by integrating the 1299, 1600, and 3400 cm−1 band, respectively. For detailed insights into compositional changes of these polymers vertex component analysis was performed on selected sample positions. Changes have been elucidated in the composition of lignin within the lignified tissues and between interfascicular fibers and xylem vessels. Hydrophobizing changes were revealed from the epidermal layer to the cuticle as well as a change in the aromatic composition within the cuticle of trichomes. To verify Raman signatures of different waterproofing polymers additionally Raman spectra of the cuticle and cutin monomer from tomato (Solanum lycopersicum) as well as aromatic model polymers (milled wood lignin and dehydrogenation polymer of coniferyl alcohol) and phenolic acids were acquired. PMID:26973831

  20. In situ Raman spectroscopy for growth monitoring of vertically aligned multiwall carbon nanotubes in plasma reactor

    SciTech Connect

    Labbaye, T.; Gaillard, M.; Lecas, T.; Kovacevic, E.; Boulmer-Leborgne, Ch.; Guimbretière, G.; Canizarès, A.; Raimboux, N.; Simon, P.; Ammar, M. R.; Strunskus, T.

    2014-11-24

    Portable and highly sensitive Raman setup was associated with a plasma-enhanced chemical vapor deposition reactor enabling in situ growth monitoring of multi-wall carbon nanotubes despite the combination of huge working distance, high growth speed and process temperature and reactive plasma condition. Near Edge X-ray absorption fine structure spectroscopy was used for ex situ sample analysis as a complementary method to in situ Raman spectroscopy. The results confirmed the fact that the “alternating” method developed here can accurately be used for in situ Raman monitoring under reactive plasma condition. The original analytic tool can be of great importance to monitor the characteristics of these nanostructured materials and readily define the ultimate conditions for targeted results.

  1. Advances in Raman spectroscopy for In Situ Identification of Minerals and Organics on Diverse Planetary Surfaces: from Mars to Titan

    NASA Astrophysics Data System (ADS)

    Blacksberg, J.; Alerstam, E.; Maruyama, Y.; Cochrane, C.; Rossman, G. R.

    2015-12-01

    We present recent developments in time-resolved Raman spectroscopy for in situ planetary surface exploration, aimed at identification of both minerals and organics. Raman is a non-destructive surface technique that requires no sample preparation. Raman spectra are highly material specific and can be used for identification of a wide range of unknown samples. In combination with micro-scale imaging and point mapping, Raman spectroscopy can be used to directly interrogate rocks and regolith materials, while placing compositional analyses within a microtextural context, essential for understanding surface evolutionary pathways. Due to these unique capabilities, Raman spectroscopy is of great interest for the exploration of all rocky and icy bodies, for example Mars, Venus, the Moon, Mars' moons, asteroids, comets, Europa, and Titan. In this work, we focus on overcoming one of the most difficult challenges faced in Raman spectroscopy: interference from background fluorescence of the very minerals and organics that we wish to characterize. To tackle this problem we use time-resolved Raman spectroscopy, which separates the Raman from background processes in the time domain. This same technique also enables operation in daylight without the need for light shielding. Two key components are essential for the success of this technique: a fast solid-state detector and a short-pulse laser. Our detector is a custom developed Single Photon Avalanche Diode (SPAD) array, capable of sub-ns time-gating. Our pulsed lasers are solid-state miniature pulsed microchip lasers. We discuss optimization of laser and detector parameters for our application. We then present Raman spectra of particularly challenging planetary analog samples to demonstrate the unique capabilities of this time-resolved Raman instrument, for example, Mars-analog clays and Titan-analog organics. The research described here was carried out at the Jet Propulsion Laboratory, California Institute of Technology, under a

  2. In situ raman spectral mapping study on the microscale fibers in blue coral (Heliopora coerulea) skeletons.

    PubMed

    Zhang, Fenfen; Cai, Weiying; Zhu, Jichun; Sun, Zhenrong; Zhang, Jing

    2011-10-15

    The presence and localization of organic matrix associated with the aragonite phase in the fibers of blue coral Heliopora coerulea skeletons were studied by in situ microRaman mapping spectra, with a spatial resolution of ~0.3 μm. Spatial variations in the amounts and chemical compositions of the fibers were imaged. The results showed that the amide I and the α-helix of amide III were perpendicular to the c-axis of fibers' growth, whereas the β-turns/sheet of amide III was in the parallel conformation. Visible S-S and C-S bonds were consistent with the XANES results, which indicated the existence of organic sulfur in coral skeletons. Regular cyclic changes between aragonite and organic matrix refined a stepping growth mode of the fibers' biomineralization. An inorganic PO(4) bond was detected and exhibited the same concentration variation trends as the v(4) aragonite bands. Instead of providing an ocean P proxy on the subseasonal to centennial scale by LA-ICPMS, the possibility was raised of producing high resolution surface ocean phosphorus records on daily environmental variation via P/Ca variation cycles determined from Raman mapping data.

  3. Imaging tree root systems in situ

    NASA Astrophysics Data System (ADS)

    Wielopolski, Lucian; Hendrey, George; Daniels, Jeffrey J.; McGuigan, Michael

    2000-04-01

    Predictions of global energy use in this century suggest a continued increase in carbon emissions and rising concentrations of carbon dioxide (CO2) in the atmosphere. This represents a serious environmental problem and contributes significantly to greenhouse gases that affect global warming. Terrestrial ecosystems are a huge natural biological scrubber for CO2 currently sequestering, directly from the atmosphere, about 25% (approximately 2 GtC) of the 7.4 Gt of anthropogenic carbon emitted annually into the atmosphere. The major carbon pathways into soil are through plant litter and roots. Presently, there are no means by which root morphology, distribution, and mass can be measured without serious sampling artifacts that alter these properties. The current methods are destructive and labor intensive. Preliminary results using a high frequency, 1.5 Ghz, impulse Ground Penetrating Radar (GPR) for nondestructive imaging of tree root systems in situ are presented. The 3D reconstructed image is used to assess root morphology and dimensions. The constraints, limitations, and potential solutions for using GPR for tree root systems imaging and analysis are discussed.

  4. Dual-Remote Raman Technology for In-Situ Identification of Tank Waste

    SciTech Connect

    Bryan, Samuel A.; Levitskaia, Tatiana G.; Lines, Amanda M.; Smith, Frances N.; Josephson, Gary B.; Bello, Job M.

    2013-02-24

    A new Raman spectroscopic system for in-situ identification of the composition of the solid nuclear tank waste is being developed by collaborative effort between Pacific Northwest National Laboratory (PNNL) and EIC, Inc. The recent advancements in the Raman technology allow probing the chemical composition of the tank waste without sample collection. In the newly tested configuration, the Raman probe is installed on the top of the tank riser and sends the incident laser beam to the bottom of the tank, 10 – 70 feet away. The returning light containing chemical information is collected by the Raman probe and transmits it via fiber optic cable to the spectrometer located outside the tank farm area. This dual remote technology significantly expands currently limited options for the safe rapid in-situ identification of the solid tank waste needed for the retrieval decisions. The developed Raman system was extensively tested for acceptability prior tank farm deployment. This testing included calibration of the system with the respect of the distance between the Raman probe and the sample, incident laser beam angle, and presence of the optical interferences. The Raman system was successfully deployed to C-111 tank at the US DOE Hanford site. As the result of this deployment, the composition of the hardpan at the bottom of C-111 tank was identified. Further development of the dual-remote Raman technology will provide a significant safety enhancement eliminating the potential of personnel radiation exposure associated with the grab sample collection and expands options of the rapid and cost-effective in-situ chemical analysis of the tank waste.

  5. Dual-Remote Raman Technology for In-Situ Identification of Tank Waste - 13549

    SciTech Connect

    Bryan, Sam; Levitskaia, Tatiana; Lines, Amanda; Smith, Frannie; Josephson, Gary; Bello, Job

    2013-07-01

    A new Raman spectroscopic system for in-situ identification of the composition of solid nuclear tank waste is being developed by collaborative effort between Pacific Northwest National Laboratory (PNNL) and EIC Laboratories, Inc. The recent advancements in Raman technology allow probing the chemical composition of the tank waste without sample collection. In the newly tested configuration, the Raman probe is installed on the top of the tank riser and sends the incident laser beam to the bottom of the tank, 10 - 70 feet away. The returning light containing chemical information is collected by the Raman probe and is transmitted via fiber optic cable to the spectrometer located outside the tank farm area. This dual remote technology significantly expands currently limited options for the safe rapid in-situ identification of the solid tank waste needed for the retrieval decisions. The developed Raman system was extensively tested for acceptability prior to tank farm deployment. This testing included calibration of the system with respect of the distance between the Raman probe and the sample, incident laser beam angle, and presence of the optical interferences. The Raman system was successfully deployed on Tank C-111 at the US DOE Hanford site. As the result of this deployment, the composition of the hardpan at the bottom of C-111 tank was identified. Further development of the dual-remote Raman technology will provide a significant safety enhancement eliminating the potential of personnel radiation exposure associated with the grab sample collection and expands options of the rapid and cost-effective in-situ chemical analysis of the tank waste. (authors)

  6. In situ confocal Raman spectroscopy of lubricants in a soft elastohydrodynamic tribological contact

    NASA Astrophysics Data System (ADS)

    Bongaerts, J. H. H.; Day, J. P. R.; Marriott, C.; Pudney, P. D. A.; Williamson, A.-M.

    2008-07-01

    This paper describes an experimental setup that combines friction measurements with in situ confocal Raman microscopy on a lubricating fluid film. The setup allows the determination of film thickness and shear-rate profiles, the position-dependent lubricant composition within the rubbing contact, as well as optical imaging of the contact and its surroundings. The tribological contact can be investigated at continuous rubbing conditions over a range of sliding speeds from 1×10-3to2m/s. The setup's capabilities are demonstrated for a soft poly(dimethylsiloxane) sphere pressed and rotated against a quartz flat. Friction forces are presented in the boundary, mixed, and elastohydrodynamic lubrication (EHL) regimes for both a hydrophilic and a hydrophobic flat surface. Optical images of the contact show that, for single-phase aqueous Newtonian lubricants in the EHL regime, starvation of the contact occurs above a critical value of the product of the entrainment speed and the lubricant viscosity. Starvation results in a lower film thickness and lower friction values than predicted by numerical calculations that do not take starvation into account. The capability to determine, using Raman spectroscopy, the composition of the lubricant within the contact is demonstrated for oil-in-water emulsions, stabilized by a nonionic surfactant (Tween 60). The oil concentration was found to depend on both the sliding speed and the position within the rubbing contact. For the investigated tribological conditions, the oil content within the contact was lower than that of the bulk emulsion. This is attributed to the fact that the aqueous matrix phase preferentially wets the hydrophilic quartz slide, which prevents oil droplets from entering the contact if the film thickness is of the order of the droplet size. The ability to determine friction forces, lubricant composition and film thickness, and shear-rate profiles will provide invaluable information in the pursuit of a better

  7. Detection of latent prints by Raman imaging

    DOEpatents

    Lewis, Linda Anne; Connatser, Raynella Magdalene; Lewis, Sr., Samuel Arthur

    2011-01-11

    The present invention relates to a method for detecting a print on a surface, the method comprising: (a) contacting the print with a Raman surface-enhancing agent to produce a Raman-enhanced print; and (b) detecting the Raman-enhanced print using a Raman spectroscopic method. The invention is particularly directed to the imaging of latent fingerprints.

  8. In-situ fiber-optic Raman study of emulsion polymerization

    SciTech Connect

    Al-Khanbashi, A.S.; Hansen, M.G.; Wachter, E.A.

    1996-12-31

    Emulsion polymerization is a major commercial process for the production of various polymers. The unique nature of the reaction offers the possibility of producing products with special properties not easily made by other types of polymerization process. The reaction is heterogeneous, with the reactants and products dispersed as a separate phase in the main aqueous medium. Since water is a weak Raman scatterer and does not interfere with the analytical peak of the reactant, Raman scattering should be an effective method for in-line monitoring of the reaction progress. Recent advances in fiber-optic Raman have attracted great attention in developing methods for monitoring chemical processes in remote and hostile environments. This work describes in-situ monitoring of the emulsion polymerization of vinyl acetate using remote Raman spectroscopy.

  9. In situ Raman monitoring of single-walled carbon nanotube filling with copper chloride

    NASA Astrophysics Data System (ADS)

    Eremin, Timofei V.; Tonkikh, Alexander A.; Kudryashova, Ekaterina M.

    2016-03-01

    In situ characterization of single-walled carbon nanotubes during their gas-phase filling with copper chloride (CuCl) was performed with Raman spectroscopy. The time dependence of positions and intensities of G, 2D, and radial breathing modes was investigated. It was demonstrated that the adsorption of copper chloride from gas phase on the external and internal surfaces of nanotubes leads to the Raman mode shifting. However, this effect is weaker than in case of formation of one-dimensional CuCl crystals inside nanotubes.

  10. Visualizing In Situ Microstructure Dependent Crack Tip Stress Distribution in IN-617 Using Nano-mechanical Raman Spectroscopy

    NASA Astrophysics Data System (ADS)

    Zhang, Yang; Mohanty, Debapriya P.; Tomar, Vikas

    2016-09-01

    Inconel 617 (IN-617) is a solid solution alloy, which is widely used in applications that require high-temperature component operation due to its high-temperature stability and strength as well as strong resistance to oxidation and carburization. The current work focuses on in situ measurements of stress distribution under 3-point bending at elevated temperature in IN-617. A nanomechanical Raman spectroscopy measurement platform was designed and built based on a combination of a customized open Raman spectroscopy (NMRS) system incorporating a motorized scanning and imaging system with a nanomechanical loading platform. Based on the scanning of the crack tip notch area using the NMRS notch tip, stress distribution under applied load with micron-scale resolution for analyzed microstructures is predicted. A finite element method-based formulation to predict crack tip stresses is presented and validated using the presented experimental data.

  11. First steps of in situ surface-enhanced Raman scattering during shipboard experiments.

    PubMed

    Péron, Olivier; Rinnert, Emmanuel; Colas, Florent; Lehaitre, Michel; Compère, Chantal

    2010-10-01

    It is shown that the surface-enhanced Raman scattering (SERS) technique can be applied to detect organic molecules during in situ experiments. To this purpose, we used trans-1,2-bis(4-pyridyl)ethylene (BPE) as a target molecule. Adsorbed on the SERS chemosensor surface and excited under laser, the vibration modes of the molecules can be identified. SERS chemosensors are based on quartz substrates functionalized by silanization and partially coated with gold nanoparticles. SERS measurements during shipboard experiments were made with a home-made in situ Raman spectrometer connected to a marinized micro-fluidic system. The device was designed to host chemosensors in order to ensure measurements with a flow cell. A theoretical limit of detection was estimated in the range of picomolar (pM) concentrations based on Freundlich isotherm calculations. PMID:20925977

  12. In-situ Raman spectroscopy mapping of Si based anode material lithiation

    NASA Astrophysics Data System (ADS)

    Yang, Junfeng; Kraytsberg, Alexander; Ein-Eli, Yair

    2015-05-01

    The lithiation/de-lithiation behavior of Cu-nanowire/Si nano-particle composite anodes with different copper current collectors is investigated using in-situ micro Raman spectroscopy. It is revealed that not all of the active material particles experience lithiation in the first cycle. It is suggested that a portion of the anode active material is electrically disconnected from the current collector to begin with. Mapping of the connectivity of the anode electrode, performed by in-situ micro-Raman revealed that the portion of the disconnected material depends on the type of the current collector and on the active material loading. The disconnected zones are distributed unevenly over the electrode area.

  13. Metallic monoclinic phase in VO2 induced by electrochemical gating: In situ Raman study

    NASA Astrophysics Data System (ADS)

    Nath Gupta, Satyendra; Pal, Anand; Muthu, D. V. S.; Kumar, P. S. Anil; Sood, A. K.

    2016-07-01

    We report in situ Raman scattering studies of electrochemically top gated VO2 thin film to address metal-insulator transition (MIT) under gating. The room temperature monoclinic insulating phase goes to metallic state at a gate voltage of 2.6 V. However, the number of Raman modes do not change with electrolyte gating showing that the metallic phase is still monoclinic. The high-frequency Raman mode A g (7) near 616 cm-1 ascribed to V-O vibration of bond length 2.06 Å in VO6 octahedra hardens with increasing gate voltage and the B g (3) mode near 654 cm-1 softens. This shows that the distortion of the VO6 octahedra in the monoclinic phase decreases with gating. The time-dependent Raman data at fixed gate voltages of 1 V (for 50 minutes, showing enhancement of conductivity by a factor of 50) and 2 V (for 130 minutes, showing further increase in conductivity by a factor of 5) show similar changes in high-frequency Raman modes A g (7) and B g (3) as observed in gating. This slow change in conductance together with Raman frequency changes show that the governing mechanism for metalization is more likely due to the diffusion-controlled oxygen vacancy formation due to the applied electric field.

  14. In Situ Raman Spectroscopy of Cave Minerals: An Analytical Tool Compatibla with the Conservation of Subterranean Heritage

    NASA Astrophysics Data System (ADS)

    Gazquez, F.; Rull, F.; Calaforra, J. M.; Sanz, A.; Medina, J.

    2014-06-01

    In this work we have studied the mineralogy of some peculiar spelothems in El Soplao Cave Northern Spain by in situ Raman spectroscopy. Spectacular helictites, anthodites and huge speleothems are the most relevant aesthetic features of this cave.

  15. In Situ Raman Spectra from the SeaCliff Hydrothermal Field (Gorda Ridge)

    NASA Astrophysics Data System (ADS)

    White, S. N.; Dunk, R. M.; Brewer, P. G.; Peltzer, E. T.; Sherman, A. D.; Freeman, J. J.

    2004-12-01

    MBARI's in situ laser Raman spectrometer (DORISS - Deep Ocean Raman In Situ Spectrometer) was deployed at the SeaCliff Hydrothermal Field on the Gorda Ridge in July 2004. The first in situ Raman spectra of hydrothermal minerals and high-temperature fluid venting from the seafloor were obtained. These spectra are analyzed and compared to laboratory measurements of samples collected from the site. Laser Raman spectroscopy is a proven, powerful geochemical technique for analyzing the chemical composition and molecular structure of solids, liquids, and gases. During an expedition to Gorda Ridge on the R/V Western Flyer in July 2004, DORISS was deployed successfully by the ROV Tiburon at hydrothermal vents on the seafloor ( ˜2700 m depth). Data were collected from hydrothermal fluids, chimney minerals (e.g., anhydrite and barite), and bacterial mats using two types of sampling optics: an immersion optic, and a non-contact optic. To collect spectra from opaque mineral samples, a precision underwater positioner (PUP) was used to position the DORISS probe head. PUP is a stand-alone, three degree-of-freedom positioner capable of moving the DORISS probe head with a precision of 0.1 mm (required by the small focal volume of the sampling optic). Raman spectra were collected of ˜300° C vent fluids with both sampling optics. The Raman spectrum of seawater contains bands from the bending ( ˜1640 cm-1) and stretching (3000-3700 cm-1) vibrational modes of the water molecule and a small peak from the S-O stretch of the sulfate ion ( ˜981 cm-1). Compared to ˜2° C ambient seawater, vent fluid spectra show changes in the intensity ratios of the water bands due to the elevated temperature, and the sulfate peak is reduced. Additional components of hydrothermal fluid are present in such low concentrations that it is difficult to detect them with the current Raman system. The chimneys in the SeaCliff field are primarily anhydrite, and debris in the area also contains barite. We were

  16. In situ electron spin resonance and Raman spectroscopic studies of the electrochemical process of conducting polypyrrole films

    SciTech Connect

    Zhong, C.J.; Tian, Z.Q.; Tian, Z.W. )

    1990-03-08

    The electrochemical redox properties of conducting polypyrrole (PPy) films coated on electrodes are investigated in aqueous solutions by use of the in situ techniques of electron spin resonance (ESR) and Raman spectroscopy. Comparisons between the experimental in situ ESR data and a theoretical kinetic prediction on the basis of the polaron-bipolaron model are presented.

  17. Shifted excitation Raman difference spectroscopy at multiple wavelengths for in-situ meat species differentiation

    NASA Astrophysics Data System (ADS)

    Sowoidnich, Kay; Kronfeldt, Heinz-Detlef

    2012-09-01

    Two miniaturized Raman measurement heads containing microsystem diode lasers emitting at 783 and 671 nm suitable for shifted excitation Raman difference spectroscopy (SERDS) were applied for the non-invasive in situ differentiation of selected meat species. This allows using the fingerprint characteristics of Raman spectra without a disturbing fluorescence background. At 783 nm, two emission lines with a spectral shift of 0.5 nm (7 cm-1) and optical powers of up to 110 mW were realized. For 671 nm excitation, the spectral shift amounts to 0.6 nm (12 cm-1) and optical powers of up to 40 mW were obtained. In both cases, meat Raman spectra could be recorded with integration times of 10 s. The investigations were carried out using selected cuts from the most commonly consumed meat species in the US and Europe, i.e. beef, pork, chicken, and turkey. A principal components analysis of the SERDS spectra revealed a clear separation of the meat species into four distinct groups for both excitation wavelengths. This classification is based on the myoglobin content and gradual differences of protein Raman band intensities and positions. The results demonstrate the potential of SERDS as rapid and non-destructive screening method for the discrimination of selected meat species.

  18. Coherent anti-Stokes Raman scattering imaging under ambient light.

    PubMed

    Zhang, Yinxin; Liao, Chien-Sheng; Hong, Weili; Huang, Kai-Chih; Yang, Huaidong; Jin, Guofan; Cheng, Ji-Xin

    2016-08-15

    We demonstrate an ambient light coherent anti-Stokes Raman scattering microscope that allows CARS imaging to be operated under environmental light for field use. The CARS signal is modulated at megahertz frequency and detected by a photodiode equipped with a lab-built resonant amplifier, then extracted through a lock-in amplifier. The filters in both the spectral domain and the frequency domain effectively blocked the room light contamination of the CARS image. In situ hyperspectral CARS imaging of tumor tissue under ambient light is demonstrated. PMID:27519113

  19. In situ surface-enhanced Raman scattering spectroscopy exploring molecular changes of drug-treated cancer cell nucleus.

    PubMed

    Liang, Lijia; Huang, Dianshuai; Wang, Hailong; Li, Haibo; Xu, Shuping; Chang, Yixin; Li, Hui; Yang, Ying-Wei; Liang, Chongyang; Xu, Weiqing

    2015-02-17

    Investigating the molecular changes of cancer cell nucleus with drugs treatment is crucial for the design of new anticancer drugs, the development of novel diagnostic strategies, and the advancement of cancer therapy efficiency. In order to better understand the action effects of drugs, accurate location and in situ acquisition of the molecular information of the cell nuclei are necessary. In this work, we report a microspectroscopic technique called dark-field and fluorescence coimaging assisted surface-enhanced Raman scattering (SERS) spectroscopy, combined with nuclear targeting nanoprobes, to in situ study Soma Gastric Cancer (SGC-7901) cell nuclei treated with two model drugs, e.g., DNA binder (Hoechst33342) and anticancer drug (doxorubicin, Dox) via spectral analysis at the molecular level. Nuclear targeting nanoprobes with an assembly structure of thiol-modified polyethylene glycol polymers (PEG) and nuclear localizing signal peptides (NLS) around gold nanorods (AuNRs) were prepared to achieve the amplified SERS signals of biomolecules in the cell nuclei. With the assistance of dark field/fluorescence imaging with simultaneous location, in situ SERS spectra in one cell nucleus were measured and analyzed to disclose the effects of Hoechst33342 and Dox on main biomolecules in the cell nuclei. The experimental results show that this method possesses great potential to investigate the targets of new anticancer drugs and the real-time monitoring of the dynamic changes of cells caused by exogenous molecules.

  20. In situ surface-enhanced Raman scattering spectroscopy exploring molecular changes of drug-treated cancer cell nucleus.

    PubMed

    Liang, Lijia; Huang, Dianshuai; Wang, Hailong; Li, Haibo; Xu, Shuping; Chang, Yixin; Li, Hui; Yang, Ying-Wei; Liang, Chongyang; Xu, Weiqing

    2015-02-17

    Investigating the molecular changes of cancer cell nucleus with drugs treatment is crucial for the design of new anticancer drugs, the development of novel diagnostic strategies, and the advancement of cancer therapy efficiency. In order to better understand the action effects of drugs, accurate location and in situ acquisition of the molecular information of the cell nuclei are necessary. In this work, we report a microspectroscopic technique called dark-field and fluorescence coimaging assisted surface-enhanced Raman scattering (SERS) spectroscopy, combined with nuclear targeting nanoprobes, to in situ study Soma Gastric Cancer (SGC-7901) cell nuclei treated with two model drugs, e.g., DNA binder (Hoechst33342) and anticancer drug (doxorubicin, Dox) via spectral analysis at the molecular level. Nuclear targeting nanoprobes with an assembly structure of thiol-modified polyethylene glycol polymers (PEG) and nuclear localizing signal peptides (NLS) around gold nanorods (AuNRs) were prepared to achieve the amplified SERS signals of biomolecules in the cell nuclei. With the assistance of dark field/fluorescence imaging with simultaneous location, in situ SERS spectra in one cell nucleus were measured and analyzed to disclose the effects of Hoechst33342 and Dox on main biomolecules in the cell nuclei. The experimental results show that this method possesses great potential to investigate the targets of new anticancer drugs and the real-time monitoring of the dynamic changes of cells caused by exogenous molecules. PMID:25602628

  1. In-SITU Raman Spectroscopy of Single Microparticle Li-Intercalation Electrodes

    NASA Technical Reports Server (NTRS)

    Dokko, Kaoru; Shi, Qing-Fang; Stefan, Ionel C.; Scherson, Daniel A.

    2003-01-01

    Modifications in the vibrational properties of a single microparticle of LiMn2O4 induced by extraction and subsequent injection of Li(+) into the lattice have been monitored in situ via simultaneous acquisition of Raman scattering spectra and cyclic voltammetry data in 1M LiC1O4 solutions in ethylene carbonate (EC):diethyl carbonate (DEC) mixtures (1:1 by volume). Statistical analyses of the spectra in the range 15 < SOD < 45%, where SOD represents the state of discharge (in percent) of the nominally fully charged material, i.e. lambda-MnO2, were found to be consistent with the coexistence of two distinct phases of lithiated metal oxide in agreement with information derived from in situ X-ray diffraction (XRD) measurements involving more conventional battery-type electrodes.

  2. In situ Raman spectroscopic study of Al-infiltrated spider dragline silk under tensile deformation.

    PubMed

    Lee, Seung-Mo; Pippel, Eckhard; Moutanabbir, Oussama; Kim, Jae-Hyun; Lee, Hak-Joo; Knez, Mato

    2014-10-01

    Natural materials consisting of protein structures impregnated with a tiny amount of metals often exhibit impressive mechanical behavior, which represents a new design paradigm for the development of biomimetic materials. Here, we produced Al-infiltrated silks by applying a modified Al2O3 atomic layer deposition process to the dragline silk of the Nephila pilipes spider, which showed unusual mechanical properties. The deformation behavior of the molecular structure of the Al-infiltrated silk was investigated by performing in situ Raman spectroscopy, where Raman shifts were measured concurrently with macroscopic mechanical deformations. For identifying the role of the infiltrated Al atoms, the study was performed in parallel with untreated silk, and the results were compared. Our experimental results revealed that superior mechanical properties of the Al-infiltrated silk are likely to be caused by the alterations of the sizes of the β-sheet crystals and their distribution.

  3. Porous silicon structural evolution from in-situ luminescence and Raman measurements

    SciTech Connect

    Tallant, D.R.; Kelly, M.J.; Guilinger, T.R.; Simpson, R.L.

    1996-05-01

    The authors performed in-situ photoluminescence and Raman measurements on an anodized silicon surface in the HF/ethanol solution used for anodization. The porous silicon thereby produced, while resident in HF/ethanol, does not immediately exhibit intense photoluminescence. Intense photoluminescence develops spontaneously in HF/ethanol after 18--24 hours or with replacement of the HF/ethanol with water. These results support a quantum confinement mechanism in which exciton migration to traps and nonradiative recombination dominates the de-excitation pathways until silicon nanocrystallites are physically separated and energetically decoupled by hydrofluoric acid etching or surface oxidation. The porous silicon surface, as produced by anodization, shows large differences in photoluminescence intensity and peak wavelength over millimeter distances. Parallel Raman measurements implicate nanometer-size silicon particles in the photoluminescence mechanism.

  4. Laboratory real-time and in situ monitoring of mechanochemical milling reactions by Raman spectroscopy.

    PubMed

    Gracin, Davor; Štrukil, Vjekoslav; Friščić, Tomislav; Halasz, Ivan; Užarević, Krunoslav

    2014-06-10

    Mechanistic understanding of mechanochemical reactions is sparse and has been acquired mostly by stepwise ex situ analysis. We describe herein an unprecedented laboratory technique to monitor the course of mechanochemical transformations at the molecular level in situ and in real time by using Raman spectroscopy. The technique, in which translucent milling vessels are used that enable the collection of a Raman scattering signal from the sample as it is being milled, was validated on mechanochemical reactions to form coordination polymers and organic cocrystals. The technique enabled the assessment of the reaction dynamics and course under different reaction conditions as well as, for the first time, direct insight into the behavior of liquid additives during liquid-assisted grinding.

  5. In situ laser Raman spectra of iron phthalocyanine adsorbed on copper and gold electrodes. [Electronic structure

    SciTech Connect

    Melendres, C.A.; Rios, C.B.; Feng, X.; McMasters, R.

    1983-01-01

    Raman spectra of iron phthalocyanine (FePc) and its tetrasulfonated derivative (FeTSPc) adsorbed on copper and gold electrodes have been observed in situ in 0.05 M H/sub 2/SO/sub 4/ solution. Results confirm the authors previous finding on the coordination of FePc to water molecules to solution. Evidence suggests that the iron phthalocyanines are probably oriented with their planes parallel to the electrode surface even in immersed electrodes. A decrease in intensity and broadening of some vibrational bands are observed on increasing cathodic polarization; these are attributed to a lifting of the degeneracy of the vibrational modes due to a change in symmetry of the adsorbed molecules brought about by polarization induced by the double-layer field. The effect of carbon on the Raman spectra is discussed. The iron phthalocyanines appear to be stable at potentials close to hydrogen evolution in the absence of oxygen. 18 references, 8 figures.

  6. In situ laser Raman spectra of iron phthalocyanine adsorbed on copper and gold electrodes

    SciTech Connect

    Melendres, C.A.; Rios, C.B.; Feng, X.; McMasters, R.

    1983-09-01

    Raman spectra of iron phthalocyanine (FePc) and its tetrasulfonated derivative (FeTSPc) adsorbed on copper and gold electrodes have been observed in situ in 0.05 M H/sub 2/SO/sub 4/ solution. Results confirm our previous finding on the coordination of FePc to water molecules to solution. Evidence suggests that the iron phthalocyanines are probably oriented with their planes parallel to the electrode surface even in immersed electrodes. A decrease in intensity and broadening of some vibrational bands are observed on increasing cathodic polarization; these are attributed to a lifting of the degeneracy of the vibrational modes due to a change in symmetry of the adsorbed molecules brought about by polarization induced by the double-layer field. The effect of carbon on the Raman spectra is discussed. The iron phthalocyanines appear to be stable at potentials close to hydrogen evolution in the absence of oxygen. 8 figures.

  7. In situ Raman spectroscopic study of Al-infiltrated spider dragline silk under tensile deformation.

    PubMed

    Lee, Seung-Mo; Pippel, Eckhard; Moutanabbir, Oussama; Kim, Jae-Hyun; Lee, Hak-Joo; Knez, Mato

    2014-10-01

    Natural materials consisting of protein structures impregnated with a tiny amount of metals often exhibit impressive mechanical behavior, which represents a new design paradigm for the development of biomimetic materials. Here, we produced Al-infiltrated silks by applying a modified Al2O3 atomic layer deposition process to the dragline silk of the Nephila pilipes spider, which showed unusual mechanical properties. The deformation behavior of the molecular structure of the Al-infiltrated silk was investigated by performing in situ Raman spectroscopy, where Raman shifts were measured concurrently with macroscopic mechanical deformations. For identifying the role of the infiltrated Al atoms, the study was performed in parallel with untreated silk, and the results were compared. Our experimental results revealed that superior mechanical properties of the Al-infiltrated silk are likely to be caused by the alterations of the sizes of the β-sheet crystals and their distribution. PMID:25203848

  8. In situ monitoring of biomolecular processes in living systems using surface-enhanced Raman scattering

    NASA Astrophysics Data System (ADS)

    Altunbek, Mine; Kelestemur, Seda; Culha, Mustafa

    2015-12-01

    Surface-enhanced Raman scattering (SERS) continues to strive to gather molecular level information from dynamic biological systems. It is our ongoing effort to utilize the technique for understanding of the biomolecular processes in living systems such as eukaryotic and prokaryotic cells. In this study, the technique is investigated to identify cell death mechanisms in 2D and 3D in vitro cell culture models, which is a very important process in tissue engineering and pharmaceutical applications. Second, in situ biofilm formation monitoring is investigated to understand how microorganisms respond to the environmental stimuli, which inferred information can be used to interfere with biofilm formation and fight against their pathogenic activity.

  9. In situ Raman estimation of irradiation-induced heating of UO2

    NASA Astrophysics Data System (ADS)

    Guimbretière, G.; Canizarès, A.; Desgranges, L.; Caraballo, R.; Duval, F.; Jegou, C.; Magnin, M.; Simon, P.

    2016-09-01

    We present an in situ Raman estimation of the temperature increase of UO2 pellets induced by cyclotron He2+ ionic irradiation in different environments (Ar gas or water): For instance, in the Ar gas environment, the sample is heated to a temperature 150-200 °C (i.e., below the annealing temperature of UO2 defects). For water, the sample is heated from 30 to 80 °C, just below the range of the studtite/metastudtite and the schoepite/metaschoepite transitions.

  10. In Situ Planetary Mineralogy Using Simultaneous Time Resolved Fluorescence and Raman Spectroscopy

    NASA Technical Reports Server (NTRS)

    Blacksberg, J.; Rossman , G.R.

    2011-01-01

    Micro-Raman spectroscopy is one of the primary methods of mineralogical analysis in the laboratory, and more recently in the field. Because of its versatility and ability to interrogate rocks in their natural form it is one of the front runners for the next generation of in situ instruments designed to explore adverse set of solar system bodies (e.g. Mars, Venus, the Moon, and other primitive bodies such as asteroids and the Martian moons Phobos and Deimos), as well as for pre-selection of rock and soil samples for potential cache and return missions.

  11. Enhanced Raman Scattering of Silicon Nanowires by Ag Nanoparticles in-situ Decoration

    NASA Astrophysics Data System (ADS)

    Peng, Zeping; Hu, Hailong; Wang, Shijie; Shen, Zexiang; Xiong, Qihua

    2010-08-01

    Recently, metallic nanoparticles decorated semiconductor nanowires, especially silicon, attract considerable attention, due to their potential applications in photocatalysis, photovoltaics, surface enhanced Raman scattering and biosensing. A common method that has been used to decorate silicon nanowires with metallic nanoparticles, e.g. Au or Pt, is galvanic displacement, in which metallic ions are reduced with electrons supplied by virtue of silicon half-cell reaction. Here we report a method to decorate silicon nanowires with Ag nanoparticles by surface reduction, in which a freshly etched silicon surface reduces Ag ions in-situ in aqueous silver nitrate solution. The as-grown Ag nanoparticles exhibit either highly single crystallinity or twinning boundaries, with most probably diameter ˜25 nm (Figure 1). Raman mapping experiments suggest that 1st order Raman band of silicon nanowires exhibit uniform contrast along wire axis for pristine silicon nanowires, while for Ag nanoparticle decorated silicon nanowires a series of "hot-spot," i.e., substantially enhanced Raman scattering were discovered along the wire axis. This was explained by local electric field enhancement due to Ag nanoparticle "nano-antenna," which was supported by the correlation between atomic force microscopy (AFM) analysis and Raman mapping (Figure 2). The enhancement is more or less delocalized in Raman mapping due to diffraction limit in our far-field mapping experiments. In addition, we also noticed a new side band feature ˜495 cm-1 for nanowires appeared after HF etching, this new feature sustained after sequential Oxygen plasma and UV/ozone treatment which excluded the possibility due to any possible surface dangling bonds. We now suspect this feature is due to porosity resulted from HF etching and it is now being subjected to further investigations.

  12. In Situ Raman Microscopy of a Single Graphite Microflake Electrode in a Li(+)-containing Electrolyte

    NASA Technical Reports Server (NTRS)

    Shi, Qing-Fang; Dokko, Kaoru; Scherson, Daniel A.

    2003-01-01

    Highly detailed Raman spectra from a single KS-44 graphite microflake electrode as a function of the applied potential have been collected in situ using a Raman microscope and a sealed spectroelectrochemical cell isolated from the laboratory environment. Correlations were found between the Raman spectral features and the various Li(+) intercalation stages while recording in real time Raman spectra during a linear potential scan from 0.7 down ca. 0.0V vs Li/Li(+) at a rate of 0.1 mV/s in a 1M LiClO4 solution in a 1:l (by volume) ethylene carbonate (EC):diethyl carbonate (DEC) mixture. In particular, clearly defined isosbestic points were observed for data collected in the potential range where the transition between dilute phase 1 and phase 4 of lithiated graphite is known to occur, i.e. 0.157 < E < 0.215 vs Li/Li(+). Statistical analysis of the spectroscopic data within this region made it possible to determine independently the fraction of each of the two phases present as a function of potential without relying on coulometric information and then predict, based on the proposed stoichiometry for the transition, a spectrally-derived voltammetric feature.

  13. Next generation in-situ optical Raman sensor for seawater investigations

    NASA Astrophysics Data System (ADS)

    Kolomijeca, A.; Kwon, Y.-H.; Ahmad, H.; Kronfeldt, H.-D.

    2012-04-01

    We introduce the next generation of optical sensors based on a combination of surfaced enhanced Raman scattering (SERS) and shifted excitation Raman difference spectroscopy (SERDS) suited for investigations of tiny concentrations of pollutions in the seawater. First field measurements were carried out in the Arctic area which is of global interest since it is more affected by global warming caused climatic changes than any other areas of our planet and it is a recipient for many toxic organic pollutants. A significant long-range atmospheric transport of pollutants to Svalbard is mainly originated from industrialized countries in Europe and North America during the last decades. Therefore, the main interest is to investigate the Arctic water column and also the sediments. Standard chemical methods for water/sediment analysis are extremely accurate but complex and time-consuming. The primary objective of our study was to develop a fast response in-situ optical sensor for easy to use and quick analysis. The system comprises several components: a handheld measurement head containing a 671 nm microsystem diode laser and the Raman optical bench, a laser driver electronics board, a custom-designed miniature spectrometer with an optical resolution of 8 cm-1 and a netbook to control the spectrometer as well as for data evaluation. We introduced for the first time the portable Raman sensor system on an Artic sea-trial during a three week cruise on board of the James Clark Ross research vessel in August 2011. Numerous Raman and SERS measurements followed by SERDS evaluations were taken around locations 78° N and 9° E. Different SERS substrates developed for SERS measurements in sea-water were tested for their capability to detect different substances (PAHs) in the water down to very small (nmol/l) concentrations. Stability tests of the substrates were carried out also for the applicability of our system e.g. on a mooring. Details of the in-situ Raman sensor were presented

  14. Confocal Raman microscopy and fluorescent in situ hybridization - A complementary approach for biofilm analysis.

    PubMed

    Kniggendorf, Ann-Kathrin; Nogueira, Regina; Kelb, Christian; Schadzek, Patrik; Meinhardt-Wollweber, Merve; Ngezahayo, Anaclet; Roth, Bernhard

    2016-10-01

    We combine confocal Raman microscopy (CRM) of wet samples with subsequent Fluorescent in situ hybridization (FISH) without significant limitations to either technique for analyzing the same sample of a microbial community on a cell-to-cell basis. This combination of techniques allows a much deeper, more complete understanding of complex environmental samples than provided by either technique alone. The minimalistic approach is based on laboratory glassware with micro-engravings for reproducible localization of the sample at cell scale combined with a fixation and de- and rehydration protocol for the respective techniques. As proof of concept, we analyzed a floc of nitrifying activated sludge, demonstrating that the sample can be tracked with cell-scale precision over different measurements and instruments. The collected information includes the microbial content, spatial shape, variant chemical compositions of the floc matrix and the mineral microparticles embedded within. In addition, the direct comparison of CRM and FISH revealed a difference in reported cell size due to the different cell components targeted by the respective technique. To the best of our knowledge, this is the first report of a direct cell-to-cell comparison of confocal Raman microscopy and Fluorescent in situ hybridization analysis performed on the same sample. An adaptation of the method to include native samples as a starting point is planned for the near future. The micro-engraving approach itself also opens up the possibility of combining other, functionally incompatible techniques as required for further in-depth investigations of low-volume samples. PMID:27423128

  15. Raman spectroscopy for in situ- evaluation of high-grade malignant gliomas induced in SCID mice

    NASA Astrophysics Data System (ADS)

    Clary, Candace E.; Dergachev, Alex Y.; Mirov, Sergey B.; Gillespie, G. Yancey

    1997-05-01

    Each year, more people at younger ages are diagnosed with primary brain tumors. Current histological discrimination between normal and diseased tissue occurs after tissue excision. A reliable optical biopsy for open craniotomy would optimize the amount and types of tissue removal by making an accurate evaluation before excision. The presented work is part of a study investigating the clinical diagnostic potential of Raman spectroscopy for gliomas. It has been shown that the optical properties of in vitro tissue are strongly dependent upon sample preparation. The investigation of the effects of time latency, paraformalin tissue fixation, and tissue perfusion with carbogen-bubbled cortical transport solution on their respective Raman spectra of brain tissue and tumors will be discussed, as well as their implications on the study of neurological tissue. The studies are conducted with in situ tissue samples from scid mice and 785 nm pulsed alexandrite laser excitation. Results illustrating positive qualitative and quantitative variations between Raman spectra of normal and malignant brain tissue will be presented.

  16. A Nanoplasmonic Strategy for Precision in-situ Measurements of Tip-enhanced Raman and Fluorescence Spectroscopy

    PubMed Central

    Meng, Lingyan; Sun, Mengtao; Chen, Jianing; Yang, Zhilin

    2016-01-01

    We theoretically investigate an optimized tip-film system that supports in-situ measurement of tip-enhanced Raman spectroscopy (TERS) and tip-enhanced fluorescence (TEF) of dye molecules. A scanning tunneling microscope (STM) is proposed to precisely control the tip-film distance, and thus in-situ measurement of TERS and TEF can be realized utilizing the specific surface plasmon resonance (SPR) properties of the tip-film system. Our calculations show that the optimized tip-film distance of 2 nm suggests a possibility of efficient acquisition of TERS and TEF in-situ. The calculated spatial resolution of TERS and spectral resolution of TEF can be down to 6.5 nm and 10 nm, respectively. Our theoretical results may find promising application in developing multiple functional nano-spectroscopy through which Raman and fluorescence can be measured in-situ at the nanoscale level. PMID:26780882

  17. Raman and FTIR imaging of dynamic polymer systems

    NASA Astrophysics Data System (ADS)

    Bobiak, John Peter

    This work aims to expand the applications of Raman and infrared imaging in materials science and engineering. Recent developments in spectroscopic imaging technology have led to relatively fast image acquisition rates, enabling the in situ analysis of various engineering processes. A brief review of spectroscopic imaging principles and existing applications is provided as background before three novel applications are set forth. First, the effectiveness of FTIR imaging for modeling polymer dissolution behavior was examined in a series of binary poly (methyl methacrylate) (PMMA) systems. The dissolution behavior was influenced by polymer conformation as well as the solvent characteristics. The results indicate that chemistry alone is a poor predictor of dissolution rate. Rather, the diffusion coefficients of both the polymer and solvent have a foremost impact on the dissolution process. One major complication in modeling diffusion-related process by FTIR imaging is the precise determination of component locations in a series of images. This issue is addressed through the introduction of a new position-reporting technique based on hypothesis testing. A rudimentary drug release system, consisting of a poly (ethylene-co-vinyl acetate) film and a nicotine solution, was used to illustrate the importance of precisely reporting the nicotine diffusion front position. The new reporting method provided an inherent level of certainty to the position report. This method was applied to qualitatively assess the uptake of nicotine from solutions containing different solubilizing agents, which were capable of either promoting or inhibiting nicotine uptake. Finally, Raman mapping and Raman line imaging were used to classify individual carbon nanotubes that were dispersed on a substrate. Individual nanotubes displayed a range of spectral characteristics, indicating that the bulk sample was a mixture of materials with different graphitic domain sizes. The results from images acquired

  18. In-situ identification of meat from different animal species by shifted excitation Raman difference spectroscopy

    NASA Astrophysics Data System (ADS)

    Sowoidnich, Kay; Kronfeldt, Heinz-Detlef

    2012-05-01

    The identification of food products and the detection of adulteration are of global interest for food safety and quality control. We present a non-invasive in-situ approach for the differentiation of meat from selected animal species using microsystem diode laser based shifted excitation Raman difference spectroscopy (SERDS) at 671 nm and 785 nm. In that way, the fingerprint Raman spectra can be used for identification without a disturbing fluorescence background masking Raman signals often occurring in the investigation of biological samples. Two miniaturized SERDS measurement heads including the diode laser and all optical elements are fiber-optically coupled to compact laboratory spectrometers. To realize two slightly shifted excitation wavelengths necessary for SERDS the 671 nm laser (spectral shift: 0.7 nm, optical power: 50 mW) comprises two separate laser cavities each with a volume Bragg grating for frequency selection whereas the 785 nm light source (spectral shift: 0.5 nm, optical power: 110 mW) is a distributed feedback laser. For our investigations we chose the most consumed meat types in the US and Europe, i.e. chicken and turkey as white meat as well as pork and beef as red meat species. The applied optical powers were sufficient to detect meat Raman spectra with integration times of 10 seconds pointing out the ability for a rapid discrimination of meat samples. Principal components analysis was applied to the SERDS spectra to reveal spectral differences between the animals suitable for their identification. The results will be discussed with respect to specific characteristics of the analyzed meat species.

  19. In situ surface-enhanced Raman scattering spectroelectrochemistry of oxygen species.

    PubMed

    Itoh, Takashi; Maeda, Toshiteru; Kasuya, Atsuo

    2006-01-01

    In situ surface-enhanced Raman scattering (SERS) combined with electrochemical analysis is applied to the determination of oxygen species on silver electrodes in alkaline hydroxide aqueous solution at room temperature and gold electrodes in carbonate melts at high temperature. This technique, referred to as SERS spectroelectrochemistry, reveals Raman spectral lines in the 500-1100 cm(-1) range under electrode potential scanning, assignable to superoxide ions (O2-) and peroxide ions (O2(2-)) on the electrode surface. These lines for oxygen molecule species have potential dependence with changing potential. In the alkaline hydroxide aqueous solution, the Raman peaks due to oxygen molecules are observed at potentials between 0.2 V and -0.8 V (vs. Ag/AgCl) only in the cathodic scan. This irreversible behavior in cyclic voltammograms indicates the existence of an intermediate stage in the oxygen reduction process, in which oxygen is released from the AgO films on the electrode at potentials corresponding to the onset of the last current peak in the voltammogram. This liberated oxygen molecule remains in solution at the interface until hydroxyls or water molecules are formed when the potential reaches the potential zero charge (PZC). In the high-temperature carbonate melts, Raman lines at 1047, 1080, and 800 cm(-1) are apparent for the eutectic (62 + 38) mol% (Li + K)CO3 melt at 923 K, and at 735 cm(-1) for the Li2CO3 melt at 1123 K. These results suggest that oxygen reduction in the Li2CO3 melt involves only peroxide ions, while that in (62 + 38) mol% (Li + K)CO3 involves both peroxide and superoxide ions at the three-phase boundary interface. PMID:16833110

  20. Portable Sequentially Shifted Excitation Raman spectroscopy as an innovative tool for in situ chemical interrogation of painted surfaces.

    PubMed

    Conti, Claudia; Botteon, Alessandra; Bertasa, Moira; Colombo, Chiara; Realini, Marco; Sali, Diego

    2016-08-01

    We present the first validation and application of portable Sequentially Shifted Excitation (SSE) Raman spectroscopy for the survey of painted layers in art. The method enables the acquisition of shifted Raman spectra and the recovery of the spectral data through the application of a suitable reconstruction algorithm. The technique has a great potentiality in art where commonly a strong fluorescence obscures the Raman signal of the target, especially when conventional portable Raman spectrometers are used for in situ analyses. Firstly, the analytical capability of portable SSE Raman spectroscopy is critically discussed using reference materials and laboratory specimens, comparing its results with other conventional high performance laboratory instruments (benchtop FT-Raman and dispersive Raman spectrometers with an external fiber optic probe); secondly, it is applied directly in situ to study the complex polychromy of Italian prestigious terracotta sculptures of the 16(th) century. Portable SSE Raman spectroscopy represents a new investigation modality in art, expanding the portfolio of non-invasive, chemically specific analytical tools.

  1. In-situ observation and atomic resolution imaging of the ion irradiation induced amorphisation of graphene

    PubMed Central

    Pan, C.-T.; Hinks, J. A.; Ramasse, Q. M.; Greaves, G.; Bangert, U.; Donnelly, S. E.; Haigh, S. J.

    2014-01-01

    Ion irradiation has been observed to induce a macroscopic flattening and in-plane shrinkage of graphene sheets without a complete loss of crystallinity. Electron diffraction studies performed during simultaneous in-situ ion irradiation have allowed identification of the fluence at which the graphene sheet loses long-range order. This approach has facilitated complementary ex-situ investigations, allowing the first atomic resolution scanning transmission electron microscopy images of ion-irradiation induced graphene defect structures together with quantitative analysis of defect densities using Raman spectroscopy. PMID:25284688

  2. In-situ observation and atomic resolution imaging of the ion irradiation induced amorphisation of graphene.

    PubMed

    Pan, C-T; Hinks, J A; Ramasse, Q M; Greaves, G; Bangert, U; Donnelly, S E; Haigh, S J

    2014-01-01

    Ion irradiation has been observed to induce a macroscopic flattening and in-plane shrinkage of graphene sheets without a complete loss of crystallinity. Electron diffraction studies performed during simultaneous in-situ ion irradiation have allowed identification of the fluence at which the graphene sheet loses long-range order. This approach has facilitated complementary ex-situ investigations, allowing the first atomic resolution scanning transmission electron microscopy images of ion-irradiation induced graphene defect structures together with quantitative analysis of defect densities using Raman spectroscopy. PMID:25284688

  3. In Situ and In Vivo Molecular Analysis by Coherent Raman Scattering Microscopy

    NASA Astrophysics Data System (ADS)

    Liao, Chien-Sheng; Cheng, Ji-Xin

    2016-06-01

    Coherent Raman scattering (CRS) microscopy is a high-speed vibrational imaging platform with the ability to visualize the chemical content of a living specimen by using molecular vibrational fingerprints. We review technical advances and biological applications of CRS microscopy. The basic theory of CRS and the state-of-the-art instrumentation of a CRS microscope are presented. We further summarize and compare the algorithms that are used to separate the Raman signal from the nonresonant background, to denoise a CRS image, and to decompose a hyperspectral CRS image into concentration maps of principal components. Important applications of single-frequency and hyperspectral CRS microscopy are highlighted. Potential directions of CRS microscopy are discussed.

  4. In situ Raman spectroscopic investigation of the structure of subduction-zone fluids

    USGS Publications Warehouse

    Mibe, Kenji; Chou, I.-Ming; Bassett, William A.

    2008-01-01

    In situ Raman spectra of synthetic subduction-zone fluids (KAlSi3O8-H2O system) were measured to 900?? and 2.3 GPa using a hydrothermal diamond-anvil cell. The structures of aqueous fluid and hydrous melt become closer when conditions approach the second critical endpoint. Almost no three-dimensional network was observed in the supercritical fluid above 2 GPa although a large amount of silicate component is dissolved, suggesting that the physical and chemical properties of these phases change drastically at around the second critical endpoint. Our experimental results indicate that the fluids released from a subducting slab change from aqueous fluid to supercritical fluid with increasing depth under the volcanic arcs. Copyright 2008 by the American Geophysical Union.

  5. In situ Raman spectroscopy study of metal-enhanced hydrogenation and dehydrogenation of VO2.

    PubMed

    Wu, Hao; Fu, Qiang; Bao, Xinhe

    2016-11-01

    Vanadium dioxide (VO2) has a phase transition from insulator to metal at 340 K, and this transition can be strongly modified by hydrogenation. In this work, two dimensional (2D) VO2 sheets have been grown on Si(1 1 1) surfaces through chemical vapor deposition, and metal (Au, Pt) thin films were deposited on VO2 surfaces by sputtering. The hydrogenation and dehydrogenation of VO2 and metal-decorated VO2 structures in H2 and in air were in situ studied by Raman. We found that hydrogenation and dehydrogenation temperatures have been significantly decreased with the VO2 surface decorated by Au and Pt. The enhanced hydrogenation and dehydrogenation reactions can be attributed to catalytic dissociation of H2 and O2 molecules on metal surfaces and subsequent spillover of dissociated H and O atoms to the oxide surfaces. PMID:27603090

  6. In situ Raman spectroscopy study of metal-enhanced hydrogenation and dehydrogenation of VO2

    NASA Astrophysics Data System (ADS)

    Wu, Hao; Fu, Qiang; Bao, Xinhe

    2016-11-01

    Vanadium dioxide (VO2) has a phase transition from insulator to metal at 340 K, and this transition can be strongly modified by hydrogenation. In this work, two dimensional (2D) VO2 sheets have been grown on Si(1 1 1) surfaces through chemical vapor deposition, and metal (Au, Pt) thin films were deposited on VO2 surfaces by sputtering. The hydrogenation and dehydrogenation of VO2 and metal-decorated VO2 structures in H2 and in air were in situ studied by Raman. We found that hydrogenation and dehydrogenation temperatures have been significantly decreased with the VO2 surface decorated by Au and Pt. The enhanced hydrogenation and dehydrogenation reactions can be attributed to catalytic dissociation of H2 and O2 molecules on metal surfaces and subsequent spillover of dissociated H and O atoms to the oxide surfaces.

  7. In situ Raman study of dissolved CaCO3 minerals under subduction zone conditions

    NASA Astrophysics Data System (ADS)

    Facq, S.; Daniel, I.; Sverjensky, D. A.

    2012-12-01

    The fate and the characteristics of the Earth's deep carbon reservoirs are still not well understood [1]. The connection between the surficial and the deep-Earth carbon cycles occurs at subduction zones where carbon is transported into the mantle and where hydrous silicates and carbonate minerals break down releasing H2O and C-species in fluids associated with mantle metasomatism and the generation of arc volcanism [2]. In order to obtain mass balance between recycling and burial in the deep mantle, the study of the dissolution of CaCO3 minerals in equilibrium with aqueous fluids under mantle conditions is crucial. We report a novel integrated experimental and theoretical study of the equilibration of CaCO3 minerals with aqueous solutions (pure water or NaCl solutions) at high pressures and temperatures (0.5 to 8 GPa and 250 to 500 °C). The fluid speciation was studied using in situ Raman spectroscopy coupled to an externally heated membrane type DAC equipped with 500 μm pure synthetic diamond anvils. In a typical experiment, the aqueous fluid and a calcite crystal [3] were loaded in a rhenium gasket. The pressure was determined from the calibrated shift of the carbonate υ1 symmetric stretching mode of aragonite and the temperature measured with a K-type thermocouple. Raman spectra were recorded using a Labram HR800 Raman spectrometer (Horiba Jobin-Yvon) coupled to a Spectra Physics Ar+ laser. At equilibrium with an aragonite crystal, the Raman data show that bicarbonate is the most abundant species in low-pressure fluids (below 4 GPa) whereas carbonate becomes progressively dominant at higher pressure. After correction from their Raman cross-sections [4], the relative amounts of dissolved carbonate and bicarbonate were estimated from the areas of the Raman bands of the carbonate and bicarbonate ions (υ1 and υ5 symmetric stretching modes, respectively). The presence of sodium chloride influences the speciation by extending the pressure field where the

  8. Boron phosphide under pressure: In situ study by Raman scattering and X-ray diffraction

    NASA Astrophysics Data System (ADS)

    Solozhenko, Vladimir L.; Kurakevych, Oleksandr O.; Le Godec, Yann; Kurnosov, Aleksandr V.; Oganov, Artem R.

    2014-07-01

    Cubic boron phosphide, BP, has been studied in situ by X-ray diffraction and Raman scattering up to 55 GPa at 300 K in a diamond anvil cell. The bulk modulus of B0 = 174(2) GPa has been established, which is in excellent agreement with our ab initio calculations. The data on Raman shift as a function of pressure, combined with equation-of-state (EOS) data, allowed us to estimate the Grüneisen parameters of the TO and LO modes of zinc-blende structure, γGTO= 1.26 and γGLO= 1.13, just like in the case of other AIIIBV diamond-like phases, for which γGTO> γGLO≅ 1. We also established that the pressure dependence of the effective electro-optical constant α is responsible for a strong change in relative intensities of the TO and LO modes from ITO/ILO ˜ 0.25 at 0.1 MPa to ITO/ILO ˜ 2.5 at 45 GPa, for which we also find excellent agreement between experiment and theory.

  9. Boron phosphide under pressure: In situ study by Raman scattering and X-ray diffraction

    SciTech Connect

    Solozhenko, Vladimir L.; Kurakevych, Oleksandr O.; Le Godec, Yann; Kurnosov, Aleksandr V.; Oganov, Artem R.

    2014-07-21

    Cubic boron phosphide, BP, has been studied in situ by X-ray diffraction and Raman scattering up to 55 GPa at 300 K in a diamond anvil cell. The bulk modulus of B{sub 0} = 174(2) GPa has been established, which is in excellent agreement with our ab initio calculations. The data on Raman shift as a function of pressure, combined with equation-of-state (EOS) data, allowed us to estimate the Grüneisen parameters of the TO and LO modes of zinc-blende structure, γ{sub G}{sup TO }= 1.26 and γ{sub G}{sup LO }= 1.13, just like in the case of other A{sup III}B{sup V} diamond-like phases, for which γ{sub G}{sup TO }> γ{sub G}{sup LO }≅ 1. We also established that the pressure dependence of the effective electro-optical constant α is responsible for a strong change in relative intensities of the TO and LO modes from I{sub TO}/I{sub LO} ∼ 0.25 at 0.1 MPa to I{sub TO}/I{sub LO} ∼ 2.5 at 45 GPa, for which we also find excellent agreement between experiment and theory.

  10. Intermediate stages of electrochemical oxidation of single-crystalline platinum revealed by in situ Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Huang, Yi-Fan; Kooyman, Patricia J.; Koper, Marc T. M.

    2016-08-01

    Understanding the atomistic details of how platinum surfaces are oxidized under electrochemical conditions is of importance for many electrochemical devices such as fuel cells and electrolysers. Here we use in situ shell-isolated nanoparticle-enhanced Raman spectroscopy to identify the intermediate stages of the electrochemical oxidation of Pt(111) and Pt(100) single crystals in perchloric acid. Density functional theory calculations were carried out to assist in assigning the experimental Raman bands by simulating the vibrational frequencies of possible intermediates and products. The perchlorate anion is suggested to interact with hydroxyl phase formed on the surface. Peroxo-like and superoxo-like two-dimensional (2D) surface oxides and amorphous 3D α-PtO2 are sequentially formed during the anodic polarization. Our measurements elucidate the process of the electrochemical oxidation of platinum single crystals by providing evidence for the structure-sensitive formation of a 2D platinum-(su)peroxide phase. These results may contribute towards a fundamental understanding of the mechanism of degradation of platinum electrocatalysts.

  11. Intermediate stages of electrochemical oxidation of single-crystalline platinum revealed by in situ Raman spectroscopy

    PubMed Central

    Huang, Yi-Fan; Kooyman, Patricia J.; Koper, Marc T. M.

    2016-01-01

    Understanding the atomistic details of how platinum surfaces are oxidized under electrochemical conditions is of importance for many electrochemical devices such as fuel cells and electrolysers. Here we use in situ shell-isolated nanoparticle-enhanced Raman spectroscopy to identify the intermediate stages of the electrochemical oxidation of Pt(111) and Pt(100) single crystals in perchloric acid. Density functional theory calculations were carried out to assist in assigning the experimental Raman bands by simulating the vibrational frequencies of possible intermediates and products. The perchlorate anion is suggested to interact with hydroxyl phase formed on the surface. Peroxo-like and superoxo-like two-dimensional (2D) surface oxides and amorphous 3D α-PtO2 are sequentially formed during the anodic polarization. Our measurements elucidate the process of the electrochemical oxidation of platinum single crystals by providing evidence for the structure-sensitive formation of a 2D platinum-(su)peroxide phase. These results may contribute towards a fundamental understanding of the mechanism of degradation of platinum electrocatalysts. PMID:27514695

  12. Intermediate stages of electrochemical oxidation of single-crystalline platinum revealed by in situ Raman spectroscopy.

    PubMed

    Huang, Yi-Fan; Kooyman, Patricia J; Koper, Marc T M

    2016-08-12

    Understanding the atomistic details of how platinum surfaces are oxidized under electrochemical conditions is of importance for many electrochemical devices such as fuel cells and electrolysers. Here we use in situ shell-isolated nanoparticle-enhanced Raman spectroscopy to identify the intermediate stages of the electrochemical oxidation of Pt(111) and Pt(100) single crystals in perchloric acid. Density functional theory calculations were carried out to assist in assigning the experimental Raman bands by simulating the vibrational frequencies of possible intermediates and products. The perchlorate anion is suggested to interact with hydroxyl phase formed on the surface. Peroxo-like and superoxo-like two-dimensional (2D) surface oxides and amorphous 3D α-PtO2 are sequentially formed during the anodic polarization. Our measurements elucidate the process of the electrochemical oxidation of platinum single crystals by providing evidence for the structure-sensitive formation of a 2D platinum-(su)peroxide phase. These results may contribute towards a fundamental understanding of the mechanism of degradation of platinum electrocatalysts.

  13. In Situ Perchlorate Determination on Purolite A850 Ion Exchange Resin via Raman Spectroscopy

    SciTech Connect

    Levitskaia, Tatiana G.; Sinkov, Sergei I.; Bryan, Samuel A.

    2007-07-17

    The reported investigation represents a first step toward development of a sensor methodology for in-situ determination of ionic species retained on ion exchange column. Raman spectroscopy was demonstrated as a detection method for determining perchlorate loading on a non-selective ion exchange resin, Purolite A850 acrylic gel. This method has been established using laboratory water (DIW) samples and actual California ground water (CAGW) samples with the complexities of competing ions, dissolved organics, and other potential interfering agents. The detection limit for this method of monitoring perchlorate on resin was measured to be 0.014 meq g-1 for both DIW and CAGW systems. The anion selectivity of the A850 resin was determined via batch contact experiments using CAGW. Linear correlation between resin loading with perchlorate and the intensity of the Raman perchlorate signal was observed and quantitatively described. The obtained relationship was applied for the determination of the perchlorate retained on the A850 resin in the column elution experiments.

  14. Hydrolysis of polycarbonate in sub-critical water in fused silica capillary reactor with in situ Raman spectroscopy

    USGS Publications Warehouse

    Pan, Z.; Chou, I.-Ming; Burruss, R.C.

    2009-01-01

    The advantages of using fused silica capillary reactor (FSCR) instead of conventional autoclave for studying chemical reactions at elevated pressure and temperature conditions were demonstrated in this study, including the allowance for visual observation under a microscope and in situ Raman spectroscopic characterization of polycarbonate and coexisting phases during hydrolysis in subcritical water. ?? 2009 The Royal Society of Chemistry.

  15. Stimulated Raman scattering microscopy for biomedical imaging

    NASA Astrophysics Data System (ADS)

    Min, Wei; Freudiger, Christian W.; Lu, Sijia; He, Chengwei; Kang, Jing X.; Xie, X. Sunney

    2009-02-01

    Label-free chemical contrast is highly desirable in biomedical imaging. Spontaneous Raman microscopy provides specific vibrational signatures of chemical bonds, but is often hindered by low sensitivity. Here we report a 3D multi-photon vibrational imaging technique based on stimulated Raman scattering (SRS). The sensitivity of SRS is significantly greater than that of spontaneous Raman scattering, and is further enhanced by high-frequency (MHz) phase-sensitive detection. SRS microscopy has a major advantage over previous coherent Raman techniques in that it offers background-free and easily interpretable chemical contrast. We show a variety of biomedical applications, such as differentiating distributions of omega-3 fatty acids and saturated lipids in living cells, imaging of brain and skin tissues based on intrinsic lipid contrast.

  16. Simulating realistic imaging conditions for in situ liquid microscopy

    SciTech Connect

    Welch, David A.; Faller, Roland; Evans, James E.; Browning, Nigel D.

    2013-12-01

    In situ transmission electron microscopy enables the imaging of biological cells, macromolecular protein complexes, nanoparticles, and other systems in a near-native environment. In order to improve interpretation of image contrast features and also predict ideal imaging conditions ahead of time, new virtual electron microscopic techniques are needed. A technique for virtual fluid-stage high-angle annular dark-field scanning transmission electron microscopy with the multislice method is presented that enables the virtual imaging of model fluid-stage systems composed of millions of atoms. The virtual technique is exemplified by simulating images of PbS nanoparticles under different imaging conditions and the results agree with previous experimental findings. General insight is obtained on the influence of the effects of fluid path length, membrane thickness, nanoparticle position, defocus and other microscope parameters on attainable image quality.

  17. Automated in situ brain imaging for mapping the Drosophila connectome.

    PubMed

    Lin, Chi-Wen; Lin, Hsuan-Wen; Chiu, Mei-Tzu; Shih, Yung-Hsin; Wang, Ting-Yuan; Chang, Hsiu-Ming; Chiang, Ann-Shyn

    2015-01-01

    Mapping the connectome, a wiring diagram of the entire brain, requires large-scale imaging of numerous single neurons with diverse morphology. It is a formidable challenge to reassemble these neurons into a virtual brain and correlate their structural networks with neuronal activities, which are measured in different experiments to analyze the informational flow in the brain. Here, we report an in situ brain imaging technique called Fly Head Array Slice Tomography (FHAST), which permits the reconstruction of structural and functional data to generate an integrative connectome in Drosophila. Using FHAST, the head capsules of an array of flies can be opened with a single vibratome sectioning to expose the brains, replacing the painstaking and inconsistent brain dissection process. FHAST can reveal in situ brain neuroanatomy with minimal distortion to neuronal morphology and maintain intact neuronal connections to peripheral sensory organs. Most importantly, it enables the automated 3D imaging of 100 intact fly brains in each experiment. The established head model with in situ brain neuroanatomy allows functional data to be accurately registered and associated with 3D images of single neurons. These integrative data can then be shared, searched, visualized, and analyzed for understanding how brain-wide activities in different neurons within the same circuit function together to control complex behaviors.

  18. Quantitative Raman Spectroscopy to monitor microbial metabolism in situ under pressure

    NASA Astrophysics Data System (ADS)

    Picard, A.; Daniel, I.; Oger, P.

    2006-12-01

    Although high hydrostatic pressure (HHP) biotopes are ubiquitous on Earth, little is known about the metabolism of piezophile organisms. Cell culture under HHP can be technically challenging, and equipment- dependent. In addition, the depressurization step required for analysis can lead to erroneous data. Therefore, to understand how piezophile organisms react to pressure, it is crucial to be able to monitor their activity in situ under HHP. We developed the use of Quantitative Raman Spectroscopy (QRS, 1) to monitor in situ the metabolism of organic molecules. This technique is based on the specific spectral signature of an analyte from which its concentration can be deduced. An application of this technique to the monitoring of alcoholic fermentation by the piezotolerant micro-eucaryote Saccharomyces cerevisiae is presented. Ethanol fermentation from glucose was monitored during 24h from ambient P up to 100 MPa in the low- pressure Diamond Anvil Cell (lpDAC, 2). The experimental compression chamber consisted in a 300 μm-thick Ni gasket in which a 500 μm-diameter hole was drilled. Early-stationnary yeast cells were inoculated into fresh low-fluorescence medium containing 0.15 M of glucose. Ethanol concentration was determined in situ by QRS using the symmetric C-C stretching mode of ethanol at 878 cm-1 normalizing the data to the intensity of the sulfate S-O stretching mode at 980 cm-1. In our setup, the detection limit of ethanol is lower than 0.05 mM with a precision below 1%. At ambient P, ethanol production in the lpDAC and in control experiments proceeds with the same kinetics. Thus, yeast is not affected by its confinement. This is further confirmed by its ability to bud with a generation time similar to control experiments performed in glass tubes at ambient pressure inside the lpDAC. Ethanol production by yeast occurs to at least 65 MPa (3). At 10 MPa, fermentation proceeds 3 times faster than at ambient P. Fermentation rates decrease linearly from 20 to

  19. Raman Hyperspectral Imaging of Microfossils: Potential Pitfalls

    PubMed Central

    Olcott Marshall, Alison

    2013-01-01

    Abstract Initially, Raman spectroscopy was a specialized technique used by vibrational spectroscopists; however, due to rapid advancements in instrumentation and imaging techniques over the last few decades, Raman spectrometers are widely available at many institutions, allowing Raman spectroscopy to become a widespread analytical tool in mineralogy and other geological sciences. Hyperspectral imaging, in particular, has become popular due to the fact that Raman spectroscopy can quickly delineate crystallographic and compositional differences in 2-D and 3-D at the micron scale. Although this rapid growth of applications to the Earth sciences has provided great insight across the geological sciences, the ease of application as the instruments become increasingly automated combined with nonspecialists using this techique has resulted in the propagation of errors and misunderstandings throughout the field. For example, the literature now includes misassigned vibration modes, inappropriate spectral processing techniques, confocal depth of laser penetration incorrectly estimated into opaque crystalline solids, and a misconstrued understanding of the anisotropic nature of sp2 carbons. Key Words: Raman spectroscopy—Raman imaging—Confocal Raman spectroscopy—Disordered sp2 carbons—Hematite—Microfossils. Astrobiology 13, 920–931. PMID:24088070

  20. In situ quantitative imaging of cellular lipids using molecular sensors

    NASA Astrophysics Data System (ADS)

    Yoon, Youngdae; Lee, Park J.; Kurilova, Svetlana; Cho, Wonhwa

    2011-11-01

    Membrane lipids are dynamic molecules that play important roles in cell signalling and regulation, but an in situ imaging method for quantitatively tracking lipids in living cells is lacking at present. Here, we report a new chemical method of quantitative lipid imaging using sensors engineered by labelling proteins with an environmentally sensitive fluorophore. A prototype sensor for phosphatidylinositol-4,5-bisphosphate (PtdIns(4,5)P2)—a key signalling lipid in diverse cellular processes—was generated by covalently attaching a single 2-dimethylamino-6-acyl-naphthalene group to the N-terminal α-helix of the engineered epsin1 ENTH domain, a protein that selectively binds PtdIns(4,5)P2. The sensor allows robust and sensitive in situ quantitative imaging in mammalian cells, providing new insight into the spatiotemporal dynamics and fluctuation of this key signalling lipid. Application of the sensor to immune cells reveals the presence of a local threshold PtdIns(4,5)P2 concentration required for triggering phagocytosis. This sensor strategy is generally applicable to in situ quantification of other cellular lipids.

  1. In Situ Raman Spectroscopic Study of Barite as a Pressure Gauge Using a Hydrothermal Diamond Anvil Cell.

    PubMed

    Liu, Chuanjiang; Wang, Duojun; Zheng, Haifei

    2016-02-01

    In situ Raman measurements of barite were performed at temperatures in the range of 298-673 K and pressures in the range of 105-1217 MPa using a hydrothermal diamond anvil cell combined with laser Raman spectroscopy. The Raman frequency and the full width at half maximum (FWHM) of the most intense ν1 Raman peak for barite as a function of pressure and temperature were obtained. In the experimental P-T ranges, the ν1Raman band systematically shifted toward low wavenumbers with increasing pressure and temperature. The positive pressure dependence of ν1Raman frequency indicates stress-induced shortening of the S-O bond, whereas the negative temperature dependence shows temperature-induced expansion of the S-O bond. In contrast, the observed ν1Raman band became broadened, which should be attributed to the reduced ordering of molecular structure. Based on the obtained data, the established relationships among the Raman shift or the FWHM, pressure and temperature can be used to obtain good estimates of the internal pressure in natural barite-bearing fluid inclusions or hydrothermal diamond anvil cell. This is a sensitive and reliable approach to the accurate determination of geological pressure. PMID:26903568

  2. In situ Raman-based detections of the hydrothermal vent and cold seep fluids

    NASA Astrophysics Data System (ADS)

    Zhang, Xin; Du, Zengfeng; Zheng, Ronger; Luan, Zhendong; Qi, Fujun; Cheng, Kai; Wang, Bing; Ye, Wangquan; Liu, Xiaorui; Chen, Changan; Guo, Jinjia; Li, Ying; Yan, Jun

    2016-04-01

    Hydrothermal vents and cold seeps, and their associated biological communities play an important role in global carbon and sulphur biogeochemical cycles. Most of the studies of fluid composition geochemistry are based on recovered samples, both with gas-tight samplers and as open specimens, but the in situ conditions are difficult to maintain in recovered samples. Determination in situ of the chemical signals of the emerging fluids are challenging due to the high pressure, often strongly acidic and temperature in which few sensors can survive. Most of those sensors used so far are based on electrochemistry, and can typically detect only a few chemical species. Here we show that direct measurement of critical chemical species of hydrothermal vents and cold seeps can be made rapidly and in situ by means of a new hybrid version of earlier deep-sea pore water Raman probe carried on the ROV (Remote Operated Vehicle) Faxian. The fluid was drawn through the probe by actuating a hydraulic pump on the ROV, and measured at the probe optical cell through a sapphire window. We have observed the concentrations of H2S, HS‑, SO42‑, HSO4‑, CO2, and H2 in hydrothermal vent fluids from the Pacmanus and Desmos vent systems in the Manus back-arc basin, Papua New Guinea. Two black smokers (279° C and 186° C) at the Pacmanus site showed the characteristic loss of SO42‑, and the increase of CO2 and well resolved H2S and HS‑ peaks. At the white smoker of Onsen site the strong HSO4‑peak observed at high temperature quickly dropped with strong accompanying increase of SO42‑and H2 peaks when the sample contained in the Raman sensing cell was removed from the hot fluid due to rapid thermal deprotonation. We report here also the finding of a new lower temperature (88° C) white smoker "Kexue" field at the Desmos site with strong H2S, HS‑ and CO2 signals. We also have detected the concentrations of CH4,H2S, HS‑, SO42‑, and S8 in cold seep fluids and the surrounding

  3. In situ Raman-based detections of the hydrothermal vent and cold seep fluids

    NASA Astrophysics Data System (ADS)

    Zhang, Xin; Du, Zengfeng; Zheng, Ronger; Luan, Zhendong; Qi, Fujun; Cheng, Kai; Wang, Bing; Ye, Wangquan; Liu, Xiaorui; Chen, Changan; Guo, Jinjia; Li, Ying; Yan, Jun

    2016-04-01

    Hydrothermal vents and cold seeps, and their associated biological communities play an important role in global carbon and sulphur biogeochemical cycles. Most of the studies of fluid composition geochemistry are based on recovered samples, both with gas-tight samplers and as open specimens, but the in situ conditions are difficult to maintain in recovered samples. Determination in situ of the chemical signals of the emerging fluids are challenging due to the high pressure, often strongly acidic and temperature in which few sensors can survive. Most of those sensors used so far are based on electrochemistry, and can typically detect only a few chemical species. Here we show that direct measurement of critical chemical species of hydrothermal vents and cold seeps can be made rapidly and in situ by means of a new hybrid version of earlier deep-sea pore water Raman probe carried on the ROV (Remote Operated Vehicle) Faxian. The fluid was drawn through the probe by actuating a hydraulic pump on the ROV, and measured at the probe optical cell through a sapphire window. We have observed the concentrations of H2S, HS-, SO42-, HSO4-, CO2, and H2 in hydrothermal vent fluids from the Pacmanus and Desmos vent systems in the Manus back-arc basin, Papua New Guinea. Two black smokers (279° C and 186° C) at the Pacmanus site showed the characteristic loss of SO42-, and the increase of CO2 and well resolved H2S and HS- peaks. At the white smoker of Onsen site the strong HSO4-peak observed at high temperature quickly dropped with strong accompanying increase of SO42-and H2 peaks when the sample contained in the Raman sensing cell was removed from the hot fluid due to rapid thermal deprotonation. We report here also the finding of a new lower temperature (88° C) white smoker "Kexue" field at the Desmos site with strong H2S, HS- and CO2 signals. We also have detected the concentrations of CH4,H2S, HS-, SO42-, and S8 in cold seep fluids and the surrounding sediment pore water from

  4. Mobile system for in-situ imaging of cultural objects

    NASA Astrophysics Data System (ADS)

    Zemlicka, J.; Jakubek, J.; Krejci, F.; Hradil, D.; Hradilova, J.; Mislerova, H.

    2012-01-01

    Non-invasive analytical techniques recently developed with the Timepix pixel detector have shown great potential for the inspection of objects of cultural heritage. We have developed new instrumentation and methodology for in-situ X-ray transmission radiography and X-ray fluorescence imaging and successfully tested and evaluated a mobile system for remote terrain tasks. The prototype portable imaging device comprises the radiation source tube and the spectral sensitive X-ray camera. Both components can be moreover mounted on independent motorized positioning systems allowing adaptation of irradiation geometry to the object shape. Both parts are placed onto a pair of universal portable holders (tripods). The detector is placed in a shielded box with exchangeable entrance window (beam filters and pinhole collimator). This adjustable setup allows performing in-situ measurements for both transmission and emission (XRF) radiography. The assembled system has been successfully tested in our laboratory with phantoms and real samples. The obtained and evaluated results are presented in this paper. Future work will include successive adaptation of the current system for real in-situ utilization and preparation of software allowing semi-automatic remote control of measurements.

  5. In-situ Raman spectroscopy and high-speed photography of a shocked triaminotrinitrobenzene based explosive

    SciTech Connect

    Saint-Amans, C.; Hébert, P. Doucet, M.; Resseguier, T. de

    2015-01-14

    We have developed a single-shot Raman spectroscopy experiment to study at the molecular level the initiation mechanisms that can lead to sustained detonation of a triaminotrinitrobenzene-based explosive. Shocks up to 30 GPa were generated using a two-stage laser-driven flyer plate generator. The samples were confined by an optical window and shock pressure was maintained for at least 30 ns. Photon Doppler Velocimetry measurements were performed at the explosive/window interface to determine the shock pressure profile. Raman spectra were recorded as a function of shock pressure and the shifts of the principal modes were compared to static high-pressure measurements performed in a diamond anvil cell. Our shock data indicate the role of temperature effects. Our Raman spectra also show a progressive extinction of the signal which disappears around 9 GPa. High-speed photography images reveal a simultaneous progressive darkening of the sample surface up to total opacity at 9 GPa. Reflectivity measurements under shock compression show that this opacity is due to a broadening of the absorption spectrum over the entire visible region.

  6. In-situ Raman spectroscopy and high-speed photography of a shocked triaminotrinitrobenzene based explosive

    NASA Astrophysics Data System (ADS)

    Saint-Amans, C.; Hébert, P.; Doucet, M.; de Resseguier, T.

    2015-01-01

    We have developed a single-shot Raman spectroscopy experiment to study at the molecular level the initiation mechanisms that can lead to sustained detonation of a triaminotrinitrobenzene-based explosive. Shocks up to 30 GPa were generated using a two-stage laser-driven flyer plate generator. The samples were confined by an optical window and shock pressure was maintained for at least 30 ns. Photon Doppler Velocimetry measurements were performed at the explosive/window interface to determine the shock pressure profile. Raman spectra were recorded as a function of shock pressure and the shifts of the principal modes were compared to static high-pressure measurements performed in a diamond anvil cell. Our shock data indicate the role of temperature effects. Our Raman spectra also show a progressive extinction of the signal which disappears around 9 GPa. High-speed photography images reveal a simultaneous progressive darkening of the sample surface up to total opacity at 9 GPa. Reflectivity measurements under shock compression show that this opacity is due to a broadening of the absorption spectrum over the entire visible region.

  7. Thermo-Raman spectroscopy in situ monitoring study of solid-state synthesis of NiO-Al 2O 3 nanoparticles and its characterization

    NASA Astrophysics Data System (ADS)

    Ghule, Anil Vithal; Ghule, Kalyani; Tzing, Shin-Hwa; Punde, Tushar H.; Chang, Hua; Ling, Yong Chien

    2009-12-01

    Hyphenation of thermogravimetric analyzer (TGA) and thermo-Raman spectrophotometer for in situ monitoring of solid-state reaction in oxygen atmosphere forming NiO-Al 2O 3 catalyst nanoparticles is investigated. In situ thermo-Raman spectra in the range from 200 to 1400 cm -1 were recorded at every degree interval from 25 to 800 °C. Thermo-Raman spectroscopic studies reveal that, although the onset of formation is around 600 °C, the bulk NiAl 2O 4 forms at temperatures above 800 °C. The X-ray diffraction (XRD) spectra and the scanning electron microscopy (SEM) images of the reaction mixtures were recorded at regular temperature intervals of 100 °C, in the temperature range from 400 to 1000 °C, which could provide information on structural and morphological evolution of NiO-Al 2O 3. Slow controlled heating of the sample enabled better control over morphology and particle size distribution (˜20-30 nm diameter). The observed results were supported by complementary characterizations using TGA, XRD, SEM, transmission electron microscopy, and energy dispersive X-ray analysis.

  8. In situ noninvasive Raman microspectroscopic investigation of polychrome plasterworks in the Alhambra.

    PubMed

    Dominguez-Vidal, Ana; de la Torre-Lopez, Maria Jose; Rubio-Domene, Ramon; Ayora-Cañada, Maria Jose

    2012-12-21

    A totally non-invasive in situ investigation in one of the main halls of the Palace of the Lions in the Alhambra (Granada, Spain) has been carried out. Analyses were made with a fiber-optic portable Raman microspectrometer placed on scaffolding platforms at a height of ca. 12 m above the ground level during the period of conservation works. The objects of this study are the decorated plasterworks in the seven vaults of the Hall of the Kings. Together with the results, the different practical problems related to the positioning of the instrumental setup and the influence of the local environment during the analysis are discussed. In general, high quality spectra were obtained despite difficulties for micro-probe head positioning and sometimes the vibrations of the corresponding scaffold. Different typical antiquity pigments have been identified: cinnabar, minium, carbon black and lapis lazuli. Furthermore, the luminescence pattern from lapis lazuli found in most blue decorations has allowed the establishment of the natural origin and provenance of the pigment. Apart from this natural lapis lazuli, synthetic ultramarine blue was also found in one of the vaults showing up a recent restoration. In addition, some degradation products of cinnabar and minium were identified, with the major advantage of providing real-time information to the conservators during their work. PMID:23085888

  9. In situ analysis of dynamic laminar flow extraction using surface-enhanced Raman spectroscopy

    PubMed Central

    Wang, Fei; Wang, Hua-Lin; Qiu, Yang; Chang, Yu-Long; Long, Yi-Tao

    2015-01-01

    In this study, we performed micro-scale dynamic laminar flow extraction and site-specific in situ chloride concentration measurements. Surface-enhanced Raman spectroscopy was utilized to investigate the diffusion process of chloride ions from an oil phase to a water phase under laminar flow. In contrast to common logic, we used SERS intensity gradients of Rhodamine 6G to quantitatively calculate the concentration of chloride ions at specific positions on a microfluidic chip. By varying the fluid flow rates, we achieved different extraction times and therefore different chloride concentrations at specific positions along the microchannel. SERS spectra from the water phase were recorded at these different positions, and the spatial distribution of the SERS signals was used to map the degree of nanoparticle aggregation. The concentration of chloride ions in the channel could therefore be obtained. We conclude that this method can be used to explore the extraction behaviour and efficiency of some ions or molecules that enhance the SERS intensity in water or oil by inducing nanoparticle aggregation. PMID:26687436

  10. Nanoscale Silicon as a Catalyst for Graphene Growth: Mechanistic Insight from in Situ Raman Spectroscopy

    DOE PAGES

    Share, Keith; Carter, Rachel E.; Nikolaev, Pavel; Hooper, Daylong; Oakes, Landon; Cohn, Adam P.; Rao, Rahul; Puretzky, Alexander A.; Geohegan, David B.; Maruyama, Benji; et al

    2016-06-08

    Nanoscale carbons are typically synthesized by thermal decomposition of a hydrocarbon at the surface of a metal catalyst. Whereas the use of silicon as an alternative to metal catalysts could unlock new techniques to seamlessly couple carbon nanostructures and semiconductor materials, stable carbide formation renders bulk silicon incapable of the precipitation and growth of graphitic structures. In this article, we provide evidence supported by comprehensive in situ Raman experiments that indicates nanoscale grains of silicon in porous silicon (PSi) scaffolds act as catalysts for hydrocarbon decomposition and growth of few-layered graphene at temperatures as low as 700 K. Self-limiting growthmore » kinetics of graphene with activation energies measured between 0.32–0.37 eV elucidates the formation of highly reactive surface-bound Si radicals that aid in the decomposition of hydrocarbons. Nucleation and growth of graphitic layers on PSi exhibits striking similarity to catalytic growth on nickel surfaces, involving temperature dependent surface and subsurface diffusion of carbon. Lastly, this work elucidates how the nanoscale properties of silicon can be exploited to yield catalytic properties distinguished from bulk silicon, opening an important avenue to engineer catalytic interfaces combining the two most technologically important materials for modern applications—silicon and nanoscale carbons.« less

  11. In situ pressure Raman spectroscopy and mechanical stability of superhard boron suboxide

    NASA Astrophysics Data System (ADS)

    Wang, Zhongwu; Zhao, Yusheng; Lazor, Peter; Annersten, Hans; Saxena, S. K.

    2005-01-01

    In situ Raman spectroscopy was used to explore the mechanical stability and electronic properties of superhard boron suboxide (B6O) under nonhydrostatic pressure. B6O stabilizes in a rhombohedral structure (R3¯m) to the peak pressure of 90GPa. The icosahedra-chain (B-O) phonon at 274cm-1 exhibits a negative pressure dependent profile of -0.21cm-1/GPa, while the intraicosahedral vibrations (B-B) between 400 and 1100cm-1 and the intericosahedral phonon at 1141cm-1 display 0.7-2.3 and 3.8cm-1/GPa, respectively. The small pressure dependencies of intraicosahedral modes resulting from the crystal lattice are significant indications of the low compressibility of B6O. Upon decompression to 3.3GPa, crystalline B6O transforms to the amorphous boron oxide and glassy boron. The structure instability of superhard B6O upon release of pressure implies its critical weakness for applications in harsh environments of dynamic impacts and high stress concentrations.

  12. In situ noninvasive Raman microspectroscopic investigation of polychrome plasterworks in the Alhambra.

    PubMed

    Dominguez-Vidal, Ana; de la Torre-Lopez, Maria Jose; Rubio-Domene, Ramon; Ayora-Cañada, Maria Jose

    2012-12-21

    A totally non-invasive in situ investigation in one of the main halls of the Palace of the Lions in the Alhambra (Granada, Spain) has been carried out. Analyses were made with a fiber-optic portable Raman microspectrometer placed on scaffolding platforms at a height of ca. 12 m above the ground level during the period of conservation works. The objects of this study are the decorated plasterworks in the seven vaults of the Hall of the Kings. Together with the results, the different practical problems related to the positioning of the instrumental setup and the influence of the local environment during the analysis are discussed. In general, high quality spectra were obtained despite difficulties for micro-probe head positioning and sometimes the vibrations of the corresponding scaffold. Different typical antiquity pigments have been identified: cinnabar, minium, carbon black and lapis lazuli. Furthermore, the luminescence pattern from lapis lazuli found in most blue decorations has allowed the establishment of the natural origin and provenance of the pigment. Apart from this natural lapis lazuli, synthetic ultramarine blue was also found in one of the vaults showing up a recent restoration. In addition, some degradation products of cinnabar and minium were identified, with the major advantage of providing real-time information to the conservators during their work.

  13. In situ analysis of dynamic laminar flow extraction using surface-enhanced Raman spectroscopy.

    PubMed

    Wang, Fei; Wang, Hua-Lin; Qiu, Yang; Chang, Yu-Long; Long, Yi-Tao

    2015-01-01

    In this study, we performed micro-scale dynamic laminar flow extraction and site-specific in situ chloride concentration measurements. Surface-enhanced Raman spectroscopy was utilized to investigate the diffusion process of chloride ions from an oil phase to a water phase under laminar flow. In contrast to common logic, we used SERS intensity gradients of Rhodamine 6G to quantitatively calculate the concentration of chloride ions at specific positions on a microfluidic chip. By varying the fluid flow rates, we achieved different extraction times and therefore different chloride concentrations at specific positions along the microchannel. SERS spectra from the water phase were recorded at these different positions, and the spatial distribution of the SERS signals was used to map the degree of nanoparticle aggregation. The concentration of chloride ions in the channel could therefore be obtained. We conclude that this method can be used to explore the extraction behaviour and efficiency of some ions or molecules that enhance the SERS intensity in water or oil by inducing nanoparticle aggregation. PMID:26687436

  14. Reduction Dynamics of Doped Ceria, Nickel Oxide, and Cermet Composites Probed Using In Situ Raman Spectroscopy

    PubMed Central

    Shearing, Paul R.; Brightman, Edward; Brett, Dan J. L.; Brandon, Nigel P.; Cohen, Lesley F.

    2016-01-01

    The redox properties of gadolinium doped ceria (CGO) and nickel oxide (NiO) composite cermets underpin the operation of solid oxide electrochemical cells. Although these systems have been widely studied, a full comprehension of the reaction dynamics at the interface of these materials is lacking. Here, in situ Raman spectroscopic monitoring of the redox cycle is used to investigate the interplay between the dynamic and competing processes of hydrogen spillover and water dissociation on the doped ceria surface. In order to elucidate these mechanisms, the redox process in pure CGO and NiO is studied when exposed to wet and dry hydrogen and is compared to the cermet behavior. In dry hydrogen, CGO reduces relatively rapidly via a series of intermediate phases, while NiO reduces via a single‐step process. In wet reducing atmospheres, however, the oxidation state of pure CGO is initially stabilized due to the dissociation of water by reduced Ce(III) and subsequent incorporation of oxygen into the structure. In the reduction process involving the composite cermet, the close proximity of the NiO improves the efficiency and speed of the composite reduction process. Although NiO is already incorporated into working cells, these observations suggest direct routes to further improve cell performance. PMID:27595058

  15. Reduction Dynamics of Doped Ceria, Nickel Oxide, and Cermet Composites Probed Using In Situ Raman Spectroscopy

    PubMed Central

    Shearing, Paul R.; Brightman, Edward; Brett, Dan J. L.; Brandon, Nigel P.; Cohen, Lesley F.

    2016-01-01

    The redox properties of gadolinium doped ceria (CGO) and nickel oxide (NiO) composite cermets underpin the operation of solid oxide electrochemical cells. Although these systems have been widely studied, a full comprehension of the reaction dynamics at the interface of these materials is lacking. Here, in situ Raman spectroscopic monitoring of the redox cycle is used to investigate the interplay between the dynamic and competing processes of hydrogen spillover and water dissociation on the doped ceria surface. In order to elucidate these mechanisms, the redox process in pure CGO and NiO is studied when exposed to wet and dry hydrogen and is compared to the cermet behavior. In dry hydrogen, CGO reduces relatively rapidly via a series of intermediate phases, while NiO reduces via a single‐step process. In wet reducing atmospheres, however, the oxidation state of pure CGO is initially stabilized due to the dissociation of water by reduced Ce(III) and subsequent incorporation of oxygen into the structure. In the reduction process involving the composite cermet, the close proximity of the NiO improves the efficiency and speed of the composite reduction process. Although NiO is already incorporated into working cells, these observations suggest direct routes to further improve cell performance.

  16. Electrolytic synthesis of aqueous aluminum nanoclusters and in situ characterization by femtosecond Raman spectroscopy and computations

    PubMed Central

    Wang, Wei; Liu, Weimin; Chang, I-Ya; Wills, Lindsay A.; Zakharov, Lev N.; Boettcher, Shannon W.; Cheong, Paul Ha-Yeon; Fang, Chong; Keszler, Douglas A.

    2013-01-01

    The selective synthesis and in situ characterization of aqueous Al-containing clusters is a long-standing challenge. We report a newly developed integrated platform that combines (i) a selective, atom-economical, step-economical, scalable synthesis of Al-containing nanoclusters in water via precision electrolysis with strict pH control and (ii) an improved femtosecond stimulated Raman spectroscopic method covering a broad spectral range of ca. 350–1,400 cm−1 with high sensitivity, aided by ab initio computations, to elucidate Al aqueous cluster structures and formation mechanisms in real time. Using this platform, a unique view of flat [Al13(μ3-OH)6(μ2-OH)18(H2O)24](NO3)15 nanocluster formation is observed in water, in which three distinct reaction stages are identified. The initial stage involves the formation of an [Al7(μ3-OH)6(μ2-OH)6(H2O)12]9+ cluster core as an important intermediate toward the flat Al13 aqueous cluster. PMID:24167254

  17. In situ metabolomic mass spectrometry imaging: recent advances and difficulties.

    PubMed

    Miura, Daisuke; Fujimura, Yoshinori; Wariishi, Hiroyuki

    2012-08-30

    MS imaging (MSI) is a remarkable new technology that enables us to determine the distribution of biological molecules present in tissue sections by direct ionization and detection. This technique is now widely used for in situ imaging of endogenous or exogenous molecules such as proteins, lipids, drugs and their metabolites, and it is a potential tool for pathological analysis and the investigation of disease mechanisms. MSI is also thought to be a technique that could be used for biomarker discovery with spatial information. The application of MSI to the study of endogenous metabolites has received considerable attention because metabolites are the result of the interactions of a system's genome with its environment and a total set of these metabolites more closely represents the phenotype of an organism under a given set of conditions. Recent studies have suggested the importance of in situ metabolite imaging in biological discovery and biomedical applications, but several issues regarding the technical application limits of MSI still remained to be resolved. In this review, we describe the capabilities of the latest MSI techniques for the imaging of endogenous metabolites in biological samples, and also discuss the technical problems and new challenges that need to be addressed for effective and widespread application of MSI in both preclinical and clinical settings.

  18. Structure sensitive in situ Raman study of iron passive films using SERS-active Fe/Au(111) substrates

    NASA Astrophysics Data System (ADS)

    Allongue, P.; Joiret, S.

    2005-03-01

    This work describes the preparation of well-defined Fe/Au(111) /mica substrates for in situ Raman studies of the iron passive film with surface-enhanced Raman scattering (SERS). It is a two-step technique in which a SERS active (111) epitaxial gold substrate is prepared by resistive evaporation on mica. An epitaxial Fe(110) film is then electrodeposited to serve as iron electrode. It is shown that the SERS enhancement factor depends primarily on the good matching between the gold film plasmon resonance wavelength λP and the excitation wavelength. The iron thickness is the second main parameter controlling the SERS enhancement factor with a maximum found for a thickness of 20 monolayers. Under optimized conditions an amplification factor of 5×104 is demonstrated with respect to the case of a bulk polycrystalline iron substrate. This technique allows the recording of Raman spectra of nm-thick passive films within a few seconds only, which opens up to nearly real-time bias-dependent investigations of the chemistry at the electrochemical interface. In addition, taking advantage of the well-defined structure of the Fe(110)/Au(111)/ mica substrates, we present a preliminary structure-sensitive in situ Raman study of the iron passive film formed in a borate solution of pH8.4 . It is thought that this simple approach of promoting SERS should find more general interest for the electrochemistry community.

  19. A virtual experiment control and data acquisition system for in situ laser heated diamond anvil cell Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Subramanian, N.; Struzhkin, Viktor V.; Goncharov, Alexander F.; Hemley, Russell J.

    2010-09-01

    Doubled-sided laser heated diamond anvil cell methods allow simultaneous in situ confocal Raman measurements of materials up to megabar pressures and high temperatures. This paper describes a virtual control and data acquisition system developed to automate setups for simultaneous Raman/laser heating experiments. The system enables reduction of experiment time by ˜90% in comparison to manual operations, allowing measurements of high quality Raman spectra of even highly reactive or diffusive samples, such as hydrogen at extreme conditions using continuous wave laser heating. These types of measurements are very difficult and often impossible to obtain in a manual operation mode. Complete data archiving and accurate control of various experimental parameters (e.g., on-the-fly temperature determination and self-adjusting data collection time to avoid signal saturation) can be done, and open up possibilities of other types of experiments involving extreme conditions.

  20. In situ protein secondary structure determination in ice: Raman spectroscopy-based process analytical tool for frozen storage of biopharmaceuticals.

    PubMed

    Roessl, Ulrich; Leitgeb, Stefan; Pieters, Sigrid; De Beer, Thomas; Nidetzky, Bernd

    2014-08-01

    A Raman spectroscopy-based method for in situ monitoring of secondary structural composition of proteins during frozen and thawed storage was developed. A set of reference proteins with different α-helix and β-sheet compositions was used for calibration and validation in a chemometric approach. Reference secondary structures were quantified with circular dichroism spectroscopy in the liquid state. Partial least squares regression models were established that enable estimation of secondary structure content from Raman spectra. Quantitative secondary structure determination in ice was accomplished for the first time and correlation with existing (qualitative) protein structural data from the frozen state was achieved. The method can be used in the presence of common stabilizing agents and is applicable in an industrial freezer setup. Raman spectroscopy represents a powerful, noninvasive, and flexibly applicable tool for protein stability monitoring during frozen storage.

  1. RNA Imaging with Multiplexed Error Robust Fluorescence in situ Hybridization

    PubMed Central

    Moffitt, Jeffrey R.; Zhuang, Xiaowei

    2016-01-01

    Quantitative measurements of both the copy number and spatial distribution of large fractions of the transcriptome in single-cells could revolutionize our understanding of a variety of cellular and tissue behaviors in both healthy and diseased states. Single-molecule Fluorescence In Situ Hybridization (smFISH)—an approach where individual RNAs are labeled with fluorescent probes and imaged in their native cellular and tissue context—provides both the copy number and spatial context of RNAs but has been limited in the number of RNA species that can be measured simultaneously. Here we describe Multiplexed Error Robust Fluorescence In Situ Hybridization (MERFISH), a massively parallelized form of smFISH that can image and identify hundreds to thousands of different RNA species simultaneously with high accuracy in individual cells in their native spatial context. We provide detailed protocols on all aspects of MERFISH, including probe design, data collection, and data analysis to allow interested laboratories to perform MERFISH measurements themselves. PMID:27241748

  2. Probing Xylan-Specific Raman Bands for Label-Free Imaging Xylan in Plant Cell Wall

    SciTech Connect

    Zeng, Yining; Yarbrough, John M.; Mittal, Ashutosh; Tucker, Melvin P.; Vinzant, Todd; Himmel, Michael E.

    2015-06-15

    Xylan constitutes a significant portion of biomass (e.g. 22% in corn stover used in this study). Xylan is also an important source of carbohydrates, besides cellulose, for renewable and sustainable energy applications. Currently used method for the localization of xylan in biomass is to use fluorescence confocal microscope to image the fluorescent dye labeled monoclonal antibody that specifically binds to xylan. With the rapid adoption of the Raman-based label-free chemical imaging techniques in biology, identifying Raman bands that are unique to xylan would be critical for the implementation of the above label-free techniques for in situ xylan imaging. Unlike lignin and cellulose that have long be assigned fingerprint Raman bands, specific Raman bands for xylan remain unclear. The major challenge is the cellulose in plant cell wall, which has chemical units highly similar to that of xylan. Here we report using xylanase to specifically remove xylan from feedstock. Under various degree of xylan removal, with minimum impact to other major cell wall components, i.e. lignin and cellulose, we have identified Raman bands that could be further tested for chemical imaging of xylan in biomass in situ.

  3. In situ Measurement of Pore-Water pH in Anoxic Sediments Using Laser Raman Spectrometry

    NASA Astrophysics Data System (ADS)

    Peltzer, E. T.; Luna, M.; Walz, P. M.; Zhang, X.; Brewer, P. G.

    2010-12-01

    Accurate measurement of the geochemical properties of sediment pore waters is of fundamental importance in ocean geochemistry and microbiology. Recent work has shown that the properties of pore waters can be measured rapidly in situ with a novel Raman based insertion probe (Zhang et al., 2010), and that data obtained from anoxic sediments on in situ dissolved methane concentrations are very different (~30x) than from recovered cores due the large scale degassing that occurs during core recovery (Zhang et al., submitted). Degassing of methane must carry with it via Henry’s Law partioning significant quantities of H2S, which is clearly detectable by smell during sample processing, and thus in situ measurement of H2S is also highly desirable. In practice, dissolved H2S is partitioned between the HS- and H2S species as a function of pH with pKa ~7 for the acid dissociation reaction. Since both species are Raman active full determination of the sulfide system is possible if the relative Raman cross sections are known. The diagenetic equations for these reactions are commonly summarized as: 2CH2O + SO4= ↔ 2HCO3- + H2S CH4 + SO4= ↔ HCO3- + HS- + H2O Three of the major components of these equations, CH4, SO4=, and H2S/HS-, are all observable directly by Raman spectroscopy; but the detection of HCO3- presents a challenge due to its low Raman cross section and thus poor sensitivity. We show that pore water pH, which is a good estimator of HCO3- if total CO2 or alkalinity are known, can be measured by observing the H2S / HS- ratio via the equation: pH = pKa + log([HS-]/[H2S]) thereby fully constraining these equations within a single measurement protocol. The Raman peak for HS- is at 2573 cm-1 and for H2S is at 2592 cm-1; thus the peaks are well separated and may easily be deconvoluted from the observed spectrum. We have determined the relative Raman cross sections by a series of laboratory measurements over a range of pH and by using the definition that when pH = p

  4. In Situ Chemical Imaging of Plant Cell Walls Using CARS/SRS Microscopy (Poster)

    SciTech Connect

    Zeng, Y.; Liu, Y. S.; Saar, B. G.; Xie, X. S.; Chen, F.; Dixon, R. A.; Himmel, M. E.; Ding S. Y.

    2009-06-01

    This poster demonstrates coherent anti-Stokes Raman scattering and stimulated Raman scattering of plant cell walls. It includes simultaneous chemical imaging of lignin and cellulose (corn stover) during acidic pretreatment.

  5. In situ mobile subaquatic archaeometry evaluated by non-destructive Raman microscopy of gemstones lying under impure waters.

    PubMed

    Smith, David C

    2003-08-01

    A series of laboratory simulations have been made in order to evaluate the credibility of carrying out physico-chemical analysis of cultural heritage items by Raman spectral fingerprinting using a mobile Raman microscope in situ under natural impure water in subaquatic or submarine conditions. Three different kinds of gemstone (zircon, microcline and sodalite) were successively placed under different kinds of impure water into which a low power microscope objective was immersed to eliminate the normal aerial pathway between the objective and the object to be analysed. According to the nature of the impurities (inorganic or organic, dissolved or suspended, transparent or coloured) the results obtained variously gave Raman band intensities stronger than, similar to or weaker than those of spectra obtained without water, i.e. in air. The significant point is that after only minor spectral treatment the less good spectra nevertheless yielded exploitable data with most, if not all, of the key Raman bands being detected. Thus the problems of fluorescence or peak absences under water are of a similar degree of magnitude to the other problems inherent with the Raman spectroscopic technique in aerial conditions, e.g. relative peak intensities varying with crystal orientation; peak positions varying with chemical composition. These results indicate that even if at certain sites of submerged cities or sunken ships, the combination of animal, vegetal, mineral and microbial impurities join together to inhibit or hinder the success of subaquatic or submarine archaeometry, there will certainly be other sites where such activity is indeed credible.

  6. In situ mobile subaquatic archaeometry evaluated by non-destructive Raman microscopy of gemstones lying under impure waters

    NASA Astrophysics Data System (ADS)

    Smith, David C.

    2003-08-01

    A series of laboratory simulations have been made in order to evaluate the credibility of carrying out physico-chemical analysis of cultural heritage items by Raman spectral fingerprinting using a mobile Raman microscope in situ under natural impure water in subaquatic or submarine conditions. Three different kinds of gemstone (zircon, microcline and sodalite) were successively placed under different kinds of impure water into which a low power microscope objective was immersed to eliminate the normal aerial pathway between the objective and the object to be analysed. According to the nature of the impurities (inorganic or organic, dissolved or suspended, transparent or coloured) the results obtained variously gave Raman band intensities stronger than, similar to or weaker than those of spectra obtained without water, i.e. in air. The significant point is that after only minor spectral treatment the less good spectra nevertheless yielded exploitable data with most, if not all, of the key Raman bands being detected. Thus the problems of fluorescence or peak absences under water are of a similar degree of magnitude to the other problems inherent with the Raman spectroscopic technique in aerial conditions, e.g. relative peak intensities varying with crystal orientation; peak positions varying with chemical composition. These results indicate that even if at certain sites of submerged cities or sunken ships, the combination of animal, vegetal, mineral and microbial impurities join together to inhibit or hinder the success of subaquatic or submarine archaeometry, there will certainly be other sites where such activity is indeed credible.

  7. In situ mobile subaquatic archaeometry evaluated by non-destructive Raman microscopy of gemstones lying under impure waters.

    PubMed

    Smith, David C

    2003-08-01

    A series of laboratory simulations have been made in order to evaluate the credibility of carrying out physico-chemical analysis of cultural heritage items by Raman spectral fingerprinting using a mobile Raman microscope in situ under natural impure water in subaquatic or submarine conditions. Three different kinds of gemstone (zircon, microcline and sodalite) were successively placed under different kinds of impure water into which a low power microscope objective was immersed to eliminate the normal aerial pathway between the objective and the object to be analysed. According to the nature of the impurities (inorganic or organic, dissolved or suspended, transparent or coloured) the results obtained variously gave Raman band intensities stronger than, similar to or weaker than those of spectra obtained without water, i.e. in air. The significant point is that after only minor spectral treatment the less good spectra nevertheless yielded exploitable data with most, if not all, of the key Raman bands being detected. Thus the problems of fluorescence or peak absences under water are of a similar degree of magnitude to the other problems inherent with the Raman spectroscopic technique in aerial conditions, e.g. relative peak intensities varying with crystal orientation; peak positions varying with chemical composition. These results indicate that even if at certain sites of submerged cities or sunken ships, the combination of animal, vegetal, mineral and microbial impurities join together to inhibit or hinder the success of subaquatic or submarine archaeometry, there will certainly be other sites where such activity is indeed credible. PMID:12909148

  8. Fluorescent In Situ Hybridization in Suspension by Imaging Flow Cytometry.

    PubMed

    Maguire, Orla; Wallace, Paul K; Minderman, Hans

    2016-01-01

    The emergence of imaging flow cytometry (IFC) has brought novel applications exploiting its advantages over conventional flow cytometry and microscopy. One of the new applications is fluorescence in situ hybridization in suspension (FISH-IS). Conventional FISH is a slide-based approach in which the spotlike imagery resulting from hybridization with fluorescently tagged probes is evaluated by fluorescence microscopy. The FISH-IS approach evaluated by IFC enables the evaluation of tens to hundreds of thousands of cells in suspension and the analysis can be automated and standardized diminishing operator bias from the analysis. The high cell number throughput of FISH-IS improves the detection of rare events compared to conventional FISH. The applicability of FISH-IS is currently limited to detection of abnormal quantitative differences of hybridization targets such as occur in numerical chromosome abnormalities, deletions and amplifications.Here, we describe a protocol for FISH-IS using chromosome enumeration probes as an example. PMID:27460240

  9. Solid-state Raman image amplification

    NASA Astrophysics Data System (ADS)

    Calmes, Lonnie Kirkland

    Amplification of low-light-level optical images is important for extending the range of lidar systems that image and detect objects in the atmosphere and underwater. The use of range-gating to produce images of particular range bins is also important in minimizing the image degradation due to light that is scattered backward from aerosols, smoke, or water along the imaging path. For practical lidar systems that must be operated within sight of unprotected observers, eye safety is of the utmost importance. This dissertation describes a new type of eye-safe, range-gated lidar sensing element based on Solid-state Raman Image Amplification (SSRIA) in a solid- state optical crystal. SSRIA can amplify low-level images in the eye-safe infrared at 1.556 μm with gains up to 106 with the addition of only quantum- limited noise. The high gains from SSRIA can compensate for low quantum efficiency detectors and can reduce the need for detector cooling. The range-gate of SSRIA is controlled by the pulsewidth of the pump laser and can be as short as 30-100 cm, using pump pulses of 2-6.7 nsec FWHM. A rate equation theoretical model is derived to help in the design of short pulsed Raman lasers. A theoretical model for the quantum noise properties of SSRIA is presented. SSRIA results in higher SNR images throughout a broad range of incident light levels, in contrast to the increasing noise factor with reduced gain in image intensified CCD's. A theoretical framework for the optical resolution of SSRIA is presented and it is shown that SSRIA can produce higher resolution than ICCD's. SSRIA is also superior in rejecting unwanted sunlight background, further increasing image SNR. Lastly, SSRIA can be combined with optical pre-filtering to perform optical image processing functions such as high-pass filtering and automatic target detection/recognition. The application of this technology to underwater imaging, called Marine Raman Image Amplification (MARIA) is also discussed. MARIA

  10. Three-Dimensional Network of Cation-Cation-Bound Neptunyl(V) Squares: Synthesis and in Situ Raman Spectroscopy Studies.

    PubMed

    Jin, Geng Bang

    2016-03-01

    Cation-cation interactions (CCIs) are an essential feature of actinyl chemistry, particularly neptunyl(V). To better understand the formation mechanisms of CCIs, the crystallization process of Np(V) CCI compounds has been explored during the evaporation of acidic Np(V) stock solutions using X-ray diffraction and both ex situ and in situ Raman spectroscopy. At least four Np solid products have been isolated from evaporation of the same Np(V) acidic solution. In situ evaporation using a continuous wave laser (532 nm) as a local heat source produced similar solid products to ex situ experiments with matching Raman signatures. The formation of these products is highly dependent on the evaporation conditions. Slower evaporation appears to favor the formation of a new neptunyl(V) compound, (NpO2)Cl(H2O)2 (1), over other solid products. The structure of 1 features a three-dimensional network of NpO2(+) cations, where neighboring Np(V) ions are only connected to each other through CCIs in a square arrangement. The O═Np═O stretching region shows similar Raman bands in both the solids and solution suggesting that CCIs between Np(V) cations exist prior to crystallization. These results provide new insight into the formation mechanism of Np(V) CCI compounds from solutions.

  11. Better understanding of dissolution behaviour of amorphous drugs by in situ solid-state analysis using Raman spectroscopy.

    PubMed

    Savolainen, M; Kogermann, K; Heinz, A; Aaltonen, J; Peltonen, L; Strachan, C; Yliruusi, J

    2009-01-01

    Amorphous drugs have a higher kinetic solubility and dissolution rate than their crystalline counterparts. However, this advantage is lost if the amorphous form converts to the stable crystalline form during the dissolution as the dissolution rate will gradually change to that of the crystalline form. The purpose of this study was to use in situ Raman spectroscopy in combination with either partial least squares discriminant analysis (PLS-DA) or partial least squares (PLS) regression analysis to monitor as well as quantify the solid-phase transitions that take place during the dissolution of two amorphous drugs, indomethacin (IMC) and carbamazepine (CBZ). The dissolution rate was higher from amorphous IMC compared to the crystalline alpha- and gamma-forms. However, the dissolution rate started to slow down during the experiment. In situ Raman analysis verified that at that time point the sample started to crystallize to the alpha-form. Amorphous CBZ instantly started to crystallize upon contact with the dissolution medium. The transition from the amorphous form to CBZ dihydrate appears to go through the anhydrate form I. Based on the PLS analysis the amount of form I formed in the sample during the dissolution affected the dissolution rate. Raman spectroscopy combined with PLS-DA was also more sensitive to the solid-state changes than X-ray powder diffraction (XRPD) and was able to detect changes in the solid-state that could not be detected with XRPD. PMID:18590816

  12. Interplay between crystallinity profiles and the performance of microcrystalline thin-film silicon solar cells studied by in-situ Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Fink, T.; Muthmann, S.; Mück, A.; Gordijn, A.; Carius, R.; Meier, M.

    2015-12-01

    The intrinsic microcrystalline absorber layer growth in thin-film silicon solar-cells is investigated by in-situ Raman spectroscopy during plasma enhanced chemical vapor deposition. In-situ Raman spectroscopy enables a detailed study of the correlation between the process settings, the evolution of the Raman crystallinity in growth direction, and the photovoltaic parameters η (solar cell conversion efficiency), JSC (short circuit current density), FF (fill factor), and VOC (open circuit voltage). Raman spectra were taken every 7 nm of the absorber layer growth depending on the process settings. The Raman crystallinity of growing microcrystalline silicon was determined with an absolute error of approximately ±5% for total absorber layer thicknesses >50 nm. Due to this high accuracy, inherent drifts of the Raman crystallinity profiles are resolvable for almost the entire absorber layer deposition. For constant process settings and optimized solar cell device efficiency Raman crystallinity increases during the absorber layer growth. To compensate the inhomogeneous absorber layer growth process settings were adjusted. As a result, absorber layers with a constant Raman crystallinity profile — as observed in-situ — were deposited. Solar cells with those absorber layers show a strongly enhanced conversion efficiency by ˜0.5% absolute. However, the highest FF, VOC, and JSC were detected for solar cells with different Raman crystallinity profiles. In particular, fill factors of 74.5% were observed for solar cells with decreasing Raman crystallinity during the later absorber layer growth. In contrast, intrinsic layers with favorable JSC are obtained for constant and increasing Raman crystallinity profiles. Therefore, monitoring the evolution of the Raman crystallinity in-situ provides sufficient information for an optimization of the photovoltaic parameters with surpassing depth resolution.

  13. Intermediates in the cation reactions in solution probed by an in situ surface enhanced Raman scattering method

    NASA Astrophysics Data System (ADS)

    Tan, Chih-Shan; Chen, Hung-Ying; Chen, Hsueh-Szu; Gwo, Shangjr; Chen, Lih-Juann

    2015-09-01

    For chemical reactions in liquid state, such as catalysis, understanding of dynamical changes is conducive to practical applications. Solvation of copper salts in aqueous solution has implications for life, the environment, and industry. In an ongoing research, the question arises that why the color of aqueous CuCl2 solution changes with solution concentration? In this work, we have developed a convenient and efficient in situ surface enhanced Raman scattering technique to probe the presence of many intermediates, some of them are responsible for color change, in crystallization of aqueous copper chloride solution. The versatility of the novel technique was confirmed in the identification of five intermediates states in the transition from CdS to MoS2 nanowires in solution. The facile in situ method is expected to be widely applicable in probing intermediate states in a variety of chemical reactions in solution.

  14. Intermediates in the cation reactions in solution probed by an in situ surface enhanced Raman scattering method.

    PubMed

    Tan, Chih-Shan; Chen, Hung-Ying; Chen, Hsueh-Szu; Gwo, Shangjr; Chen, Lih-Juann

    2015-01-01

    For chemical reactions in liquid state, such as catalysis, understanding of dynamical changes is conducive to practical applications. Solvation of copper salts in aqueous solution has implications for life, the environment, and industry. In an ongoing research, the question arises that why the color of aqueous CuCl2 solution changes with solution concentration? In this work, we have developed a convenient and efficient in situ surface enhanced Raman scattering technique to probe the presence of many intermediates, some of them are responsible for color change, in crystallization of aqueous copper chloride solution. The versatility of the novel technique was confirmed in the identification of five intermediates states in the transition from CdS to MoS2 nanowires in solution. The facile in situ method is expected to be widely applicable in probing intermediate states in a variety of chemical reactions in solution. PMID:26333518

  15. Intermediates in the cation reactions in solution probed by an in situ surface enhanced Raman scattering method

    PubMed Central

    Tan, Chih-Shan; Chen, Hung-Ying; Chen, Hsueh-Szu; Gwo, Shangjr; Chen, Lih-Juann

    2015-01-01

    For chemical reactions in liquid state, such as catalysis, understanding of dynamical changes is conducive to practical applications. Solvation of copper salts in aqueous solution has implications for life, the environment, and industry. In an ongoing research, the question arises that why the color of aqueous CuCl2 solution changes with solution concentration? In this work, we have developed a convenient and efficient in situ surface enhanced Raman scattering technique to probe the presence of many intermediates, some of them are responsible for color change, in crystallization of aqueous copper chloride solution. The versatility of the novel technique was confirmed in the identification of five intermediates states in the transition from CdS to MoS2 nanowires in solution. The facile in situ method is expected to be widely applicable in probing intermediate states in a variety of chemical reactions in solution. PMID:26333518

  16. Mechanochemical C-H bond activation: rapid and regioselective double cyclopalladation monitored by in situ Raman spectroscopy.

    PubMed

    Juribašić, Marina; Užarević, Krunoslav; Gracin, Davor; Ćurić, Manda

    2014-09-14

    The first direct mechanochemical transition-metal-mediated activation of strong phenyl C-H bonds is reported. The mechanochemical procedure, resulting in cyclopalladated complexes, is quantitative and significantly faster than solution synthesis and allows highly regioselective activation of two C-H bonds by palladium(II) acetate in asymmetrically substituted azobenzene. Milling is monitored by in situ solid-state Raman spectroscopy which in combination with quantum-chemical calculations enabled characterization of involved reaction species, direct insight into the dynamics and reaction pathways, as well as the optimization of a milling process.

  17. Practical in-situ determination of ortho-para hydrogen ratios via fiber-optic based Raman spectroscopy

    DOE PAGES

    Sutherland, Liese -Marie; Knudson, James N.; Mocko, Michal; Renneke, Richard M.

    2015-12-17

    An experiment was designed and developed to prototype a fiber-optic-based laser system, which measures the ratio of ortho-hydrogen to para-hydrogen in an operating neutron moderator system at the Los Alamos Neutron Science Center (LANSCE) spallation neutron source. Preliminary measurements resulted in an ortho to para ratio of 3.06:1, which is within acceptable agreement with the previously published ratio. As a result, the successful demonstration of Raman Spectroscopy for this measurement is expected to lead to a practical method that can be applied for similar in-situ measurements at operating neutron spallation sources.

  18. In situ Raman analyses of deep-sea hydrothermal and cold seep systems (Gorda Ridge and Hydrate Ridge)

    NASA Astrophysics Data System (ADS)

    White, S. N.; Dunk, R. M.; Peltzer, E. T.; Freeman, J. J.; Brewer, P. G.

    2006-05-01

    The Deep Ocean Raman In Situ Spectrometer (DORISS) instrument was deployed at the Sea Cliff Hydrothermal Field and Hydrate Ridge in July 2004. The first in situ Raman spectra of hydrothermal minerals, fluids, and bacterial mats were obtained. These spectra were analyzed and compared to laboratory Raman measurements of standards and samples collected from the site. Spectra of vent fluid (˜294°C at the orifice) at ˜2700 m depth were collected with noncontact and immersion sampling optics. Compared to spectra of ambient (˜2°C) seawater, the vent fluid spectra show changes in the intensity and positions of the water O-H stretch bands due to the elevated temperature. The sulfate band observed in seawater spectra is reduced in vent fluid spectra as sulfate is removed from vent fluid in the subseafloor. Additional components of hydrothermal fluid are present in concentrations too low to be detected with the current Raman system. A precision underwater positioner (PUP) was used to focus the laser spot on opaque samples such as minerals and bacterial mats. Spectra were obtained of anhydrite from actively venting chimneys, and of barite deposits in hydrothermal crusts. Laboratory analysis of rock samples collected in the vent field also detected the presence of gypsum. Spectra of bacterial mats revealed the presence of elemental sulfur (S8) and the carotenoid beta-carotene. Challenges encountered include strong fluorescence from minerals and organics and insufficient sensitivity of the instrument. The next generation DORISS instrument addresses some of these challenges and holds great potential for use in deep-sea vent environments.

  19. Raman shifts and in situ TEM electrical degradation of electron-irradiated monolayer MoS2

    NASA Astrophysics Data System (ADS)

    Parkin, William M.; Balan, Adrian; Liang, Liangbo; Masih Das, Paul; Lamparski, Michael; Naylor, Carl; Rodriguez-Manzo, Julio A.; Johnson, Alan T.; Meunier, Vincent; Drndic, Marija

    We report how the presence of electron-beam-induced vacancies affects first-order Raman modes and correlate this effect with the evolution of in situ TEM two-terminal conductivity of monolayer MoS2 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, we show that irradiation causes partial removal of sulfur and correlate the dependence of the Raman peak shifts with S vacancy density (a few percent), which is confirmed by first-principles density functional theory calculations. Insitu 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 accurately characterize MoS2-based transport channels. This work was supported by the NIH Grant R21HG004767 and NIH Grant R21HG007856. Theoretical work at RPI was supported the NYSTAR program C080117 and the Office of Naval Research. C.H.N. and A.T.C.J. acknowledge support from UES/Air Force Research Lab.

  20. Rapid in situ detection of street samples of drugs of abuse on textile substrates using microRaman spectroscopy

    NASA Astrophysics Data System (ADS)

    Ali, Esam M. A.; Edwards, Howell G. M.; Scowen, Ian J.

    2011-10-01

    Trace amounts of street samples of cocaine hydrochloride and N-methyl-3,4-methylenedioxy-amphetamine (MDMA) on natural and synthetic textiles were successfully detected in situ using confocal Raman microscopy. The presence of some excipient bands in the spectra of the drugs did not prevent the unambiguous identification of the drugs. Raman spectra of the drugs were readily obtained without significant interference from the fibre substrates. Interfering bands arising from the fibre natural or synthetic polymer structure and/or dye molecules did not overlap with the characteristic Raman bands of the drugs. If needed, interfering bands could be successfully removed by spectral subtraction. Also, Raman spectra could be acquired from drug particles trapped between the fibres of highly fluorescent textile specimens. The total acquisition time of the spectra of the drug particles was 90 s accomplished non-destructively and without detachment from their substrates. Sample preparation was not required and spectra of the drugs could be obtained non-invasively preserving the integrity of the evidential material for further analysis.

  1. 3D imaging of enzymes working in situ.

    PubMed

    Jamme, F; Bourquin, D; Tawil, G; Viksø-Nielsen, A; Buléon, A; Réfrégiers, M

    2014-06-01

    Today, development of slowly digestible food with positive health impact and production of biofuels is a matter of intense research. The latter is achieved via enzymatic hydrolysis of starch or biomass such as lignocellulose. Free label imaging, using UV autofluorescence, provides a great tool to follow one single enzyme when acting on a non-UV-fluorescent substrate. In this article, we report synchrotron DUV fluorescence in 3-dimensional imaging to visualize in situ the diffusion of enzymes on solid substrate. The degradation pathway of single starch granules by two amylases optimized for biofuel production and industrial starch hydrolysis was followed by tryptophan autofluorescence (excitation at 280 nm, emission filter at 350 nm). The new setup has been specially designed and developed for a 3D representation of the enzyme-substrate interaction during hydrolysis. Thus, this tool is particularly effective for improving knowledge and understanding of enzymatic hydrolysis of solid substrates such as starch and lignocellulosic biomass. It could open up the way to new routes in the field of green chemistry and sustainable development, that is, in biotechnology, biorefining, or biofuels. PMID:24796213

  2. Direct Raman imaging spectroscopy of lung cancer cells and apoptotic cells

    NASA Astrophysics Data System (ADS)

    Oshima, Yusuke; Furihata, Chie; Sato, Hidetoshi

    2009-02-01

    A Raman spectroscopic technique enables to observe intracellular molecules without fixation or labeling procedures in situ. We demonstrated a classification of human lung cancer cells with Raman spectroscopy and principal component analysis. Normal lung cell-lines and 4 pathological types of cancer cell-lines were seeded on culture dishes and examined. It was as a preliminary study for direct Raman imaging spectroscopy, which could be available for clinical use, to diagnose cancer. The result suggests that Raman spectroscopy could be a complementary method for immunohistology study. We also constructed a new direct Raman imaging system consisting of a high sensitive CCD image sensor, narrow band pass-filters, and a background-free electrically tunable Ti:Sapphire laser. The observation wavelengths can be switched immediately for the purpose of malignancy rapid diagnosis or real time measurement for apoptotic cells. The potential ability of the direct Raman imaging system is supposed to evaluate apoptosis by UV irradiation and anticancer drug-treatment for living lung cancer cells.

  3. Image formation using stimulated raman scattering gain

    NASA Astrophysics Data System (ADS)

    Bespalov, V. G.; Makarov, E. A.; Stasel'ko, D. I.

    2016-07-01

    Theoretical analysis of the spatial, noise, and energy characteristics of an amplifier has been performed in the mode of spectral and time selection using subnanosecond stimulated Raman Scattering gain of weak echo signals in crystalline active media that are known for high (up to 10-1 cm/MW) gain coefficients. The possibility to reach high gain values has been demonstrated for weak signals from objects at acceptable angular sizes of the field of vision of an amplifier. To provide a signal-to-noise ratio that exceeds unity over the entire field of vision, the number of photons at the input to an amplifier that is required has to exceed the number of its resolution elements. Accurate determination of the possibilities of recording of weak echo signals and quality of images of targets that are obtained using amplifiers under stimulated Raman Scattering requires additional special experiments.

  4. Label-free in situ imaging of lignification in plant cell walls.

    PubMed

    Schmidt, Martin; Perera, Pradeep; Schwartzberg, Adam M; Adams, Paul D; Schuck, P James

    2010-11-01

    -destructive and comparatively inexpensive measurements with minimal sample preparation, giving insights into chemical composition and molecular structure in a close to native state. Chemical imaging by confocal Raman microscopy has been previously used for the visualization of the spatial distribution of cellulose and lignin in wood cell walls. Based on these earlier results, we have recently adopted this method to compare lignification in wild type and lignin-deficient transgenic Populus trichocarpa (black cottonwood) stem wood. Analyzing the lignin Raman bands in the spectral region between 1,600 and 1,700 cm⁻¹, lignin signal intensity and localization were mapped in situ. Our approach visualized differences in lignin content, localization, and chemical composition. Most recently, we demonstrated Raman imaging of cell wall polymers in Arabidopsis thaliana with lateral resolution that is sub-μm. Here, this method is presented affording visualization of lignin in plant cell walls and comparison of lignification in different tissues, samples or species without staining or labeling of the tissues.

  5. In vivo Coherent Raman Imaging for Neuroscience Applications

    NASA Astrophysics Data System (ADS)

    Cote, Daniel

    2010-08-01

    The use of coherent Raman imaging is described for applications in neuroscience. Myelin imaging of the spinal cord can be performed with Raman imaging through the use of the vibration in carbon-hydrogen bonds, dominant in lipids. First, we demonstrate in vivo histomorphometry in live animal for characterization of myelin-related nervous system pathologies. This is used to characterize spinal cord health during multiple sclerosis. Second, Raman spectroscopy of tissue is discussed. We discuss the challenges that live animal imaging brings, together with important aspects of coherent Raman imaging in tissue.

  6. Observing Metal-Catalyzed Chemical Reactions in Situ Using Surface-Enhanced Raman Spectroscopy on Pd–Au Nanoshells

    PubMed Central

    Heck, Kimberly N.; Janesko, Benjamin G.; Scuseria, Gustavo E.

    2016-01-01

    Insight into the nature of transient reaction intermediates and mechanistic pathways involved in heterogeneously catalyzed chemical reactions is obtainable from a number of surface spectroscopic techniques. Carrying out these investigations under actual reaction conditions is preferred but remains challenging, especially for catalytic reactions that occur in water. Here, we report the direct spectroscopic study of the catalytic hydrodechlorination of 1,1-dichloroethene in H2O using surface-enhanced Raman spectroscopy (SERS). With Pd islands grown on Au nanoshell films, this reaction can be followed in situ using SERS, exploiting the high enhancements and large active area of Au nanoshell SERS substrates, the transparency of Raman spectroscopy to aqueous solvents, and the catalytic activity enhancement of Pd by the underlying Au metal. The formation and subsequent transformation of several adsorbate species was observed. These results provide the first direct evidence of the room-temperature catalytic hydrodechlorination of a chlorinated solvent, a potentially important pathway for groundwater cleanup, as a sequence of dechlorination and hydrogenation steps. More broadly, the results highlight the exciting prospects of studying catalytic processes in water in situ, like those involved in biomass conversion and proton-exchange membrane fuel cells. PMID:19554693

  7. 671-nm microsystem diode laser based on portable Raman sensor device for in-situ identification of meat spoilage

    NASA Astrophysics Data System (ADS)

    Sowoidnich, Kay; Schmidt, Heinar; Schwägele, Fredi; Kronfeldt, Heinz-Detlef

    2011-05-01

    Based on a miniaturized optical bench with attached 671 nm microsystem diode laser we present a portable Raman system for the rapid in-situ characterization of meat spoilage. It consists of a handheld sensor head (dimensions: 210 x 240 x 60 mm3) for Raman signal excitation and collection including the Raman optical bench, a laser driver, and a battery pack. The backscattered Raman radiation from the sample is analyzed by means of a custom-designed miniature spectrometer (dimensions: 200 x 190 x 70 mm3) with a resolution of 8 cm-1 which is fiber-optically coupled to the sensor head. A netbook is used to control the detector and for data recording. Selected cuts from pork (musculus longissimus dorsi and ham) stored refrigerated at 5 °C were investigated in timedependent measurement series up to three weeks to assess the suitability of the system for the rapid detection of meat spoilage. Using a laser power of 100 mW at the sample meat spectra can be obtained with typical integration times of 5 - 10 seconds. The complex spectra were analyzed by the multivariate statistical tool PCA (principal components analysis) to determine the spectral changes occurring during the storage period. Additionally, the Raman data were correlated with reference analyses performed in parallel. In that way, a distinction between fresh and spoiled meat can be found in the time slot of 7 - 8 days after slaughter. The applicability of the system for the rapid spoilage detection of meat and other food products will be discussed.

  8. Multimodality Raman and photoacoustic imaging of surface-enhanced-Raman-scattering-targeted tumor cells

    NASA Astrophysics Data System (ADS)

    Shi, Wei; Paproski, Robert J.; Shao, Peng; Forbrich, Alexander; Lewis, John D.; Zemp, Roger J.

    2016-02-01

    A multimodality Raman and photoacoustic imaging system is presented. This system has ultralow background and can detect tumor cells labeled with modified surface-enhanced-Raman-scattering (SERS) nanoparticles in vivo. Photoacoustic imaging provides microvascular context and can potentially be used to guide magnetic trapping of circulating tumor cells for SERS detection in animal models.

  9. Development of microfluidic devices for in situ investigation of cells using surface-enhanced Raman spectroscopy (Conference Presentation)

    NASA Astrophysics Data System (ADS)

    Ho, Yu-Han; Galvan, Daniel D.; Yu, Qiuming

    2016-03-01

    Surface-enhanced Raman spectroscopy (SERS) has immerged as a power analytical and sensing technique for many applications in biomedical diagnosis, life sciences, food safety, and environment monitoring because of its molecular specificity and high sensitivity. The inactive Raman scattering of water molecule makes SERS a suitable tool for studying biological systems. Microfluidic devices have also attracted a tremendous interest for the aforementioned applications. By integrating SERS-active substrates with microfluidic devices, it offers a new capability for in situ investigation of biological systems, their dynamic behaviors, and response to drugs or microenvironment changes. In this work, we designed and fabricated a microfluidic device with SERS-active substrates surrounding by cell traps in microfluidic channels for in situ study of live cells using SERS. The SERS-active substrates are quasi-3D plasmonic nanostructure array (Q3D-PNA) made in h-PDMS/PMDS with physically separated gold film with nanoholes op top and gold nanodisks at the bottom of nanowells. 3D finite-difference time-domain (3D-FDTD) electromagnetic simulations were performed to design Q3D-PNAs with the strongest local electric fields (hot spots) at the top or bottom water/Au interfaces for sensitive analysis of cells and small components, respectively. The Q3D-PNAs with the hot spots on top and bottom were placed at the up and down stream of the microfluidic channel, respectively. Each Q3D-PNA pattern was surrounded with cell trapping structures. The microfluidic device was fabricated via soft lithography. We demonstrated that normal (COS-7) and cancer (HpeG2) cells were captured on the Q3D-PNAs and investigated in situ using SERS.

  10. In situ mineral identification - Raman technique in future robotic explorations on planetary surfaces

    SciTech Connect

    Wang, A.; Jolliff, B.L.; Haskin, L.A.

    1995-12-31

    Rover and lander missions are being continually planned for the characterization of planetary surface materials. With a series of simulated Raman measurements of lunar soils, rock chips and Martian analogues, we have demonstrated that mineral identification for the main phases in these planetary materials can be unambiguously achieved. We also obtained significant information on composition and structural features of important phases, such as the Mg/(Mg+Fe) ration in olivines, the dominant structural forms of pyroxenes, and the characteristics of hydrous components and cations in carbonates and sulfates, that are very important for Martian geology. Recent developments of Raman spectroscopic instrumentation make it possible to build a small, sensitive, and robust Raman system for rover and lander missions. Compared to other spectroscopic techniques (VIS-NIR, mid-IR and Moessbauer spectroscopy) that have been used or proposed for planetary application, Raman spectroscopy has many advantages, such as sharp, non-overlapping peaks in mineral spectra, no need for spectral deconvolution in order to identify the phases, and operation in visible spectral region. A rover Raman system could work nicely as a mineral indicator in future missions to Mars and Moon.

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

    NASA Astrophysics Data System (ADS)

    Polisetti, Sneha; Baig, Nameera; Bible, Amber; Morrell-Falvey, Jennifer; Doktycz, Mitchel; Bohn, Paul W.

    2015-08-01

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

  12. Multiferroic CuCrO₂ under high pressure: In situ X-ray diffraction and Raman spectroscopic studies

    SciTech Connect

    Garg, Alka B. Mishra, A. K.; Pandey, K. K.; Sharma, Surinder M.

    2014-10-07

    The compression behavior of delafossite compound CuCrO₂ has been investigated by in situ x-ray diffraction (XRD) and Raman spectroscopic measurements up to 23.2 and 34 GPa, respectively. X-ray diffraction data show the stability of ambient rhombohedral structure up to ~23 GPa. Material shows large anisotropy in axial compression with c-axis compressibility, κ{sub c} = 1.26 × 10⁻³(1) GPa⁻¹ and a-axis compressibility, κ{sub a} = 8.90 × 10⁻³(6) GPa⁻¹. Our XRD data show an irreversible broadening of diffraction peaks. Pressure volume data when fitted to 3rd order Birch-Murnaghan equation of state give the value of bulk modulus, B₀ = 156.7(2.8) GPa with its pressure derivative, B₀{sup ’} as 5.3(0.5). All the observed vibrational modes in Raman measurements show hardening with pressure. Appearance of a new mode at ~24 GPa indicates the structural phase transition in the compound. Our XRD and Raman results indicate that CuCrO{sub 2} may be transforming to an ordered rocksalt type structure under compression.

  13. Improving the Detection Limit in a Capillary Raman System for In Situ Gas Analysis by Means of Fluorescence Reduction

    PubMed Central

    Rupp, Simone; Off, Andreas; Seitz-Moskaliuk, Hendrik; James, Timothy M.; Telle, Helmut H.

    2015-01-01

    Raman spectroscopy for low-pressure or trace gas analysis is rather challenging, in particular in process control applications requiring trace detection and real-time response; in general, enhancement techniques are required. One possible enhancement approach which enjoys increasing popularity makes use of an internally-reflective capillary as the gas cell. However, in the majority of cases, such capillary systems were often limited in their achievable sensitivity by a significant fluorescence background, which is generated as a consequence of interactions between the laser light and optical glass components in the setup. In order to understand and counteract these problems we have investigated a range of fluorescence-reducing measures, including the rearrangement of optical elements, and the replacement of glass components—including the capillary itself—by metal alternatives. These studies now have led to a capillary setup in which fluorescence is practically eliminated and substantial signal enhancement over standard Raman setups is achieved. With this improved (prototype) setup, detection limits of well below 1 mbar could be obtained in sub-second acquisition times, demonstrating the potential of capillary Raman spectroscopy for real-time, in situ gas sensing and process control applications, down to trace level concentrations. PMID:26378545

  14. Mechanism of ceroid formation in atherosclerotic plaque: in situ studies using a combination of Raman and fluorescence spectroscopy

    NASA Astrophysics Data System (ADS)

    Haka, Abigail S.; Kramer, John R.; Dasari, Ramachandra R.; Fitzmaurice, Maryann

    2011-01-01

    Accumulation of the lipid-protein complex ceroid is a characteristic of atherosclerotic plaque. The mechanism of ceroid formation has been extensively studied, because the complex is postulated to contribute to plaque irreversibility. Despite intensive research, ceroid deposits are defined through their fluorescence and histochemical staining properties, while their composition remains unknown. Using Raman and fluorescence spectral microscopy, we examine the composition of ceroid in situ in aorta and coronary artery plaque. The synergy of these two types of spectroscopy allows for identification of ceroid via its fluorescence signature and elucidation of its chemical composition through the acquisition of a Raman spectrum. In accordance with in vitro predictions, low density lipoprotein (LDL) appears within the deposits primarily in its peroxidized form. The main forms of modified LDL detected in both coronary artery and aortic plaques are peroxidation products from the Fenton reaction and myeloperoxidase-hypochlorite pathway. These two peroxidation products occur in similar concentrations within the deposits and represent ~40 and 30% of the total LDL (native and peroxidized) in the aorta and coronary artery deposits, respectively. To our knowledge, this study is the first to successfully employ Raman spectroscopy to unravel a metabolic pathway involved in disease pathogenesis: the formation of ceroid in atherosclerotic plaque.

  15. In-SITU, Time-resolved Raman Spectro-micro-topography of an Operating Lithium Ion Battery

    NASA Technical Reports Server (NTRS)

    Luo, Yu; Cai, Wen-Bin; Xing, Xue-Kun; Scherson, Daniel A.

    2003-01-01

    A Raman microscope has been coupled to a computer-controlled, two-dimensional linear translator attached to a custom-designed, sealed optical chamber to allow in situ acquisition of space-, and time-resolved spectra of an operating thin graphite/LiCoO2 Li-ion battery. This unique arrangement made it possible to collect continuously series of Raman spectra from a sharply defined edge of the battery exposing the anode (A), separator (S), and cathode (C), during charge and discharge, while the device was moved back and forth under the fixed focused laser beam along an axis normal to the layered A/S/C plane. Clear spectral evidence was obtained for changes in the amount of Li(+) within particles of graphite in the anode, and, to a lesser extent, of LiCoO2 in the cathode, during battery discharge both as a function of position and time. Analysis of time-resolved Raman spectro-micro-topography (SMT) measurements of the type described in this work are expected to open new prospects for assessing the validity of theoretical models aimed at simulating the flow of Li(+) within Li-ion batteries under operating conditions.

  16. In-Situ Characterization of Electrode-Solution Interfacial Processes by Atomic-Resolution Scanning Tunneling Microscopy and Surface Enhanced Raman Spectroscopy.

    NASA Astrophysics Data System (ADS)

    Gao, Xiaoping

    1992-01-01

    The author's research is directed towards the atomic-molecular-level understanding of electrochemical interfacial processes, utilizing in-situ atomic-resolution scanning tunneling microscopy (STM) and surface enhanced Raman spectroscopy (SERS). The majority of this research effort has focussed on a systematic STM study of potential -induced surface reconstruction of gold single crystal electrodes and combined atomic-resolution STM and surface vibrational spectroscopy as in-situ probes of molecular adsorption and electrooxidation on metal electrodes. We have demonstrated for the first time that truly atomic-resolution STM images of gold surface reconstruction and molecular transformation can be observed at electrochemical interfaces under potential control conditions. The findings illustrate in a more general vein the power of STM for elucidating previously unobtainable details of surface atomic structure at electrochemical interfaces. The STM study shows that Au(111), (100), (110), (311), and (533) are observed to undergo reconstruction at the potentials corresponding to small (ca. 10-15 muc cm^{-2}) negative electrode charges. Some information regarding the mechanisms of the changes in atomic density required for reconstruction can be obtained from time- and potential -dependent sequences of STM images. In-situ potential-dependent STM studies of electrochemical processes of sulfide and iodide on Au(111), carbon monoxide on Rh(111) and (110) in aqueous solutions have been carried out and compared with SER spectra or infrared spectra. The details of potential-dependent adlayer structures and the formation of electrooxidation products, such as S _8 rings, polyiodide chains and crystal films, were observed and the results are in good agreement with the surface vibrational spectra. The orientation of adsorbed benzene and monosubstituted benzenes on gold electrodes have also been studied using SER spectroscopy. The results provide strong evidence that SERS selection

  17. In-Situ Lake Bio-Geochemistry Using Laser Raman Spectroscopy and Optrode Sensing

    NASA Astrophysics Data System (ADS)

    Sobron, P.; Sanz, A.; Thompson, C.; Cabrol, N.; Planetary Lake Lander Project Team

    2014-06-01

    We have used LRS for characterizing the organic content of a lake through real-time, in-situ analyses and through lab analyses of returned samples. β-carotene and fatty acids (triglycerides) were identified as major components of the organic samples.

  18. In situ monitoring of powder blending by non-invasive Raman spectrometry with wide area illumination.

    PubMed

    Allan, Pamela; Bellamy, Luke J; Nordon, Alison; Littlejohn, David; Andrews, John; Dallin, Paul

    2013-03-25

    A 785nm diode laser and probe with a 6mm spot size were used to obtain spectra of stationary powders and powders mixing at 50rpm in a high shear convective blender. Two methods of assessing the effect of particle characteristics on the Raman sampling depth for microcrystalline cellulose (Avicel), aspirin or sodium nitrate were compared: (i) the information depth, based on the diminishing Raman signal of TiO(2) in a reference plate as the depth of powder prior to the plate was increased, and (ii) the depth at which a sample became infinitely thick, based on the depth of powder at which the Raman signal of the compound became constant. The particle size, shape, density and/or light absorption capability of the compounds were shown to affect the "information" and "infinitely thick" depths of individual compounds. However, when different sized fractions of aspirin were added to Avicel as the main component, the depth values of aspirin were the same and matched that of the Avicel: 1.7mm for the "information" depth and 3.5mm for the "infinitely thick" depth. This latter value was considered to be the minimum Raman sampling depth when monitoring the addition of aspirin to Avicel in the blender. Mixing profiles for aspirin were obtained non-invasively through the glass wall of the vessel and could be used to assess how the aspirin blended into the main component, identify the end point of the mixing process (which varied with the particle size of the aspirin), and determine the concentration of aspirin in real time. The Raman procedure was compared to two other non-invasive monitoring techniques, near infrared (NIR) spectrometry and broadband acoustic emission spectrometry. The features of the mixing profiles generated by the three techniques were similar for addition of aspirin to Avicel. Although Raman was less sensitive than NIR spectrometry, Raman allowed compound specific mixing profiles to be generated by studying the mixing behaviour of an aspirin

  19. A Microfluidic Bioreactor with in Situ SERS Imaging for the Study of Controlled Flow Patterns of Biofilm Precursor Materials

    PubMed Central

    Paquet-Mercier, François; Aznaveh, Nahid Babaei; Safdar, Muhammad; Greener, Jesse

    2013-01-01

    A microfluidic bioreactor with an easy to fabricate nano-plasmonic surface is demonstrated for studies of biofilms and their precursor materials via Surface Enhanced Raman Spectroscopy (SERS). The system uses a novel design to induce sheath flow confinement of a sodium citrate biofilm precursor stream against the SERS imaging surface to measure spatial variations in the concentration profile. The unoptimised SERS enhancement was approximately 2.5 × 104, thereby improving data acquisition time, reducing laser power requirements and enabling a citrate detection limit of 0.1 mM, which was well below the concentrations used in biofilm nutrient solutions. The flow confinement was observed by both optical microscopy and SERS imaging with good complementarity. We demonstrate the new bioreactor by growing flow-templated biofilms on the microchannel wall. This work opens the way for in situ spectral imaging of biofilms and their biochemical environment under dynamic flow conditions. PMID:24172286

  20. In situ Raman and electrochemical characterization of the role of electrolyte additives in Li/SOCl2 batteries

    NASA Astrophysics Data System (ADS)

    Kovac, M.; Milicev, S.; Kovac, A.; Pejovnik, S.

    1995-05-01

    A simple glass cell has been constructed for in situ Raman characterization of discharge products in Li/SOCl2 batteries with polyvinyl chloride (PVC) and LiAl(SO3Cl4) additives. The assembly enables the characterization of catholyte-soluble discharge products in the electrolyte as well as products on the lithium and carbon electrode surfaces. The effect of the additives was also examined by scanning electron microscopy/energy dispersive spectroscopy and impedance spectroscopy and correlated to the voltage delay in batteries. The best results, as regards to the elimination of the delay effect, were obtained with a new electrolyte consisting of LiAlCl4/SOCl2 with an admixture of PVC and LiAl(SO3Cl4).

  1. Mapping Li(+) Concentration and Transport via In Situ Confocal Raman Microscopy.

    PubMed

    Forster, Jason D; Harris, Stephen J; Urban, Jeffrey J

    2014-06-01

    We demonstrate confocal Raman microscopy as a general, nonperturbative tool to measure spatially resolved lithium ion concentrations in liquid electrolytes. By combining this high-spatial-resolution technique with a simple microfluidic device, we are able to measure the diffusion coefficient of lithium ions in dimethyl carbonate in two different concentration regimes. Because lithium ion transport plays a key role in the function of a variety of electrochemical devices, quantifying and visualizing this process is crucial for understanding device performance. This method for detecting lithium ions should be immediately useful in the study of lithium-ion-based devices, ion transport in porous media, and at electrode-electrolyte interfaces, and the analytical framework is useful for any system exhibiting a concentration-dependent Raman spectrum. PMID:26273887

  2. Fast Vibrational Imaging of Single Cells and Tissues by Stimulated Raman Scattering Microscopy

    PubMed Central

    2015-01-01

    Conspectus Traditionally, molecules are analyzed in a test tube. Taking biochemistry as an example, the majority of our knowledge about cellular content comes from analysis of fixed cells or tissue homogenates using tools such as immunoblotting and liquid chromatography–mass spectrometry. These tools can indicate the presence of molecules but do not provide information on their location or interaction with each other in real time, restricting our understanding of the functions of the molecule under study. For real-time imaging of labeled molecules in live cells, fluorescence microscopy is the tool of choice. Fluorescent labels, however, are too bulky for small molecules such as fatty acids, amino acids, and cholesterol. These challenges highlight a critical need for development of chemical imaging platforms that allow in situ or in vivo analysis of molecules. Vibrational spectroscopy based on spontaneous Raman scattering is widely used for label-free analysis of chemical content in cells and tissues. However, the Raman process is a weak effect, limiting its application for fast chemical imaging of a living system. With high imaging speed and 3D spatial resolution, coherent Raman scattering microscopy is enabling a new approach for real-time vibrational imaging of single cells in a living system. In most experiments, coherent Raman processes involve two excitation fields denoted as pump at ωp and Stokes at ωs. When the beating frequency between the pump and Stokes fields (ωp – ωs) is resonant with a Raman-active molecular vibration, four major coherent Raman scattering processes occur simultaneously, namely, coherent anti-Stokes Raman scattering (CARS) at (ωp – ωs) + ωp, coherent Stokes Raman scattering (CSRS) at ωs – (ωp – ωs), stimulated Raman gain (SRG) at ωs, and stimulated Raman loss (SRL) at ωp. In SRG, the Stokes beam experiences a gain in intensity, whereas in SRL, the pump beam experiences a loss. Both SRG and SRL belong to

  3. Fast vibrational imaging of single cells and tissues by stimulated Raman scattering microscopy.

    PubMed

    Zhang, Delong; Wang, Ping; Slipchenko, Mikhail N; Cheng, Ji-Xin

    2014-08-19

    Traditionally, molecules are analyzed in a test tube. Taking biochemistry as an example, the majority of our knowledge about cellular content comes from analysis of fixed cells or tissue homogenates using tools such as immunoblotting and liquid chromatography-mass spectrometry. These tools can indicate the presence of molecules but do not provide information on their location or interaction with each other in real time, restricting our understanding of the functions of the molecule under study. For real-time imaging of labeled molecules in live cells, fluorescence microscopy is the tool of choice. Fluorescent labels, however, are too bulky for small molecules such as fatty acids, amino acids, and cholesterol. These challenges highlight a critical need for development of chemical imaging platforms that allow in situ or in vivo analysis of molecules. Vibrational spectroscopy based on spontaneous Raman scattering is widely used for label-free analysis of chemical content in cells and tissues. However, the Raman process is a weak effect, limiting its application for fast chemical imaging of a living system. With high imaging speed and 3D spatial resolution, coherent Raman scattering microscopy is enabling a new approach for real-time vibrational imaging of single cells in a living system. In most experiments, coherent Raman processes involve two excitation fields denoted as pump at ωp and Stokes at ωs. When the beating frequency between the pump and Stokes fields (ωp - ωs) is resonant with a Raman-active molecular vibration, four major coherent Raman scattering processes occur simultaneously, namely, coherent anti-Stokes Raman scattering (CARS) at (ωp - ωs) + ωp, coherent Stokes Raman scattering (CSRS) at ωs - (ωp - ωs), stimulated Raman gain (SRG) at ωs, and stimulated Raman loss (SRL) at ωp. In SRG, the Stokes beam experiences a gain in intensity, whereas in SRL, the pump beam experiences a loss. Both SRG and SRL belong to stimulated Raman scattering (SRS

  4. In situ monitoring of pH titration by Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Elbagerma, M. A.; Azimi, Gholamhassan; Edwards, H. G. M.; Alajtal, A. I.; Scowen, I. J.

    2010-05-01

    Molecular speciation of organic compounds in solution is essential for the understanding of ionic complexation. The Raman technique was chosen because it allows the identification of compounds in different states, and it can give information about the molecular geometry from the analysis of the vibrational spectra. The effect of pH on organic compounds can give information about the ionisation of molecule species. In this study the ionisation steps of salicylic acid and paracetamol have been studied by means of potentiometry coupled with Raman spectroscopy at 30.0 °C in a solution of ionic strength 0.96 mol dm -3 (KNO 3) and 0.04 mol dm -3 (HNO 3). The protonation and deprotonation behaviour of the molecules were studied in different pH regions. The abundance of the three different species in the Raman spectra of aqueous salicylic acid have been identified satisfactorily, characterised, and determined by numeric treatment of the data using a multiwavelength curve-fitting program and confirmed with the observed spectral information.

  5. In situ Raman study of redox state changes of mitochondrial cytochromes in a perfused rat heart.

    PubMed

    Brazhe, Nadezda A; Treiman, Marek; Faricelli, Barbara; Vestergaard, Jakob H; Sosnovtseva, Olga

    2013-01-01

    We developed a Raman spectroscopy-based approach for simultaneous study of redox changes in c-and b-type cytochromes and for a semiquantitative estimation of the amount of oxygenated myoglobin in a perfused rat heart. Excitation at 532 nm was used to obtain Raman scattering of the myocardial surface of the isolated heart at normal and hypoxic conditions. Raman spectra of the heart under normal pO2 demonstrate unique peaks attributable to reduced c-and b-type cytochromes and oxymyoglobin (oMb). The cytochrome peaks decreased in intensity upon FCCP treatment, as predicted from uncoupling mitochondrial respiration. Conversely, transient hypoxia causes the reversible increase in the intensity of peaks assigned to cytochromes c and c1, reflecting electron stacking proximal to cytochrome oxidase due to the lack of terminal electron acceptor O2. Intensities of peaks assigned to oxy- and deoxyhemoglobin were used for the semiquantitative estimation of oMb deoxygenation that was found to be of approximately 50[Formula: see text] under hypoxia conditions.

  6. Spectrometer-free vibrational imaging by retrieving stimulated Raman signal from highly scattered photons

    PubMed Central

    Liao, Chien-Sheng; Wang, Pu; Wang, Ping; Li, Junjie; Lee, Hyeon Jeong; Eakins, Gregory; Cheng, Ji-Xin

    2015-01-01

    In vivo vibrational spectroscopic imaging is inhibited by relatively slow spectral acquisition on the second scale and low photon collection efficiency for a highly scattering system. Recently developed multiplex coherent anti-Stokes Raman scattering and stimulated Raman scattering techniques have improved the spectral acquisition time down to microsecond scale. These methods using a spectrometer setting are not suitable for turbid systems in which nearly all photons are scattered. We demonstrate vibrational imaging by spatial frequency multiplexing of incident photons and single photodiode detection of a stimulated Raman spectrum within 60 μs. Compared to the spectrometer setting, our method improved the photon collection efficiency by two orders of magnitude for highly scattering specimens. We demonstrated in vivo imaging of vitamin E distribution on mouse skin and in situ imaging of human breast cancerous tissues. The reported work opens new opportunities for spectroscopic imaging in a surgical room and for development of deep-tissue Raman spectroscopy toward molecular level diagnosis. PMID:26601311

  7. Coherent Raman Scattering: Methods Towards Imaging with High Sensitivity

    NASA Astrophysics Data System (ADS)

    Bachler, Brandon Richard

    Coherent Raman spectroscopy is a powerful tool for molecular identification. For imaging applications, Raman spectroscopy techniques have offered a way of achieving endogenous chemical contrast without the need for fluorescent labeling. Increasing the sensitivity of Raman scattering microscopy is vital to performing high speed, chemically selective imaging. This thesis presents three experiments with the ultimate goal of increasing the sensitivity and quantifying limitations of different Raman techniques. The first experiment is a comparison of spontaneous and coherent Raman signal strengths under biological imaging conditions. While it is commonly stated in the literature that coherent Raman techniques provide orders of magnitude higher signal than spontaneous Raman, such a comparison has not been done under the low concentration, low excitation power conditions relevant for biological imaging. We determine a critical power above which coherent Raman methods provide higher signal and below which spontaneous Raman methods provide higher sensitivity. Contrary to what is commonly stated in the literature, spontaneous Raman can provide higher signal levels under common biological imaging conditions. The second experiment is a demonstration of the first multiplexed Raman-induced Kerr effect (BIKES) microscopy setup to date. We compare the signal-to-noise ratios between femtosecond stimulated Raman (FSRS) and RIKES for spectroscopy applications in solution and for microscopy applications with polystyrene beads. We find that for our samples, RIKES consistently provides a higher signal-to-noise ratio than FSRS for both applications. We also use RIKES microscopy to map out the distribution of cytoplasm in onion cells. Finally, a surface-enhanced Raman experiment is performed to observe and compare highly enhanced signals for spontaneous and coherent Raman spectroscopy. We use a commercial SERS substrate and observe significantly enhanced spontaneous Raman signals from

  8. High-pressure characterization of nitrogen-rich bis-triaminoguanidinium azotetrazolate (TAGzT) by in situ Raman spectroscopy.

    PubMed

    Behler, K D; Ciezak-Jenkins, J A; Sausa, R C

    2013-02-28

    Compounds rich in nitrogen are attracting significant interest not only because of their high energy content but also because they are potentially more environmentally benign in comparison to conventional energetic materials. Given this interest, it is desirable to understand their molecular composition and structural variations with pressure to derive their stability and determine the conditions in which they transform physically or chemically. In this study, we examine the room-temperature isothermal compression behavior of bis-triaminoguanidinium azotetrazolate (TAGzT) by in situ Raman spectroscopy to pressures near 17 GPa. We assign the characteristic vibrational bands and report the effects of pressure on band intensity, line width, and frequency shift. Two prominent peaks near 1370 and 1470 cm(-1) arise from the C-N and N═N symmetric stretches, respectively. Overall, the intensity of these bands and others diminishes with pressure, and their spectral linewidths increase monotonically upon compression. The vibrational frequency modes blue shift linearly upon compression, indicating a generalized stiffening of the bonds as the pressure increases. These results, together with micro Raman spectroscopic analyses of the recovered, decompressed samples, suggest that TAGzT does not undergo any phase transitions within this pressure range. We estimate and report the C-N and N═N intermolecular bond lengths under compression. PMID:23343336

  9. Surface-enhanced in-situ Raman-sensor applied in the arctic area for analyses of water and sediment

    NASA Astrophysics Data System (ADS)

    Kolomijeca, Anna; Kwon, Yong-Hyok; Kronfeldt, Heinz-Detlef

    2012-06-01

    Investigations on the seafloor in the arctic area are of great scientific interest as well as of progressive economic importance. Therefore, measurements in the water column and of sediments were carried out by applying different analytical methods. In JCR 253 arctic cruise a microsystem diode laser with reflection Bragg grating emitting at 671 nm was introduced and integrated into an optode housing which was laboratory pressure tested up to 200 bar. The connection to the mobile spectrometer is realized through an optical fiber. All performed measurements were carried out on the James-Clark-Ross research vessel during a three week experiment in August 2011. Conventional Raman spectra and SERS spectra of arctic surface water and sediment acquired from locations around 78° N and 9° E will be presented. Selected SERS substrates developed for SERS measurements in sea-water were tested for their capability to detect different substances in the water down to very small (pmol/l) concentrations. Additionally, the applicability of shifted excitation Raman difference spectroscopy (SERDS) and a combination of SERS with SERDS for analytical applications during sea-trials for in-situ analyses of sea-water and sediments will be discussed.

  10. Sensitive Glycoprotein Sandwich Assays by the Synergistic Effect of In Situ Generation of Raman Probes and Plasmonic Coupling of Ag Core-Au Satellite Nanostructures.

    PubMed

    Bi, Xiaoshuang; Li, Xueyuan; Chen, Dong; Du, Xuezhong

    2016-05-01

    Sensitive surface-enhanced Raman scattering (SERS) assays of glycoproteins have been proposed using p-aminothiophenol (PATP)-embedded Ag core-Au satellite nanostructures modified with p-mercaptophenylboronic acid (PMBA) and the self-assembled monolayer of PMBA on a smooth gold-coated wafer. The apparent Raman probe PATP on the surfaces of the Ag cores underwent a photodimerization to generate 4,4'-dimercaptoazobenzene (DMAB) in situ upon excitation of laser, and the in situ generated DMAB acted as the actual Raman probe with considerably strong SERS signals, which was further enhanced by the plasmonic coupling of the Ag core-Au satellite nanostructures due to the synergistic effect. The sandwich assays of glycoproteins showed high sensitivity and excellent selectivity against nonglycoproteins. The Ag core-Au satellite SERS nanostructures can be used for highly sensitive SERS assays of other analytes.

  11. In Situ Confocal Raman Microscopy of Hydrated Early Stages of Bacterial Biofilm Formation on Various Surfaces in a Flow Cell.

    PubMed

    Smith-Palmer, Truis; Lin, Sicheng; Oguejiofor, Ikenna; Leng, Tianyang; Pustam, Amanda; Yang, Jin; Graham, Lori L; Wyeth, Russell C; Bishop, Cory D; DeMont, M Edwin; Pink, David

    2016-02-01

    Bacterial biofilms are precursors to biofouling by other microorganisms. Understanding their initiation may allow us to design better ways to inhibit them, and thus to inhibit subsequent biofouling. In this study, the ability of confocal Raman microscopy to follow the initiation of biofouling by a marine bacterium, Pseudoalteromonas sp. NCIMB 2021 (NCIMB 2021), in a flow cell, using optical and confocal Raman microscopy, was investigated. The base of the flow cell comprised a cover glass. The cell was inoculated and the bacteria attached to, and grew on, the cover glass. Bright field images and Raman spectra were collected directly from the hydrated biofilms over several days. Although macroscopically the laser had no effect on the biofilm, within the first 24 h cells migrated away from the position of the laser beam. In the absence of flow, a buildup of extracellular substances occurred at the base of the biofilm. When different coatings were applied to cover glasses before they were assembled into the flow cells, the growth rate, structure, and composition of the resulting biofilm was affected. In particular, the ratio of Resonance Raman peaks from cytochrome c (CC) in the extracellular polymeric substances, to the Raman phenylalanine (Phe) peak from protein in the bacteria, depended on both the nature of the surface and the age of the biofilm. The ratios were highest for 24 h colonies on a hydrophobic surface. Absorption of a surfactant with an ethyleneoxy chain into the hydrophobic coating created a surface similar to that given with a simple PEG coating, where bacteria grew in colonies away from the surface rather than along the surface, and CC:Phe ratios were initially low but increased at least fivefold in the first 48 h. PMID:26903564

  12. In Situ Confocal Raman Microscopy of Hydrated Early Stages of Bacterial Biofilm Formation on Various Surfaces in a Flow Cell.

    PubMed

    Smith-Palmer, Truis; Lin, Sicheng; Oguejiofor, Ikenna; Leng, Tianyang; Pustam, Amanda; Yang, Jin; Graham, Lori L; Wyeth, Russell C; Bishop, Cory D; DeMont, M Edwin; Pink, David

    2016-02-01

    Bacterial biofilms are precursors to biofouling by other microorganisms. Understanding their initiation may allow us to design better ways to inhibit them, and thus to inhibit subsequent biofouling. In this study, the ability of confocal Raman microscopy to follow the initiation of biofouling by a marine bacterium, Pseudoalteromonas sp. NCIMB 2021 (NCIMB 2021), in a flow cell, using optical and confocal Raman microscopy, was investigated. The base of the flow cell comprised a cover glass. The cell was inoculated and the bacteria attached to, and grew on, the cover glass. Bright field images and Raman spectra were collected directly from the hydrated biofilms over several days. Although macroscopically the laser had no effect on the biofilm, within the first 24 h cells migrated away from the position of the laser beam. In the absence of flow, a buildup of extracellular substances occurred at the base of the biofilm. When different coatings were applied to cover glasses before they were assembled into the flow cells, the growth rate, structure, and composition of the resulting biofilm was affected. In particular, the ratio of Resonance Raman peaks from cytochrome c (CC) in the extracellular polymeric substances, to the Raman phenylalanine (Phe) peak from protein in the bacteria, depended on both the nature of the surface and the age of the biofilm. The ratios were highest for 24 h colonies on a hydrophobic surface. Absorption of a surfactant with an ethyleneoxy chain into the hydrophobic coating created a surface similar to that given with a simple PEG coating, where bacteria grew in colonies away from the surface rather than along the surface, and CC:Phe ratios were initially low but increased at least fivefold in the first 48 h.

  13. Two-wavelength Raman imaging for non-intrusive monitoring of transient temperature in microfluidic devices

    NASA Astrophysics Data System (ADS)

    Kuriyama, Reiko; Sato, Yohei

    2014-09-01

    The present study proposes a non-intrusive visualization technique based on two-wavelength Raman imaging for in-situ monitoring of the unsteady temperature field in microfluidic systems. The measurement principle relies on the contrasting temperature dependencies of hydrogen-bonded and non-hydrogen-bonded OH stretching modes of the water Raman band, whose intensities were simultaneously captured by two cameras equipped with corresponding bandpass filters. The temperature distributions were then determined from the intensity ratio of the simultaneously-obtained Raman images, which enables compensation for temporal fluctuation and spatial inhomogeneity of the excitation laser intensity. A calibration experiment exhibited a linear relationship between the temperature and the intensity ratio in the range 293-343 K and least-regression analysis gave an uncertainty of 1.43 K at 95% confidence level. By applying the calibration data, time series temperature distributions were quantitatively visualized in a Y-shaped milli-channel at a spatial resolution of 6.0  ×  6.0 µm2 with an acquisition time of 16.5 s. The measurement result clearly exhibited the temporal evolution of the temperature field and was compared with the values obtained by thermocouples. This paper therefore demonstrates the viability of employing the two-wavelength Raman imaging technique for temperature measurements in microfluidic devices.

  14. Hyperspectral coherent anti-Stokes Raman scattering microscopy for in situ analysis of solid-state crystal polymorphs

    NASA Astrophysics Data System (ADS)

    Garbacik, E. T.; Fussell, A. L.; Güres, S.; Korterik, J. P.; Otto, C.; Herek, J. L.; Offerhaus, H. L.

    2013-02-01

    Hyperspectral coherent anti-Stokes Raman scattering (CARS) microscopy is quickly becoming a prominent imaging modality because of its many advantages over the traditional paradigm of multispectral CARS. In particular, recording a significant portion of the vibrational spectrum at each spatial pixel allows image-wide spectral analysis at much higher rates than can be achieved with spontaneous Raman. We recently developed a hyperspectral CARS method, the driving principle behind which is the fast acquisition and display of a hyperspectral datacube as a set of intuitive images wherein each material in a sample appears with a unique trio of colors. Here we use this system to image and analyze two types of polymorphic samples: the pseudopolymorphic hydration of theophylline, and the packing polymorphs of the sugar alcohol mannitol. In addition to these solid-state form modifications we have observed spectral variations of crystalline mannitol and diprophylline as functions of their orientations relative to the optical fields. We use that information to visualize the distributions of these compounds in a pharmaceutical solid oral dosage form.

  15. XRD, TEM, IR, Raman and NMR Spectroscopy of In Situ Crystallization of Lithium Disilicate Glass

    NASA Technical Reports Server (NTRS)

    Fuss, T.; Mogus-Milankovic, A.; Ray, C. S.; Lesher, C. E.; Youngman, R.; Day, D. E.

    2006-01-01

    The structure of a Li2O-2SiO2 (LS2) glass was investigated as a function of pressure and temperature up to 6 GPa and 750 C respectively, using XRD, TEM, IR, Raman and NMR spectroscopy. Glass densified at 6 GPa has an average Si-O-Si bond angle approx.7deg lower than that found in glass processed at 4.5 GPa. At 4.5 GPa, lithium disilicate crystallizes from the glass, while at 6 GPa a new high pressure form of lithium metasilicate crystallizes. The new phase, while having lithium metasilicate crystal symmetry, contains at least 4 different Si sites. NMR results for 6 GPa sample indicate the presence of Q4 species with (Q(sup 4))Si-O-Si(Q(sup 4)) bond angles of approx.157deg. This is the first reported occurrence of Q(sup 4) species with such large bond angles in alumina free alkali silicate glass. No five- or six- coordinated Si are found.

  16. In situ detection and identification of hair dyes using surface-enhanced Raman spectroscopy (SERS).

    PubMed

    Kurouski, Dmitry; Van Duyne, Richard P

    2015-03-01

    Hair is one of the most common types of physical evidence found at a crime scene. Forensic examination may suggest a connection between a suspect and a crime scene or victim, or it may demonstrate an absence of such associations. Therefore, forensic analysis of hair evidence is invaluable to criminal investigations. Current hair forensic examinations are primarily based on a subjective microscopic comparison of hair found at the crime scene with a sample of suspect's hair. Since this is often inconclusive, the development of alternative and more-accurate hair analysis techniques is critical. In this study, we utilized surface-enhanced Raman spectroscopy (SERS) to demonstrate that artificial dyes can be directly detected on hair. This spectroscopic technique is capable of a confirmatory identification of analytes with single molecule resolution, requires minimal sample, and has the advantage of fluorescence quenching. Our study reveals that SERS can (1) identify whether hair was artificially dyed or not, (2) determine if a permanent or semipermanent colorants were used, and (3) distinguish the commercial brands that are utilized to dye hair. Such analysis is rapid, minimally destructive, and can be performed directly at the crime scene. This study provides a novel perspective of forensic investigations of hair evidence. PMID:25635868

  17. In situ Raman study of electrochemical lithium insertion into mesocarbon microbeads heat-treated at various temperatures

    SciTech Connect

    Inaba, Minoru; Yoshida, Hiroyuki; Ogumi, Zempachi

    1996-08-01

    In situ Raman spectra were measured to elucidate the electrochemical lithium insertion mechanism of mesocarbon microbeads (MCMBs) heat-treated at 700 to 2,800 C. The spectral changes of the Raman E{sub 2g2} band of MCMBs heat-treated at 2,800 C showed that the lithium insertion mechanism into the microbeads is similar to that into graphite via the formation of staged graphite intercalation compounds, although a clear phase transition from dilute stage 1 to stage 4 was not observed. For MCMBs heat-treated at 1,800 and 1,000 C the E{sub 2g2} band shifted downward and upward upon charging and discharging, respectively. No discontinuous change suggesting the formation of staged phases was observed, which indicated that lithium is inserted randomly between graphene layers without the formation of staged phases. The charge and discharge profile of MCMBs heat-treated at 700 C showed a large hysteresis. A potential plateau appeared at about 1 V on the discharge curve, which led to a high capacity of 710 mAh/g. In the case of MCMBs heat-treated at 700 C, the peak wave number of the E{sub 2g2} band did not shift at all in the whole potential range during charging and discharging. It was considered that the plateau region of MCMBs heat-treated at 700 C giving the high discharge capacity originates not from lithium species inserted between organized graphene layers, but from lithium doped into regions without organized graphitic structure.

  18. In-situ stress analysis of the Zr/ZrO2 system as studied by Raman spectroscopy and deflection test in monofacial oxidation techniques

    NASA Astrophysics Data System (ADS)

    Kurpaska, L.; Favergeon, J.; Grosseau-Poussard, J.-L.; Lahoche, L.; Moulin, G.

    2016-11-01

    A comparison of measurements performed in in-situ conditions using Raman spectroscopy and Deflection Test in Monofacial Oxidation techniques were employed to study stress states developed in zirconia films grown at 500 °C is presented. The results show a good correlation between recorded Raman peak displacement and sample deflection angle. Considering analyzed volume of the material, Raman analysis represents a local measurement while the deflection test is a global response of the material. Reported stress components: (i) hydrostatic - resulted from Raman spectroscopy and (ii) in-plane - resulted from deflection test technique have been analyzed in comparison to each of the described techniques and aim to explain the behavior of zirconia at high temperatures.

  19. In situ imaging of interfacial precipitation of phosphate on Goethite.

    PubMed

    Wang, Lijun; Putnis, Christine V; Ruiz-Agudo, Encarnación; Hövelmann, Jörn; Putnis, Andrew

    2015-04-01

    Adsorption and subsequent immobilization of orthophosphate on iron oxides is of considerable importance in soil fertility and eutrophication studies. Here, in situ atomic force microscopy (AFM) has been used to probe the interaction of phosphate-bearing solutions with goethite, α-FeOOH, (010) cleavage surfaces. During the dissolution of goethite we observed simultaneous nucleation of nanoparticles (1.0-3.0 nm in height) of iron phosphate (Fe-P) phases at the earliest nucleation stages, subsequent aggregation to form secondary particles (about 6.0 nm in height) and layered precipitates under various pH values and ionic strengths relevant to acid soil solution conditions. The heterogeneous nucleation rates of Fe-P precipitates at phosphate concentrations ranging from 5.0 to 50.0 mM were quantitatively defined. Enhanced goethite dissolution in the presence of high concentration NaCl or AlCl3 leads to a rapid increase in Fe-P nucleation rates, whereas low concentration MgCl2 inhibits goethite dissolution, this in turn influences Fe-P nucleation. Moreover, kinetic data analyses show that low concentrations of citrate caused an increase in the nucleation rate of Fe-P phases. However, at higher concentrations of citrate, nucleation acceleration was reversed with much longer induction times to form Fe-P nuclei. These in situ observations may improve the mechanistic understanding of processes resulting in phosphate immobilization by goethite-rich acid soils in the presence of various inorganic and organic additive molecules. PMID:25763812

  20. Optical cell for combinatorial in situ Raman spectroscopic measurements of hydrogen storage materials at high pressures and temperatures

    NASA Astrophysics Data System (ADS)

    Hattrick-Simpers, Jason R.; Hurst, Wilbur S.; Srinivasan, Sesha S.; Maslar, James E.

    2011-03-01

    An optical cell is described for high-throughput backscattering Raman spectroscopic measurements of hydrogen storage materials at pressures up to 10 MPa and temperatures up to 823 K. High throughput is obtained by employing a 60 mm diameter × 9 mm thick sapphire window, with a corresponding 50 mm diameter unobstructed optical aperture. To reproducibly seal this relatively large window to the cell body at elevated temperatures and pressures, a gold o-ring is employed. The sample holder-to-window distance is adjustable, making this cell design compatible with optical measurement systems incorporating lenses of significantly different focal lengths, e.g., microscope objectives and single element lenses. For combinatorial investigations, up to 19 individual powder samples can be loaded into the optical cell at one time. This cell design is also compatible with thin-film samples. To demonstrate the capabilities of the cell, in situ measurements of the Ca(BH4)2 and nano-LiBH4-LiNH2-MgH2 hydrogen storage systems at elevated temperatures and pressures are reported.

  1. In Situ Fabrication of 3D Ag@ZnO Nanostructures for Microfluidic Surface-Enhanced Raman Scattering Systems

    PubMed Central

    2015-01-01

    In this work, we develop an in situ method to grow highly controllable, sensitive, three-dimensional (3D) surface-enhanced Raman scattering (SERS) substrates via an optothermal effect within microfluidic devices. Implementing this approach, we fabricate SERS substrates composed of Ag@ZnO structures at prescribed locations inside microfluidic channels, sites within which current fabrication of SERS structures has been arduous. Conveniently, properties of the 3D Ag@ZnO nanostructures such as length, packing density, and coverage can also be adjusted by tuning laser irradiation parameters. After exploring the fabrication of the 3D nanostructures, we demonstrate a SERS enhancement factor of up to ∼2 × 106 and investigate the optical properties of the 3D Ag@ZnO structures through finite-difference time-domain simulations. To illustrate the potential value of our technique, low concentrations of biomolecules in the liquid state are detected. Moreover, an integrated cell-trapping function of the 3D Ag@ZnO structures records the surface chemical fingerprint of a living cell. Overall, our optothermal-effect-based fabrication technique offers an effective combination of microfluidics with SERS, resolving problems associated with the fabrication of SERS substrates in microfluidic channels. With its advantages in functionality, simplicity, and sensitivity, the microfluidic-SERS platform presented should be valuable in many biological, biochemical, and biomedical applications. PMID:25402207

  2. In-situ plasmon-driven chemical reactions revealed by high vacuum tip-enhanced Raman spectroscopy

    PubMed Central

    Sun, Mengtao; Zhang, Zhenglong; Zheng, Hairong; Xu, Hongxing

    2012-01-01

    With strong surface plasmons excited at the metallic tip, tip-enhanced Raman spectroscopy (TERS) has both high spectroscopic sensitivity and high spatial resolution, and is becoming an essential tool for chemical analysis. It is a great challenge to combine TERS with a high vacuum system due to the poor optical collection efficiency. We used our innovatively designed home-built high vacuum TERS (HV-TERS) to investigate the plasmon-driven in-situ chemical reaction of 4-nitrobenzenethiol dimerizing to dimercaptoazobenzene. The chemical reactions can be controlled by the plasmon intensity, which in turn can be controlled by the incident laser intensity, tunneling current and bias voltage. The temperature of such a chemical reaction can also be obtained by the clearly observed Stokes and Anti-Stokes HV-TERS peaks. Our findings offer a new way to design a highly efficient HV-TERS system and its applications to chemical catalysis and synthesis of molecules, and significantly extend the studies of chemical reactions. PMID:22970339

  3. In Situ Analysis of a Silver Nanoparticle-Precipitating Shewanella Biofilm by Surface Enhanced Confocal Raman Microscopy.

    PubMed

    Schkolnik, Gal; Schmidt, Matthias; Mazza, Marco G; Harnisch, Falk; Musat, Niculina

    2015-01-01

    Shewanella oneidensis MR-1 is an electroactive bacterium, capable of reducing extracellular insoluble electron acceptors, making it important for both nutrient cycling in nature and microbial electrochemical technologies, such as microbial fuel cells and microbial electrosynthesis. When allowed to anaerobically colonize an Ag/AgCl solid interface, S. oneidensis has precipitated silver nanoparticles (AgNp), thus providing the means for a surface enhanced confocal Raman microscopy (SECRaM) investigation of its biofilm. The result is the in-situ chemical mapping of the biofilm as it developed over time, where the distribution of cytochromes, reduced and oxidized flavins, polysaccharides and phosphate in the undisturbed biofilm is monitored. Utilizing AgNp bio-produced by the bacteria colonizing the Ag/AgCl interface, we could perform SECRaM while avoiding the use of a patterned or roughened support or the introduction of noble metal salts and reducing agents. This new method will allow a spatially and temporally resolved chemical investigation not only of Shewanella biofilms at an insoluble electron acceptor, but also of other noble metal nanoparticle-precipitating bacteria in laboratory cultures or in complex microbial communities in their natural habitats.

  4. In Situ Analysis of a Silver Nanoparticle-Precipitating Shewanella Biofilm by Surface Enhanced Confocal Raman Microscopy

    PubMed Central

    Schkolnik, Gal; Schmidt, Matthias; Mazza, Marco G.; Harnisch, Falk; Musat, Niculina

    2015-01-01

    Shewanella oneidensis MR-1 is an electroactive bacterium, capable of reducing extracellular insoluble electron acceptors, making it important for both nutrient cycling in nature and microbial electrochemical technologies, such as microbial fuel cells and microbial electrosynthesis. When allowed to anaerobically colonize an Ag/AgCl solid interface, S. oneidensis has precipitated silver nanoparticles (AgNp), thus providing the means for a surface enhanced confocal Raman microscopy (SECRaM) investigation of its biofilm. The result is the in-situ chemical mapping of the biofilm as it developed over time, where the distribution of cytochromes, reduced and oxidized flavins, polysaccharides and phosphate in the undisturbed biofilm is monitored. Utilizing AgNp bio-produced by the bacteria colonizing the Ag/AgCl interface, we could perform SECRaM while avoiding the use of a patterned or roughened support or the introduction of noble metal salts and reducing agents. This new method will allow a spatially and temporally resolved chemical investigation not only of Shewanella biofilms at an insoluble electron acceptor, but also of other noble metal nanoparticle-precipitating bacteria in laboratory cultures or in complex microbial communities in their natural habitats. PMID:26709923

  5. In-situ plasmon-driven chemical reactions revealed by high vacuum tip-enhanced Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Sun, Mengtao; Zhang, Zhenglong; Zheng, Hairong; Xu, Hongxing

    2012-09-01

    With strong surface plasmons excited at the metallic tip, tip-enhanced Raman spectroscopy (TERS) has both high spectroscopic sensitivity and high spatial resolution, and is becoming an essential tool for chemical analysis. It is a great challenge to combine TERS with a high vacuum system due to the poor optical collection efficiency. We used our innovatively designed home-built high vacuum TERS (HV-TERS) to investigate the plasmon-driven in-situ chemical reaction of 4-nitrobenzenethiol dimerizing to dimercaptoazobenzene. The chemical reactions can be controlled by the plasmon intensity, which in turn can be controlled by the incident laser intensity, tunneling current and bias voltage. The temperature of such a chemical reaction can also be obtained by the clearly observed Stokes and Anti-Stokes HV-TERS peaks. Our findings offer a new way to design a highly efficient HV-TERS system and its applications to chemical catalysis and synthesis of molecules, and significantly extend the studies of chemical reactions.

  6. In-situ laser Raman scattering and far infrared spectroscopy studies of corrosion-passivation phenomena in metals.

    SciTech Connect

    Melendres, C. A.

    1999-06-28

    Vibrational spectroscopic and electrochemical techniques are among the most useful tools for the elucidation of corrosion-passivation phenomena in metals. The former can provide information on the structure and composition of corrosion films ''in situ'' in aqueous solution environments, while thermodynamic and kinetic information may be obtained using electrochemical techniques. In this paper, we demonstrate the application of Laser Raman Scattering (LRS) and Synchrotrons Far Infrared Reflectance Spectroscopy (SFIRS), coupled with electrochemical methods, for the determination of the structure and composition of surface films on nickel and copper in aqueous solution environment. The corrosion film on nickel has been found to consist of NiO and Ni(OH){sub 2} in the passive region of potential and NiOOH in the transpassive region. The film on copper consists of Cu{sub 2}O, CUO and Cu(OH){sub 2}. We also show for the first time that SFIRS can be used to obtain information on the adsorption of ions on a metal surface with sub-monolayer sensitivity. Adsorption of Cl{sup {minus}}, Br{sup {minus}}, SO{sup {minus}2}, and PO{sub 4}{sup {minus}3} was found to occur at gold electrodes in perchloric acid solution. We also observed that when two different ions are present in solution, the more strongly adsorbed ion determined the corrosion behavior of the metal.

  7. Time-lapse Raman imaging of osteoblast differentiation

    NASA Astrophysics Data System (ADS)

    Hashimoto, Aya; Yamaguchi, Yoshinori; Chiu, Liang-Da; Morimoto, Chiaki; Fujita, Katsumasa; Takedachi, Masahide; Kawata, Satoshi; Murakami, Shinya; Tamiya, Eiichi

    2015-07-01

    Osteoblastic mineralization occurs during the early stages of bone formation. During this mineralization, hydroxyapatite (HA), a major component of bone, is synthesized, generating hard tissue. Many of the mechanisms driving biomineralization remain unclear because the traditional biochemical assays used to investigate them are destructive techniques incompatible with viable cells. To determine the temporal changes in mineralization-related biomolecules at mineralization spots, we performed time-lapse Raman imaging of mouse osteoblasts at a subcellular resolution throughout the mineralization process. Raman imaging enabled us to analyze the dynamics of the related biomolecules at mineralization spots throughout the entire process of mineralization. Here, we stimulated KUSA-A1 cells to differentiate into osteoblasts and conducted time-lapse Raman imaging on them every 4 hours for 24 hours, beginning 5 days after the stimulation. The HA and cytochrome c Raman bands were used as markers for osteoblastic mineralization and apoptosis. From the Raman images successfully acquired throughout the mineralization process, we found that β-carotene acts as a biomarker that indicates the initiation of osteoblastic mineralization. A fluctuation of cytochrome c concentration, which indicates cell apoptosis, was also observed during mineralization. We expect time-lapse Raman imaging to help us to further elucidate osteoblastic mineralization mechanisms that have previously been unobservable.

  8. Time-lapse Raman imaging of osteoblast differentiation

    PubMed Central

    Hashimoto, Aya; Yamaguchi, Yoshinori; Chiu, Liang-da; Morimoto, Chiaki; Fujita, Katsumasa; Takedachi, Masahide; Kawata, Satoshi; Murakami, Shinya; Tamiya, Eiichi

    2015-01-01

    Osteoblastic mineralization occurs during the early stages of bone formation. During this mineralization, hydroxyapatite (HA), a major component of bone, is synthesized, generating hard tissue. Many of the mechanisms driving biomineralization remain unclear because the traditional biochemical assays used to investigate them are destructive techniques incompatible with viable cells. To determine the temporal changes in mineralization-related biomolecules at mineralization spots, we performed time-lapse Raman imaging of mouse osteoblasts at a subcellular resolution throughout the mineralization process. Raman imaging enabled us to analyze the dynamics of the related biomolecules at mineralization spots throughout the entire process of mineralization. Here, we stimulated KUSA-A1 cells to differentiate into osteoblasts and conducted time-lapse Raman imaging on them every 4 hours for 24 hours, beginning 5 days after the stimulation. The HA and cytochrome c Raman bands were used as markers for osteoblastic mineralization and apoptosis. From the Raman images successfully acquired throughout the mineralization process, we found that β-carotene acts as a biomarker that indicates the initiation of osteoblastic mineralization. A fluctuation of cytochrome c concentration, which indicates cell apoptosis, was also observed during mineralization. We expect time-lapse Raman imaging to help us to further elucidate osteoblastic mineralization mechanisms that have previously been unobservable. PMID:26211729

  9. Structural evolution of NM (Ni and Mn) lithium-rich layered material revealed by in-situ electrochemical Raman spectroscopic study

    NASA Astrophysics Data System (ADS)

    Huang, Jing-Xin; Li, Bing; Liu, Bo; Liu, Bi-Ju; Zhao, Jin-Bao; Ren, Bin

    2016-04-01

    Li-rich layered materials are one of promising candidates of cathode materials for energy storage in electric vehicles (EVs) due to their high energy density. The practical application of these materials relies on the in-depth understanding of the crystal structures and reaction mechanisms during the electrochemical processes to overcome the potential decay issue. In this work, in-situ electrochemical Raman spectroscopy has been developed and used to investigate the structural evolution of the Li-rich layered material (0.5LiNi0.5Mn0.5O2·0.5Li2MnO3). An electrochemical Raman spectroscopic cell with an excellent air-tightness and optical signal collection efficiency has been designed and used for in-situ investigation of the NM Li-rich material during the very first two electrochemical cycles. We found that the reactions of Ni2+ to Ni3+ and Ni3+ to Ni4+ appearing in the potential range of from 3.70 V to 4.45 V show a good reversibility. The in-situ Raman spectra after the first two electrochemical cycles also indicate the activation of Li2MnO3 changes the ionic local coordination structure and increases the ionic disorder of the pristine NM Li-rich layered material. This structural change has a great impact on the subsequent electrochemical cycles. The in-situ Raman spectroscopy results can help to improve the performance of NM Li-rich layered materials.

  10. MicroRaman Spectroscopy and Raman Imaging of Basal Cell Carcinoma

    NASA Astrophysics Data System (ADS)

    Short, M. A.; Zeng, H.; Lui, H.

    2005-03-01

    We have measured the Raman spectra of normal and cancerous skin tissues using a confocal microRaman spectrograph with a sub-micron spatial resolution. We found that the Raman spectrum of a cell nucleolus is different from the spectra measured outside the nucleolus and considerably different from those measured outside the nucleus. In addition, we found significant spectroscopic differences between normal and cancer-bearing sites in the dermis region. In order to utilize these differences for non-invasive skin cancer diagnosis, we have developed a Raman imaging system that clearly demonstrates the structure, location and distribution of cells in unstained skin biopsy samples. Our method is expected to be useful for the detection and characterization of skin cancer based on the known distinct cellular differences between normal and malignant skin.

  11. In situ dissolution analysis of pharmaceutical dosage forms using coherent anti-Stokes Raman scattering (CARS) microscopy

    NASA Astrophysics Data System (ADS)

    Fussell, A. L.; Garbacik, E. T.; Löbmann, K.; Offerhaus, H. L.; Kleinebudde, P.; Strachan, C. J.

    2014-02-01

    A custom-built intrinsic flow-through dissolution setup was developed and incorporated into a home-built CARS microscope consisting of a synchronously pumped optical parametric oscillator (OPO) and an inverted microscope with a 20X/0.5NA objective. CARS dissolution images (512×512 pixels) were collected every 1.12s for the duration of the dissolution experiment. Hyperspectral CARS images were obtained pre- and postdissolution by rapidly imaging while sweeping the wavelength of the OPO in discrete steps so that each frame in the data stack corresponds to a vibrational frequency. An image-processing routine projects this hyperspectral data into a single image wherein each compound appears with a unique color. Dissolution was conducted using theophylline and cimetidine-naproxen co-amorphous mixture. After 15 minutes of theophylline dissolution, hyperspectral imaging showed a conversion of theophylline anhydrate to the monohydrate, confirmed by a peak shift in the CARS spectra. CARS dissolution images showed that monohydrate crystal growth began immediately and reached a maximum with complete surface coverage at about 300s. This result correlated with the UV dissolution data where surface crystal growth on theophylline compacts resulted in a rapidly reducing dissolution rate during the first 300s. Co-amorphous cimetidinenaproxen didn't appear to crystallize during dissolution. We observed solid-state conversions on the compact's surface in situ during dissolution. Hyperspectral CARS imaging allowed visual discrimination between the solid-state forms on the compact's surface. In the case of theophylline we were able to correlate the solid-state change with a change in dissolution rate.

  12. RAMAN spectroscopy imaging improves the diagnosis of papillary thyroid carcinoma

    PubMed Central

    Rau, Julietta V.; Graziani, Valerio; Fosca, Marco; Taffon, Chiara; Rocchia, Massimiliano; Crucitti, Pierfilippo; Pozzilli, Paolo; Onetti Muda, Andrea; Caricato, Marco; Crescenzi, Anna

    2016-01-01

    Recent investigations strongly suggest that Raman spectroscopy (RS) can be used as a clinical tool in cancer diagnosis to improve diagnostic accuracy. In this study, we evaluated the efficiency of Raman imaging microscopy to discriminate between healthy and neoplastic thyroid tissue, by analyzing main variants of Papillary Thyroid Carcinoma (PTC), the most common type of thyroid cancer. We performed Raman imaging of large tissue areas (from 100 × 100 μm2 up to 1 × 1 mm2), collecting 38 maps containing about 9000 Raman spectra. Multivariate statistical methods, including Linear Discriminant Analysis (LDA), were applied to translate Raman spectra differences between healthy and PTC tissues into diagnostically useful information for a reliable tissue classification. Our study is the first demonstration of specific biochemical features of the PTC profile, characterized by significant presence of carotenoids with respect to the healthy tissue. Moreover, this is the first evidence of Raman spectra differentiation between classical and follicular variant of PTC, discriminated by LDA with high efficiency. The combined histological and Raman microscopy analyses allow clear-cut integration of morphological and biochemical observations, with dramatic improvement of efficiency and reliability in the differential diagnosis of neoplastic thyroid nodules, paving the way to integrative findings for tumorigenesis and novel therapeutic strategies. PMID:27725756

  13. RAMAN spectroscopy imaging improves the diagnosis of papillary thyroid carcinoma

    NASA Astrophysics Data System (ADS)

    Rau, Julietta V.; Graziani, Valerio; Fosca, Marco; Taffon, Chiara; Rocchia, Massimiliano; Crucitti, Pierfilippo; Pozzilli, Paolo; Onetti Muda, Andrea; Caricato, Marco; Crescenzi, Anna

    2016-10-01

    Recent investigations strongly suggest that Raman spectroscopy (RS) can be used as a clinical tool in cancer diagnosis to improve diagnostic accuracy. In this study, we evaluated the efficiency of Raman imaging microscopy to discriminate between healthy and neoplastic thyroid tissue, by analyzing main variants of Papillary Thyroid Carcinoma (PTC), the most common type of thyroid cancer. We performed Raman imaging of large tissue areas (from 100 × 100 μm2 up to 1 × 1 mm2), collecting 38 maps containing about 9000 Raman spectra. Multivariate statistical methods, including Linear Discriminant Analysis (LDA), were applied to translate Raman spectra differences between healthy and PTC tissues into diagnostically useful information for a reliable tissue classification. Our study is the first demonstration of specific biochemical features of the PTC profile, characterized by significant presence of carotenoids with respect to the healthy tissue. Moreover, this is the first evidence of Raman spectra differentiation between classical and follicular variant of PTC, discriminated by LDA with high efficiency. The combined histological and Raman microscopy analyses allow clear-cut integration of morphological and biochemical observations, with dramatic improvement of efficiency and reliability in the differential diagnosis of neoplastic thyroid nodules, paving the way to integrative findings for tumorigenesis and novel therapeutic strategies.

  14. Morphology-dependent stimulated Raman scattering imaging. I. Theoretical aspects

    SciTech Connect

    Aker, P.M.; Moortgat, P.A.; Zhang, J.

    1996-11-01

    Morphology-dependent stimulated Raman scattering is a nonlinear laser Raman spectroscopy that relies on using the cavity modes associated with micron-sized structures to enhance optical signal generation. Since different cavity modes occupy different regions in space, location-specific spectra can be generated. Here we outline the physics behind morphology-dependent stimulated Raman scattering imaging and model the signal generation process. The results show that a simple tailoring of the illumination conditions allows signal from single, but selectable, cavity modes to be generated. Thus, this nonlinear Raman technique can be used to image spatial variations in chemical composition and/or molecular structure within microstructures. {copyright} {ital 1996 American Institute of Physics.}

  15. High-Speed Coherent Raman Fingerprint Imaging of Biological Tissues

    PubMed Central

    Camp, Charles H.; Lee, Young Jong; Heddleston, John M.; Hartshorn, Christopher M.; Hight Walker, Angela R.; Rich, Jeremy N.; Lathia, Justin D.; Cicerone, Marcus T.

    2014-01-01

    An imaging platform based on broadband coherent anti-Stokes Raman scattering (BCARS) has been developed which provides an advantageous combination of speed, sensitivity and spectral breadth. The system utilizes a configuration of laser sources that probes the entire biologically-relevant Raman window (500 cm−1 to 3500 cm−1) with high resolution (< 10 cm−1). It strongly and efficiently stimulates Raman transitions within the typically weak “fingerprint” region using intrapulse 3-colour excitation, and utilizes the nonresonant background (NRB) to heterodyne amplify weak Raman signals. We demonstrate high-speed chemical imaging in two- and three-dimensional views of healthy murine liver and pancreas tissues and interfaces between xenograft brain tumours and the surrounding healthy brain matter. PMID:25621002

  16. High-speed coherent Raman fingerprint imaging of biological tissues

    NASA Astrophysics Data System (ADS)

    Camp, Charles H., Jr.; Lee, Young Jong; Heddleston, John M.; Hartshorn, Christopher M.; Walker, Angela R. Hight; Rich, Jeremy N.; Lathia, Justin D.; Cicerone, Marcus T.

    2014-08-01

    An imaging platform based on broadband coherent anti-Stokes Raman scattering has been developed that provides an advantageous combination of speed, sensitivity and spectral breadth. The system utilizes a configuration of laser sources that probes the entire biologically relevant Raman window (500-3,500 cm-1) with high resolution (<10 cm-1). It strongly and efficiently stimulates Raman transitions within the typically weak ‘fingerprint’ region using intrapulse three-colour excitation, and utilizes the non-resonant background to heterodyne-amplify weak Raman signals. We demonstrate high-speed chemical imaging in two- and three-dimensional views of healthy murine liver and pancreas tissues as well as interfaces between xenograft brain tumours and the surrounding healthy brain matter.

  17. Raman Imaging with a Fiber-Coupled Multichannel Spectrograph

    PubMed Central

    Schmälzlin, Elmar; Moralejo, Benito; Rutowska, Monika; Monreal-Ibero, Ana; Sandin, Christer; Tarcea, Nicolae; Popp, Jürgen; Roth, Martin M.

    2014-01-01

    Until now, spatially resolved Raman Spectroscopy has required to scan a sample under investigation in a time-consuming step-by-step procedure. Here, we present a technique that allows the capture of an entire Raman image with only one single exposure. The Raman scattering arising from the sample was collected with a fiber-coupled high-performance astronomy spectrograph. The probe head consisting of an array of 20 × 20 multimode fibers was linked to the camera port of a microscope. To demonstrate the high potential of this new concept, Raman images of reference samples were recorded. Entire chemical maps were received without the need for a scanning procedure. PMID:25420149

  18. The OCT penlight: in-situ image guidance for microsurgery

    NASA Astrophysics Data System (ADS)

    Galeotti, John; Sajjad, Areej; Wang, Bo; Kagemann, Larry; Shukla, Gaurav; Siegel, Mel; Wu, Bing; Klatzky, Roberta; Wollstein, Gadi; Schuman, Joel S.; Stetten, George

    2010-02-01

    We have developed a new image-based guidance system for microsurgery using optical coherence tomography (OCT), which presents a virtual image in its correct location inside the scanned tissue. Applications include surgery of the cornea, skin, and other surfaces below which shallow targets may advantageously be displayed for the naked eye or low-power magnification by a surgical microscope or loupes (magnifying eyewear). OCT provides real-time highresolution (3 micron) images at video rates within a two or more millimeter axial range in soft tissue, and is therefore suitable for guidance to various shallow targets such as Schlemm's canal in the eye (for treating Glaucoma) or skin tumors. A series of prototypes of the "OCT penlight" have produced virtual images with sufficient resolution and intensity to be useful under magnification, while the geometrical arrangement between the OCT scanner and display optics (including a half-silvered mirror) permits sufficient surgical access. The two prototypes constructed thus far have used, respectively, a miniature organic light emitting diode (OLED) display and a reflective liquid crystal on silicon (LCoS) display. The OLED has the advantage of relative simplicity, satisfactory resolution (15 micron), and color capability, whereas the LCoS can produce an image with much higher intensity and superior resolution (12 micron), although it is monochromatic and more complicated optically. Intensity is a crucial limiting factor, since light flux is greatly diminished with increasing magnification, thus favoring the LCoS as the more practical system.

  19. Surface enhanced Raman spectroscopy hyphenated with surface microextraction for in-situ detection of polycyclic aromatic hydrocarbons on food contact materials.

    PubMed

    Zhang, Min; Zhang, Xiaoli; Shi, Yu-E; Liu, Zhen; Zhan, Jinhua

    2016-09-01

    Highly bioaccumulated polycyclic aromatic hydrocarbons (PAHs) have cause health concerns because of their carcinogenic properties. PAHs could migrate to food from contaminated food contact materials. In this study, a hyphenated technique combining surface enhanced Raman spectroscopy (SERS) with surface microextraction was developed for in-situ on site screening of PAHs on food contact materials. Methanol and 1-propanethiol-modified silver nanoparticles (PTH-Ag NPs) were used to perform the in-situ microextraction and detection of PAHs, respectively. The SERS spectra can be obtained by a portable Raman spectrometer. The vibration of the C-C bond of PTH at 1030cm(-1) was chosen as an internal standard peak. The PTH-Ag NPs showed high uniformity with an RSD of 2.96%. A plot of the normalized SERS intensity against fluoranthene concentration showed a linear relationship (R(2)=0.98). The detection limit could reach 0.27ngcm(-2). The in-situ microextraction-SERS hyphenated technique for the detection of three PAHs at five food contact materials was demonstrated. The method can be also applied to detect PAH mixtures. This in-situ microextraction-SERS hyphenated method demonstrated its ability to rapidly screen PAHs on contaminated food contact materials free from complex sample pretreatment. PMID:27343612

  20. Dental caries imaging using hyperspectral stimulated Raman scattering microscopy

    NASA Astrophysics Data System (ADS)

    Wang, Zi; Zheng, Wei; Jian, Lin; Huang, Zhiwei

    2016-03-01

    We report the development of a polarization-resolved hyperspectral stimulated Raman scattering (SRS) imaging technique based on a picosecond (ps) laser-pumped optical parametric oscillator system for label-free imaging of dental caries. In our imaging system, hyperspectral SRS images (512×512 pixels) in both fingerprint region (800-1800 cm-1) and high-wavenumber region (2800-3600 cm-1) are acquired in minutes by scanning the wavelength of OPO output, which is a thousand times faster than conventional confocal micro Raman imaging. SRS spectra variations from normal enamel to caries obtained from the hyperspectral SRS images show the loss of phosphate and carbonate in the carious region. While polarization-resolved SRS images at 959 cm-1 demonstrate that the caries has higher depolarization ratio. Our results demonstrate that the polarization resolved-hyperspectral SRS imaging technique developed allows for rapid identification of the biochemical and structural changes of dental caries.

  1. Microscopic structural changes of SiO2 glasses as a function of temperature investigated by in situ Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Shimodaira, N.; Saito, K.; Sekiya, E. H.; Ikushima, A. J.

    2006-06-01

    In situ Raman spectroscopic measurements with a useful peak deconvolution technique were attempted in this paper to quantitatively investigate the structural changes of silica glass as a function of temperature in the range from room temperature to 1300°C . By utilizing an F-doped silica glass having a fictive temperature Tf(=Tg)=700°C , we have made clear observations of the structural relaxation in the supercooled liquid state as well as the thermal expansion in the glassy state. From the frequency shift of fundamental vibrations with the increase of temperature, it was deduced that the decreases of both the Si-O-Si average bond angle θ and the Si-O bond-stretching force constant α simultaneously occur by thermal expansion. Contrary to a previous report, the rates of change of band frequencies with temperature are definitely less sensitive to Tg , while the D2 (and D1 ) intensity explicitly increases above Tg . The activation energy of D2 formation was determined by using actual temperature to be 0.43±0.02eV , which is close to the previously obtained ones in pure silica glass by using Tf evaluated at room temperature. Based on the central-force network model and the so-called “Badger’s law,” it was evaluated from the shift of ω4 frequency that the rate of change of θ as a function of temperature, Δθ/ΔT , is approximately -0.02°/°C , and is a few times larger than Δθ/ΔTf , approximately -0.005°/°C . The intrinsic mechanism of the angular change with Tf in silica glass is also explained from these results.

  2. Ice particle crystallization in the presence of ethanol: an in situ study by Raman and X-ray diffraction.

    PubMed

    Facq, Sébastien; Danède, Florence; Chazallon, Bertrand

    2013-06-13

    Two distinct ethanol aqueous solution droplets ((X(EtOH))L = 8.7 wt % and 46.5 wt %) are investigated by in situ Raman spectroscopy and X-ray diffraction between 253 and 88 K. Structural changes are identified by modifications in the O-H and C-H stretching modes (2800-3800 cm(-1) spectral region) during freezing and annealing events. They are attributed to the formation of ice and/or different hydrate structures in the EtOH-water system. At high initial ethanol concentration, the particle is found to be composed of a modified clathrate I (cubic structure) at 211 K on cooling and transformed into an ethanol hydrate II (monoclinic structure) on annealing between ∼143 and 173 K. This latter decomposes at ∼200 K and leaves an aqueous solution and ice Ih which further dissociates above ∼230 K. At low initial concentration, ice first forms on cooling and the particle consists of a crystalline ice core embedded in a liquid layer of high ethanol content at ~200 K (or an amorphous layer at lower T). A new hydrate (IV) of distinct structure (orthorhombic) is observed on annealing (from 100 K) between ∼123 K and ∼142 K (depending on initial composition), which transforms into the ethanol hydrate II at ∼160 K. The hydrate II decomposes at ∼200 K, and ice Ih remains (and dissociate above ∼220 K) in coexistence with the liquid layer of high ethanol content. It is proposed that the complex crystalline ice particles formed may have the potential to impact several atmospherical processes differently in comparison to the pure ice case. PMID:23682626

  3. Raman chemical imaging of the rhizosphere bacterium Pantoea sp. YR343 and its co-culture with Arabidopsis thaliana

    DOE PAGES

    Polisetti, Sneha; Bible, Amber N.; Morrell-Falvey, Jennifer L.; Bohn, Paul W.

    2016-02-29

    Chemical imaging of plant-bacteria co-cultures renders it possible to characterize bacterial populations and behaviors and their interactions with proximal organisms, under conditions closest to the environment in the rhizosphere. Here Raman micro-spectroscopy and confocal Raman imaging are used as minimally invasive probes to study the rhizosphere bacterial isolate, Pantoea sp. YR343, and its co-culture with model plant Arabidopsis thaliana by combining enhanced Raman spectroscopies with electron microscopy and principal component analysis (PCA). The presence of carotenoid pigments in the wild type Pantoea sp. YR343 was characterized using resonance Raman scattering, which was also used to confirm successful disruption of themore » crtB gene in an engineered carotenoid mutant strain. Other components of the Pantoea sp. YR343 cells were imaged in the presence of resonantly enhanced pigments using a combination of surface enhanced Raman imaging and PCA. Pantoea sp. YR343 cells decorated with Ag colloid synthesized ex situ gave spectra dominated by carotenoid scattering, whereas colloids synthesized in situ produced spectral signatures characteristic of flavins in the cell membrane. Scanning electron microscopy (SEM) of whole cells and transmission electron microscopy (TEM) images of thinly sliced cross-sections were used to assess structural integrity of the coated cells and to establish the origin of spectral signatures based on the position of Ag nanoparticles in the cells. Finally, raman imaging was also used to characterize senescent green Arabidopsis thaliana plant roots inoculated with Pantoea sp. YR343, and PCA was used to distinguish spectral contributions from plant and bacterial cells, thereby establishing the potential of Raman imaging to visualize the distribution of rhizobacteria on plant roots.« less

  4. Raman chemical imaging of the rhizosphere bacterium Pantoea sp. YR343 and its co-culture with Arabidopsis thaliana.

    PubMed

    Polisetti, Sneha; Bible, Amber N; Morrell-Falvey, Jennifer L; Bohn, Paul W

    2016-04-01

    Chemical imaging of plant-bacteria co-cultures makes it possible to characterize bacterial populations and behaviors and their interactions with proximal organisms, under conditions closest to the environment in the rhizosphere. Here Raman micro-spectroscopy and confocal Raman imaging are used as minimally invasive probes to study the rhizosphere bacterial isolate, Pantoea sp. YR343, and its co-culture with model plant Arabidopsis thaliana by combining enhanced Raman spectroscopies with electron microscopy and principal component analysis (PCA). The presence of carotenoid pigments in the wild type Pantoea sp. YR343 was characterized using resonance Raman scattering, which was also used to confirm successful disruption of the crtB gene in an engineered carotenoid mutant strain. Other components of the Pantoea sp. YR343 cells were imaged in the presence of resonantly enhanced pigments using a combination of surface enhanced Raman imaging and PCA. Pantoea sp. YR343 cells decorated with Ag colloid synthesized ex situ gave spectra dominated by carotenoid scattering, whereas colloids synthesized in situ produced spectral signatures characteristic of flavins in the cell membrane. Scanning electron microscopy (SEM) of whole cells and transmission electron microscopy (TEM) images of thinly sliced cross-sections were used to assess structural integrity of the coated cells and to establish the origin of spectral signatures based on the position of Ag nanoparticles in the cells. Raman imaging was also used to characterize senescent green Arabidopsis thaliana plant roots inoculated with Pantoea sp. YR343, and PCA was used to distinguish spectral contributions from plant and bacterial cells, thereby establishing the potential of Raman imaging to visualize the distribution of rhizobacteria on plant roots. PMID:26948490

  5. Ultrasonic separation of a suspension for in situ spectroscopic imaging

    NASA Astrophysics Data System (ADS)

    Nogo, Kosuke; Qi, Wei; Mori, Keita; Ogawa, Satoshi; Inohara, Daichi; Hosono, Satsuki; Kawashima, Natsumi; Nishiyama, Akira; Wada, Kenji; Ishimaru, Ichiro

    2016-04-01

    Application of spectroscopic techniques to suspensions is difficult because optical scattering caused by solid particles reduces the accuracy. At the extreme, dense suspensions like blood cannot be analyzed by spectroscopic techniques. In the present study, an ultrasonic standing wave was used to agglomerate fluorescent particles in an aqueous ethanol suspension at the nodes of the standing wave. Relatively clear liquid regions, which contained few particles that could cause optical scattering, appeared around the anti-nodes and were used for spectroscopic imaging. This produced a spectrum that was similar to that of clear aqueous ethanol without any fluorescent particles.

  6. Making colourful sense of Raman images of single cells.

    PubMed

    Ashton, Lorna; Hollywood, Katherine A; Goodacre, Royston

    2015-03-21

    In order to understand biological systems it is important to gain pertinent information on the spatial localisation of chemicals within cells. With the relatively recent advent of high-resolution chemical imaging this is being realised and one rapidly developing area of research is the Raman mapping of single cells, an approach whose success has vast potential for numerous areas of biomedical research. However, there is a danger of undermining the potential routine use of Raman mapping due to a lack of consistency and transparency in the way false-shaded Raman images are constructed. In this study we demonstrate, through the use of simulated data and real Raman maps of single human keratinocyte (HaCaT) cells, how changes in the application of colour shading can dramatically alter the final Raman images. In order to avoid ambiguity and potential subjectivity in image interpretation we suggest that data distribution plots are used to aid shading approaches and that extreme care is taken to use the most appropriate false-shading for the biomedical question under investigation.

  7. Separation of true fat and water images by correcting magnetic field inhomogeneity in-situ

    SciTech Connect

    Yeung, H.N.; Kormos, D.W.

    1986-06-01

    Dixon's method of chemical shift imaging of a two-component system is modified and extended without requiring additional imaging time. The modified method allows one to obtain truly segregated fat and water images of animal tissues. This is accomplished by acquiring additional image data from which information about in situ magnetic field inhomogeneity and bulk magnetic susceptibility can be derived. Applications to various anatomic sections of the normal human body are illustrated. The method is compared with the standard Dixon technique of chemical shift image separation.

  8. Tissue and cell imaging in situ: potential for applications in pathology and endoscopy.

    PubMed

    Scoazec, J-Y

    2003-06-01

    Morphological sciences have recently experienced a significant technological breakthrough that offers new opportunities for cell and tissue imaging in situ but also raises new challenges to pathologists, who must adapt to a rapidly evolving environment. New partners, such as cell and molecular biologists, have provided pathologists with highly powerful tools for cell and subcellular imaging. They include: (a) the adaptation of techniques derived from molecular biology and cytogenetics, (b) the development of new microscopic tools, such as confocal microscopy, and (c) the emergence of new preparative techniques, such as microdissection or tissue arrays. However, recent technological progresses in various fields, from endoscopy to genomics, also raise new challenges to pathologists. Pathologists must therefore be prepared to redefine their area of expertise: this will be achieved through a continuous collaboration with all the partners involved in cell and tissue imaging and analysis but also by emphasising the importance of the informations provided by cell and tissue imaging in situ.

  9. Tissue and cell imaging in situ: potential for applications in pathology and endoscopy

    PubMed Central

    Scoazec, J

    2003-01-01

    Morphological sciences have recently experienced a significant technological breakthrough that offers new opportunities for cell and tissue imaging in situ but also raises new challenges to pathologists, who must adapt to a rapidly evolving environment. New partners, such as cell and molecular biologists, have provided pathologists with highly powerful tools for cell and subcellular imaging. They include: (a) the adaptation of techniques derived from molecular biology and cytogenetics, (b) the development of new microscopic tools, such as confocal microscopy, and (c) the emergence of new preparative techniques, such as microdissection or tissue arrays. However, recent technological progresses in various fields, from endoscopy to genomics, also raise new challenges to pathologists. Pathologists must therefore be prepared to redefine their area of expertise: this will be achieved through a continuous collaboration with all the partners involved in cell and tissue imaging and analysis but also by emphasising the importance of the informations provided by cell and tissue imaging in situ. PMID:12746261

  10. Confocal Raman imaging of crystalline an glassy materials

    SciTech Connect

    Bradley, N.L.; Morris, M.D.

    1995-12-31

    Spatial distribution of materials components can be measured by confocal Raman imaging. We describe a confocal line-imaging system in which the spectrograph entrance slit functions as a spatial filter. The instrument uses a scanning galvanometer mirror to generate uniform intensity line illumination. A flexure mount with better than 0.1 micrometer positioning accuracy moves the sample under the fixed optical system. The Raman scatter is collected and projected along the entrance slit of an axial transmissive spectrograph. A CCD collects spatially resolved spectra.

  11. Development and integration of Raman imaging capabilities to Sandia National Laboratories hyperspectral fluorescence imaging instrument.

    SciTech Connect

    Timlin, Jerilyn Ann; Nieman, Linda T.

    2005-11-01

    Raman spectroscopic imaging is a powerful technique for visualizing chemical differences within a variety of samples based on the interaction of a substance's molecular vibrations with laser light. While Raman imaging can provide a unique view of samples such as residual stress within silicon devices, chemical degradation, material aging, and sample heterogeneity, the Raman scattering process is often weak and thus requires very sensitive collection optics and detectors. Many commercial instruments (including ones owned here at Sandia National Laboratories) generate Raman images by raster scanning a point focused laser beam across a sample--a process which can expose a sample to extreme levels of laser light and requires lengthy acquisition times. Our previous research efforts have led to the development of a state-of-the-art two-dimensional hyperspectral imager for fluorescence imaging applications such as microarray scanning. This report details the design, integration, and characterization of a line-scan Raman imaging module added to this efficient hyperspectral fluorescence microscope. The original hyperspectral fluorescence instrument serves as the framework for excitation and sample manipulation for the Raman imaging system, while a more appropriate axial transmissive Raman imaging spectrometer and detector are utilized for collection of the Raman scatter. The result is a unique and flexible dual-modality fluorescence and Raman imaging system capable of high-speed imaging at high spatial and spectral resolutions. Care was taken throughout the design and integration process not to hinder any of the fluorescence imaging capabilities. For example, an operator can switch between the fluorescence and Raman modalities without need for extensive optical realignment. The instrument performance has been characterized and sample data is presented.

  12. In situ calibration of an infrared imaging video bolometer in the Large Helical Device

    SciTech Connect

    Mukai, K. Peterson, B. J.; Pandya, S. N.; Sano, R.

    2014-11-15

    The InfraRed imaging Video Bolometer (IRVB) is a powerful diagnostic to measure multi-dimensional radiation profiles in plasma fusion devices. In the Large Helical Device (LHD), four IRVBs have been installed with different fields of view to reconstruct three-dimensional profiles using a tomography technique. For the application of the measurement to plasma experiments using deuterium gas in LHD in the near future, the long-term effect of the neutron irradiation on the heat characteristics of an IRVB foil should be taken into account by regular in situ calibration measurements. Therefore, in this study, an in situ calibration system was designed.

  13. In situ Raman spectroscopy of the graphene/water interface of a solution-gated field-effect transistor: electron-phonon coupling and spectroelectrochemistry

    NASA Astrophysics Data System (ADS)

    Binder, J.; Urban, J. M.; Stepniewski, R.; Strupinski, W.; Wysmolek, A.

    2016-01-01

    We present a novel measurement approach which combines the electrical characterization of solution-gated field-effect transistors based on epitaxial bilayer graphene on 4H-SiC (0001) with simultaneous Raman spectroscopy. By changing the gate voltage, we observed Raman signatures related to the resonant electron-phonon coupling. An analysis of these Raman bands enabled the extraction of the geometrical capacitance of the system and an accurate calculation of the Fermi levels for bilayer graphene. An intentional application of higher gate voltages allowed us to trigger electrochemical reactions, which we followed in situ by Raman spectroscopy. The reactions showed a partially reversible character, as indicated by an emergence/disappearance of peaks assigned to C-H and Si-H vibration modes as well as an increase/decrease of the defect-related Raman D band intensity. Our setup provides a highly interesting platform for future spectroelectrochemical research on electrically-induced sorption processes of graphene on the micrometer scale.

  14. Towards eye-safe standoff Raman imaging systems

    NASA Astrophysics Data System (ADS)

    Glimtoft, Martin; Bââth, Petra; Saari, Heikki; Mäkynen, Jussi; Näsilä, Antti; Östmark, Henric

    2014-05-01

    Standoff Raman imaging systems have shown the ability to detect single explosives particles. However, in many cases, the laser intensities needed restrict the applications where they can be safely used. A new generation imaging Raman system has been developed based on a 355 nm UV laser that, in addition to eye safety, allows discrete and invisible measurements. Non-dangerous exposure levels for the eye are several orders of magnitude higher in UVA than in the visible range that previously has been used. The UV Raman system has been built based on an UV Fabry-Perot Interferometer (UV-FPI) developed by VTT. The design allows for precise selection of Raman shifts in combination with high out-of-band blocking. The stable operation of the UV-FPI module under varying environmental conditions is arranged by controlling the temperature of the module and using a closed loop control of the FPI air gap based on capacitive measurement. The system presented consists of a 3rd harmonics Nd:YAG laser with 1.5 W average output at 1000 Hz, a 200 mm Schmidt-Cassegrain telescope, UV-FPI filter and an ICCD camera for signal gating and detection. The design principal leads to a Raman spectrum in each image pixel. The system is designed for field use and easy manoeuvring. Preliminary results show that in measurements of <60 s on 10 m distance, single AN particles of <300 μm diameter can be identified.

  15. Interactions between Coronal Mass Ejections Viewed in Coordinated Imaging and In Situ Observations

    NASA Technical Reports Server (NTRS)

    Liu, Ying D.; Luhmann, Janet G.; Moestl, Christian; Martinez-Oliveros, Juan C.; Bale, Stewart D.; Lin, Robert P.; Harrison, Richard A.; Temmer, Manuela; Webb, David F.; Odstrcil, Dusan

    2013-01-01

    The successive coronal mass ejections (CMEs) from 2010 July 30 - August 1 present us the first opportunity to study CME-CME interactions with unprecedented heliospheric imaging and in situ observations from multiple vantage points. We describe two cases of CME interactions: merging of two CMEs launched close in time and overtaking of a preceding CME by a shock wave. The first two CMEs on August 1 interact close to the Sun and form a merged front, which then overtakes the July 30 CME near 1 AU, as revealed by wide-angle imaging observations. Connections between imaging observations and in situ signatures at 1 AU suggest that the merged front is a shock wave, followed by two ejecta observed at Wind which seem to have already merged. In situ measurements show that the CME from July 30 is being overtaken by the shock at 1 AU and is significantly compressed, accelerated and heated. The interaction between the preceding ejecta and shock also results in variations in the shock strength and structure on a global scale, as shown by widely separated in situ measurements from Wind and STEREO B. These results indicate important implications of CME-CME interactions for shock propagation, particle acceleration and space weather forecasting.

  16. INTERACTIONS BETWEEN CORONAL MASS EJECTIONS VIEWED IN COORDINATED IMAGING AND IN SITU OBSERVATIONS

    SciTech Connect

    Liu, Ying D.; Luhmann, Janet G.; Moestl, Christian; Martinez-Oliveros, Juan C.; Bale, Stuart D.; Lin, Robert P.; Harrison, Richard A.; Temmer, Manuela; Webb, David F.; Odstrcil, Dusan

    2012-02-20

    The successive coronal mass ejections (CMEs) from 2010 July 30 to August 1 present us the first opportunity to study CME-CME interactions with unprecedented heliospheric imaging and in situ observations from multiple vantage points. We describe two cases of CME interactions: merging of two CMEs launched close in time and overtaking of a preceding CME by a shock wave. The first two CMEs on August 1 interact close to the Sun and form a merged front, which then overtakes the July 30 CME near 1 AU, as revealed by wide-angle imaging observations. Connections between imaging observations and in situ signatures at 1 AU suggest that the merged front is a shock wave, followed by two ejecta observed at Wind which seem to have already merged. In situ measurements show that the CME from July 30 is being overtaken by the shock at 1 AU and is significantly compressed, accelerated, and heated. The interaction between the preceding ejecta and shock also results in variations in the shock strength and structure on a global scale, as shown by widely separated in situ measurements from Wind and STEREO B. These results indicate important implications of CME-CME interactions for shock propagation, particle acceleration, and space weather forecasting.

  17. Laser wavelength selection for Raman spectroscopy of microbial pigments in situ in Antarctic desert ecosystem analogues of former habitats on Mars

    NASA Astrophysics Data System (ADS)

    Edwards, Howell G. M.; Newton, Emma M.; Wynn-Williams, David D.; Dickensheets, David; Schoen, Chris; Crowder, Chelle

    2002-10-01

    The vital ultraviolet- (UV-) protective and photosynthetic pigments of cyanobacteria and lichens (microbial symbioses) that dominate primary production in Antarctic desert ecosystems auto-fluoresce at short wavelengths. We therefore use a long-wavelength (1064 nm) infrared laser for non-intrusive in situ Raman spectrometry of their ecologically significant compounds (especially pigments). To confirm that the power loss at this longer wavelength is justified to avoid swamping by background fluorescence, we compared Raman spectra obtained with excitation at 1064, 852, 830, 785, 633 and 515 nm. These are typical of lasers used for Raman spectroscopy. We analysed communities of the cyanobacterium Nostoc commune and the highly pigmented lichens Acarospora chlorophana and Caloplaca saxicola. These require screening compounds (e.g. pigments such as scytonemin in cyanobacteria and rhizocarpic acid in the fungal symbiont of lichens). They are augmented by quenching pigments (e.g. carotenoids) to dissipate the energy of free radicals generated by penetrating UV. We also analysed organisms having avoidance strategies (e.g. endolithic communities within translucent rocks, including the common cyanobacterium Chroococcidiopsis). These require accessory pigments for photosynthesis at very low light intensities. Although some organisms gave useable Raman spectra with short-wavelength lasers, 1064 nm was the only excitation that was consistently excellent for all organisms. We conclude that a 1064 nm Raman spectrometer, miniaturized using an InGaAs detector, is the optimal instrument for in situ studies of pigmented microbial communities at the limits of life on Earth. This has practical potential for the quest for biomolecules residual from any former surface life on Mars.

  18. Achieving molecular selectivity in imaging using multiphoton Raman spectroscopy techniques

    SciTech Connect

    Holtom, Gary R. ); Thrall, Brian D. ); Chin, Beek Yoke ); Wiley, H Steven ); Colson, Steven D. )

    2000-12-01

    In the case of most imaging methods, contrast is generated either by physical properties of the sample (Differential Image Contrast, Phase Contrast), or by fluorescent labels that are localized to a particular protein or organelle. Standard Raman and infrared methods for obtaining images are based upon the intrinsic vibrational properties of molecules, and thus obviate the need for attached flurophores. Unfortunately, they have significant limitations for live-cell imaging. However, an active Raman method, called Coherent Anti-Stokes Raman Scattering (CARS), is well suited for microscopy, and provides a new means for imaging specific molecules. Vibrational imaging techniques, such as CARS, avoid problems associated with photobleaching and photo-induced toxicity often associated with the use of fluorescent labels with live cells. Because the laser configuration needed to implement CARS technology is similar to that used in other multiphoton microscopy methods, such as two -photon fluorescence and harmonic generation, it is possible to combine imaging modalities, thus generating simultaneous CARS and fluorescence images. A particularly powerful aspect of CARS microscopy is its ability to selectively image deuterated compounds, thus allowing the visualization of molecules, such as lipids, that are chemically indistinguishable from the native species.

  19. Combined analysis of cervical smears. Cytopathology, image cytometry and in situ hybridization.

    PubMed

    Multhaupt, H; Bruder, E; Elit, L; Rothblat, I; Warhol, M

    1993-01-01

    This study was an attempt to correlate the Bethesda System of Papanicolaou smear classification with DNA content by image analysis and the presence of human papillomavirus (HPV) as determined by in situ hybridization. DNA histograms were classified as normal diploid, diploid proliferative, polyploid and aneuploid. HPV in situ hybridization was performed with a cocktail of probes specific to HPV types 6, 11, 16 and 18. There was a good correlation between normal cytology and normal DNA histograms. Cytologically normal smears with bacterial or fungal infections showed a high proliferation index. HPV infection correlated with DNA polyploidy but was seen in 15 of 29 smears classified as cytologically normal. Morphologically abnormal Papanicolaou smears correlated with aneuploid DNA content. Smears classified as intraepithelial neoplasia correlated with aneuploid DNA content in all 12 cases. Four of five cases cytologically suspicious for HPV infection had HPV by in situ hybridization.

  20. Raman spectra and optical coherent tomography images of skin

    NASA Astrophysics Data System (ADS)

    Villanueva-Luna, A. E.; Castro-Ramos, J.; Vazquez-Montiel, S.; Flores-Gil, A.; Delgado-Atencio, J. A.; Vazquez-Villa, A.

    2011-03-01

    The optical coherence tomography images are useful to see the internal profile and the structure of material samples. In this work, OCT images were recorded in 10 volunteers with different skin tone which were related to Raman spectra. The areas where we obtained OCT images and Raman spectra were a) index finger nail, b) between index finger and middle finger, c) middle finger tip, d) half of middle finger, e) the thumb finger tip and f) between index finger and thumb, areas measured were for the purpose of finding extracellular fluids with contain triglycerides, cholesterol and glucose that are reported in the literature. The excitation wavelength used for this work was 785 nm, a spectrometer of 6 cm-1 resolution. The spectral region used ranges from 300 to 1800 cm-1. We use an OCT with 930 nm of Central Wavelength, 1.6 mm of Image Depth, 6 mm of image width and 6.2 μm of axial resolution.

  1. Imaging EGFR distribution using surface-enhanced Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Lucas, L.; Chen, X. K.; Smith, A.; Korbelik, M.; Zeng, H.; Lee, P. W. K.; Hewitt, K. C.

    2009-02-01

    The purpose of this study is to explore the feasibility of using Surface Enhanced Raman Spectroscopy (SERS) to image the distribution of Epidermal Growth Factor Receptor (EGFR) in cells. To accomplish this task, 30 nm gold nanoparticles (AuNPs) tagged with antibodies to EGFR (1012 per ml) are incubated with cells (106 per ml) of the A431 human epidermoid carcinoma cell line and normal human bronchial epithelial (NHBE) cells. Using the 632.8 nm excitation line of a He-Ne laser, Raman spectroscopy measurements are performed using a point mapping scheme. SERS signals are observed with an overall enhancement of 4-7 orders of magnitude. Raman intensity maps of the 1480 and 1583 cm-1 peaks correlate well with the expected distribution of AuNPs and EGFR. Normal cells show little to no enhancement. The results therefore present a simple yet effective means to image EGFR over-expression.

  2. In Situ Casting and Imaging of the Rat Airway Tree for Accurate 3D Reconstruction

    SciTech Connect

    Jacob, Rick E.; Colby, Sean M.; Kabilan, Senthil; Einstein, Daniel R.; Carson, James P.

    2013-08-01

    The use of anatomically accurate, animal-specific airway geometries is important for understanding and modeling the physiology of the respiratory system. One approach for acquiring detailed airway architecture is to create a bronchial cast of the conducting airways. However, typical casting procedures either do not faithfully preserve the in vivo branching angles, or produce rigid casts that when removed for imaging are fragile and thus easily damaged. We address these problems by creating an in situ bronchial cast of the conducting airways in rats that can be subsequently imaged in situ using 3D micro-CT imaging. We also demonstrate that deformations in airway branch angles resulting from the casting procedure are small, and that these angle deformations can be reversed through an interactive adjustment of the segmented cast geometry. Animal work was approved by the Institutional Animal Care and Use Committee of Pacific Northwest National Laboratory.

  3. In Situ Casting and Imaging of the Rat Airway Tree for Accurate 3D Reconstruction

    PubMed Central

    Jacob, Richard E.; Colby, Sean M.; Kabilan, Senthil; Einstein, Daniel R.; Carson, James P.

    2014-01-01

    The use of anatomically accurate, animal-specific airway geometries is important for understanding and modeling the physiology of the respiratory system. One approach for acquiring detailed airway architecture is to create a bronchial cast of the conducting airways. However, typical casting procedures either do not faithfully preserve the in vivo branching angles or produce rigid casts that when removed for imaging are fragile and thus easily damaged. We address these problems by creating an in situ bronchial cast of the conducting airways in rats that can be subsequently imaged in situ using 3D micro-CT imaging. We also demonstrate that deformations in airway branch angles resulting from the casting procedure are small, and that these angle deformations can be reversed through an interactive adjustment of the segmented cast geometry. Animal work was approved by the Institutional Animal Care and Use Committee of Pacific Northwest National Laboratory. PMID:23786464

  4. Enhanced Raman Microprobe Imaging of Single-Wall Carbon Nanotubes

    NASA Technical Reports Server (NTRS)

    Hadjiev, V. G.; Arepalli, S.; Nikolaev, P.; Jandl, S.; Yowell, L.

    2003-01-01

    We explore Raman microprobe capabilities to visualize single wall carbon nanotubes (SWCNTs). Although this technique is limited to a micron scale, we demonstrate that images of individual SWCNTs, bundles or their agglomerates can be generated by mapping Raman active elementary excitations. We measured the Raman response from carbon vibrations in SWCNTs excited by confocal scanning of a focused laser beam. Carbon vibrations reveal key characteristics of SWCNTs as nanotube diameter distribution (radial breathing modes, RBM, 100-300 cm(exp -1)), presence of defects and functional groups (D-mode, 1300-1350 cm(exp -1)), strain and oxidation states of SWCNTs, as well as metallic or semiconducting character of the tubes encoded in the lineshape of the G-modes at 1520-1600 cm(exp - 1). In addition, SWCNTs are highly anisotropic scatterers. The Raman response from a SWCNT is maximal for incident light polarization parallel to the tube axis and vanishing for perpendicular directions. We show that the SWCNT bundle shape or direction can be determined, with some limitations, from a set of Raman images taken at two orthogonal directions of the incident light polarization.

  5. Detecting multiple adulterants in dry milk using Raman chemical imaging

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A Raman chemical imaging method was developed for detecting the presence of multiple chemical adulterants in dry milk powder. Four chemicals (ammonium sulfate, dicyandiamide, melamine, and urea) were added in equal concentrations, between 0.1% and 5.0%, to nonfat dry milk. An area of 25×25 mm2 for e...

  6. Development of an Integrated Raman and Turbidity Fiber Optic Sensor for the In-Situ Analysis of High Level Nuclear Waste

    SciTech Connect

    Gasbarro, Christina; Bello, Job M.; Bryan, Samuel A.; Lines, Amanda M.; Levitskaia, Tatiana G.

    2013-02-24

    Stored nuclear waste must be retrieved from storage, treated, separated into low- and high-level waste streams, and finally put into a disposal form that effectively encapsulates the waste and isolates it from the environment for a long period of time. Before waste retrieval can be done, waste composition needs to be characterized so that proper safety precautions can be implemented during the retrieval process. In addition, there is a need for active monitoring of the dynamic chemistry of the waste during storage since the waste composition can become highly corrosive. This work describes the development of a novel, integrated fiber optic Raman and light scattering probe for in situ use in nuclear waste solutions. The dual Raman and turbidity sensor provides simultaneous chemical identification of nuclear waste as well as information concerning the suspended particles in the waste using a common laser excitation source.

  7. Development of an Integrated Raman and Turbidity Fiber Optic Sensor for the In-Situ Analysis of High Level Nuclear Waste - 13532

    SciTech Connect

    Gasbarro, Christina; Bello, Job; Bryan, Samuel; Lines, Amanda; Levitskaia, Tatiana

    2013-07-01

    Stored nuclear waste must be retrieved from storage, treated, separated into low- and high-level waste streams, and finally put into a disposal form that effectively encapsulates the waste and isolates it from the environment for a long period of time. Before waste retrieval can be done, waste composition needs to be characterized so that proper safety precautions can be implemented during the retrieval process. In addition, there is a need for active monitoring of the dynamic chemistry of the waste during storage since the waste composition can become highly corrosive. This work describes the development of a novel, integrated fiber optic Raman and light scattering probe for in situ use in nuclear waste solutions. The dual Raman and turbidity sensor provides simultaneous chemical identification of nuclear waste as well as information concerning the suspended particles in the waste using a common laser excitation source. (authors)

  8. In situ Raman and UV-vis spectroscopic studies of polypyrrole and poly(pyrrole-2,6-dimethyl-β-cyclodextrin).

    PubMed

    Arjomandi, Jalal; Shah, Anwar-ul-Haq Ali; Bilal, Salma; Van Hoang, Hung; Holze, Rudolf

    2011-01-01

    Polypyrrole (PPy) and poly(pyrrole-2,6-dimethyl-β-cyclodextrin) [P(Py-β-DMCD)] films prepared by potential cycling in aqueous acidic solutions on indium tin oxide (ITO)-coated glass and gold electrodes were studied by in situ UV-vis and Raman spectroscopy. Characteristic UV-vis and Raman bands were identified and their dependencies on the electrode potential have been discussed. Spectroelectrochemical results reveal differences both in the position of the spectral bands and their potential dependence for PPy and P(Py-β-DMCD) films indicating interactions between polymer chains and CDs during electropolymerization process. The films were also characterized by cyclic voltammetry and FT-IR spectroscopy.

  9. In situ Raman and UV-vis spectroscopic studies of polypyrrole and poly(pyrrole-2,6-dimethyl-β-cyclodextrin)

    NASA Astrophysics Data System (ADS)

    Arjomandi, Jalal; Shah, Anwar-ul-Haq Ali; Bilal, Salma; Van Hoang, Hung; Holze, Rudolf

    2011-01-01

    Polypyrrole (PPy) and poly(pyrrole-2,6-dimethyl-β-cyclodextrin) [P(Py-β-DMCD)] films prepared by potential cycling in aqueous acidic solutions on indium tin oxide (ITO)-coated glass and gold electrodes were studied by in situ UV-vis and Raman spectroscopy. Characteristic UV-vis and Raman bands were identified and their dependencies on the electrode potential have been discussed. Spectroelectrochemical results reveal differences both in the position of the spectral bands and their potential dependence for PPy and P(Py-β-DMCD) films indicating interactions between polymer chains and CDs during electropolymerization process. The films were also characterized by cyclic voltammetry and FT-IR spectroscopy.

  10. Identification of biotic and abiotic particles by using a combination of optical tweezers and in situ Raman spectroscopy.

    PubMed

    Gessner, R; Winter, C; Rösch, P; Schmitt, M; Petry, R; Kiefer, W; Lankers, M; Popp, J

    2004-08-20

    A highly versatile setup, which introduces an optical gradient trap into a Raman spectrometer, is presented. The particular configuration, which consists of two lasers, makes trapping independent from the Raman excitation laser and allows a separate adjustment of the trapping and excitation wavelengths. Thus, the excitation wavelength can be chosen according to the needs of the application. We describe the successful application of an optical gradient trap on transparent as well as on reflective, metal-coated microparticles. Raman spectra were recorded from optically trapped polystyrene beads and from single biological cells (e.g., erythrocytes, yeast cells). Also, metal-coated microparticles were trapped and used as surface enhanced Raman spectroscopy (SERS) substrates for tests on yeast cells. Furthermore, the optical gradient trap was combined with a SERS fiber probe. Raman spectra were recorded from trapped red blood cells using the SERS fiber probe for excitation.

  11. Improving sensitivity in nonlinear Raman microspectroscopy imaging and sensing

    PubMed Central

    Arora, Rajan; Petrov, Georgi I.; Liu, Jian; Yakovlev, Vladislav V.

    2011-01-01

    Nonlinear Raman microspectroscopy based on a broadband coherent anti-Stokes Raman scattering is an emerging technique for noninvasive, chemically specific, microscopic analysis of tissues and large population of cells and particles. The sensitivity of this imaging is a critical aspect of a number of the proposed biomedical application. It is shown that the incident laser power is the major parameter controlling this sensitivity. By careful optimizing the laser system, the high-quality vibrational spectra acquisition at the multi-kHz rate becomes feasible. PMID:21361677

  12. Laser-induced oxidation kinetics of bismuth surface microdroplets on GaAsBi studied in situ by Raman microprobe analysis.

    PubMed

    Steele, J A; Lewis, R A

    2014-12-29

    We report the cw-laser-induced oxidation of molecular-beam-epitaxy grown GaAsBi bismuth surface microdroplets investigated in situ by micro-Raman spectroscopy under ambient conditions as a function of irradiation power and time. Our results reveal the surface droplets are high-purity crystalline bismuth and the resultant Bi2O3 transformation to be β-phase and stable at room temperature. A detailed Raman study of Bi microdroplet oxidation kinetics yields insights into the laser-induced oxidation process and offers useful real-time diagnostics. The temporal evolution of new β-Bi2O3 Raman modes is shown to be well described by Johnson-Mehl-Avrami-Kolmogorov kinetic transformation theory and while this study limits itself to the laser-induced oxidation of GaAsBi bismuth surface droplets, the results will find application within the wider context of bismuth laser-induced oxidation and direct Raman laser processing.

  13. Detecting multiple adulterants in dry milk using Raman chemical imaging

    NASA Astrophysics Data System (ADS)

    Qin, Jianwei; Chao, Kuanglin; Kim, Moon S.

    2012-05-01

    This study investigated the potential of Raman chemical imaging for simultaneously detecting multiple adulterants in milk powder. Potential chemical adulterants, including ammonium sulfate, dicyandiamide, melamine, and urea, were together mixed into nonfat dry milk in the concentration range of 0.1%-5.0% for each adulterant. A benchtop point-scan Raman imaging system using a 785-nm laser was assembled to acquire hyperspectral images in the wavenumber range of 102-2538 cm-1. Each mixture was imaged in an area of 25×25 mm2 with a spatial resolution of 0.25 mm. Selfmodeling mixture analysis (SMA) was used to extract pure component spectra, by which the four types of the adulterants were identified at all concentration levels based on their spectral information divergence values to the reference spectra. Raman chemical images were created using the contribution images from SMA, and their use to effectively visualize identification and spatial distribution of the multiple adulterant particles in the dry milk was demonstrated.

  14. In situ recognition of cell-surface glycans and targeted imaging of cancer cells

    PubMed Central

    Xu, Xiao-Ding; Cheng, Han; Chen, Wei-Hai; Cheng, Si-Xue; Zhuo, Ren-Xi; Zhang, Xian-Zheng

    2013-01-01

    Fluorescent sensors capable of recognizing cancer-associated glycans, such as sialyl Lewis X (sLex) tetrasaccharide, have great potential for cancer diagnosis and therapy. Studies on water-soluble and biocompatible sensors for in situ recognition of cancer-associated glycans in live cells and targeted imaging of cancer cells are very limited at present. Here we report boronic acid-functionalized peptide-based fluorescent sensors (BPFSs) for in situ recognition and differentiation of cancer-associated glycans, as well as targeted imaging of cancer cells. By screening BPFSs with different structures, it was demonstrated that BPFS1 with a FRGDF peptide could recognize cell-surface glycan of sLex with high specificity and thereafter fluorescently label and discriminate cancer cells through the cooperation with the specific recognition between RGD and integrins. The newly developed peptide-based sensor will find great potential as a fluorescent probe for cancer diagnosis. PMID:24042097

  15. Making a Hybrid Microfluidic Platform Compatible for In Situ Imaging by Vacuum-Based Techniques

    SciTech Connect

    Yang, Li; Yu, Xiao-Ying; Zhu, Zihua; Thevuthasan, Suntharampillai; Cowin, James P.

    2011-10-26

    A self-contained microfluidic-based device was designed and fabricated for in situ imaging of aqueous surfaces using vacuum techniques. The device is a hybrid between a microfluidic PDMS block and external accessories, all portable on a small platform (10 cm-8 cm). The key feature is that a small aperture with a diameter of 2-3 micrometers is opened to the vacuum, which serves as a detection window for in situ imaging of aqueous surfaces. Vacuum compatibility and temperature drop due to water vaporization are the two most important challenges in this invention. Theoretical calculations and fabrication strategies are presented from multiple design aspects. In addition, results from the time-of-flight secondary ion mass spectrometry (ToF-SIMS) of aqueous surfaces are presented.

  16. Raman characterization of high temperature materials using an imaging detector

    SciTech Connect

    Rosenblatt, G.M.; Veirs, D.K.

    1989-03-01

    The characterization of materials by Raman spectroscopy has been advanced by recent technological developments in light detectors. Imaging photomultiplier-tube detectors are now available that impart position information in two dimensions while retaining photon-counting sensitivity, effectively greatly reducing noise. The combination of sensitivity and reduced noise allows smaller amounts of material to be analyzed. The ability to observe small amount of material when coupled with position information makes possible Raman characterization in which many spatial elements are analyzed simultaneously. Raman spectroscopy making use of these capabilities has been used, for instance, to analyze the phases present in carbon films and fibers and to map phase-transformed zones accompanying crack propagation in toughened zirconia ceramics. 16 refs., 6 figs., 2 tabs.

  17. Analysis of In-Situ Organic and Mineral Compounds Relevant to Martian Astrobiology Using 266 nm Raman Spectroscopy

    NASA Astrophysics Data System (ADS)

    Eshelman, E.; Daly, M. G.; Slater, G.; Dietrich, P.; Gravel, J. F.; Cloutis, E.

    2014-12-01

    Raman spectroscopy has become increasingly desirable for astrobiological investigations on Mars due to the potential for stand-off measurements, sensitivity to organic and mineral targets, and detection on unprepared surfaces. While the majority of existing Raman instruments intended for planetary exploration operate in the visible or near infrared, an ultraviolet Raman wavelength offers potential advantages including increased Raman cross section, decreased fluorescence in the Raman window, and increased signal due to resonance with some organics. This work presents a Raman spectrometer with an excitation of 266 nm, designed around the putative requirements of a flight instrument. We demonstrate spatial mapping of organic and mineral compounds on Mars analogue samples from the Canadian Arctic and the Atacama Desert, showcasing the reduced fluorescence and increased scattering efficiency compared to longer wavelengths. The Raman window provided by a 266 nm excitation is advantageously positioned to observe fluorescence bands that are characteristic to terrestrial bacteria yet do not overlap with the Raman signal. We present the potential for time-resolved nanosecond scale gating of the detector in characterizing mineral and organic fluorescence by measuring the fluorescence lifetime of endoliths in gypsum. The characteristic short lifetime of the bacterial fluorescence provides additional information regarding the presence of organic carbon in the sample, and therefore combined Raman-fluorescence measurements may increase the sensitivity of the instrument to organic carbon. This research was carried out at the Planetary Instrumentation Laboratory at York University, and supported in part by both the Canadian Space Agency (CSA) and by the Natural Sciences and Engineering Research Council of Canada (NSERC).

  18. Miniature Variable Pressure Scanning Electron Microscope for In-Situ Imaging and Chemical Analysis

    NASA Technical Reports Server (NTRS)

    Gaskin, Jessica A.; Jerman, Gregory; Gregory, Don; Sampson, Allen R.

    2012-01-01

    NASA Marshall Space Flight Center (MSFC) is leading an effort to develop a Miniaturized Variable Pressure Scanning Electron Microscope (MVP-SEM) for in-situ imaging and chemical analysis of uncoated samples. This instrument development will be geared towards operation on Mars and builds on a previous MSFC design of a mini-SEM for the moon (funded through the NASA Planetary Instrument Definition and Development Program). Because Mars has a dramatically different environment than the moon, modifications to the MSFC lunar mini-SEM are necessary. Mainly, the higher atmospheric pressure calls for the use of an electron gun that can operate at High Vacuum, rather than Ultra-High Vacuum. The presence of a CO2-rich atmosphere also allows for the incorporation of a variable pressure system that enables the in-situ analysis of nonconductive geological specimens. Preliminary testing of Mars meteorites in a commercial Environmental SEM(Tradmark) (FEI) confirms the usefulness of lowcurrent/low-accelerating voltage imaging and highlights the advantages of using the Mars atmosphere for environmental imaging. The unique capabilities of the MVP-SEM make it an ideal tool for pursuing key scientific goals of NASA's Flagship Mission Max-C; to perform in-situ science and collect and cache samples in preparation for sample return from Mars.

  19. Stream temperature estimated in situ from thermal-infrared images: best estimate and uncertainty

    NASA Astrophysics Data System (ADS)

    Iezzi, F.; Todisco, M. T.

    2015-11-01

    The paper aims to show a technique to estimate in situ the stream temperature from thermal-infrared images deepening its best estimate and uncertainty. Stream temperature is an important indicator of water quality and nowadays its assessment is important particularly for thermal pollution monitoring in water bodies. Stream temperature changes are especially due to the anthropogenic heat input from urban wastewater and from water used as a coolant by power plants and industrial manufacturers. The stream temperatures assessment using ordinary techniques (e.g. appropriate thermometers) is limited by sparse sampling in space due to a spatial discretization necessarily punctual. Latest and most advanced techniques assess the stream temperature using thermal-infrared remote sensing based on thermal imagers placed usually on aircrafts or using satellite images. These techniques assess only the surface water temperature and they are suitable to detect the temperature of vast water bodies but do not allow a detailed and precise surface water temperature assessment in limited areas of the water body. The technique shown in this research is based on the assessment of thermal-infrared images obtained in situ via portable thermal imager. As in all thermographic techniques, also in this technique, it is possible to estimate only the surface water temperature. A stream with the presence of a discharge of urban wastewater is proposed as case study to validate the technique and to show its application limits. Since the technique analyzes limited areas in extension of the water body, it allows a detailed and precise assessment of the water temperature. In general, the punctual and average stream temperatures are respectively uncorrected and corrected. An appropriate statistical method that minimizes the errors in the average stream temperature is proposed. The correct measurement of this temperature through the assessment of thermal- infrared images obtained in situ via portable

  20. Toward Surface-Enhanced Raman Imaging of Latent Fingerprints

    SciTech Connect

    Connatser, Raynella M; Prokes, Sharka M.; Glembocki, Orest; Schuler, Rebecca A.; Gardner, Charles W.; Lewis Sr, Samuel Arthur; Lewis, Linda A

    2010-01-01

    Exposure to light or heat, or simply a dearth of fingerprint material, renders some latent fingerprints undetectable using conventional methods. We begin to address such elusive fingerprints using detection targeting photo- and thermally stable fingerprint constituents: surface-enhanced Raman spectroscopy (SERS). SERS can give descriptive vibrational spectra of amino acids, among other robust fingerprint constituents, and good sensitivity can be attained by improving metal-dielectric nanoparticle substrates. With SERS chemical imaging, vibrational bands intensities recreate a visual of fingerprint topography. The impact of nanoparticle synthesis route, dispersal methodology-deposition solvent, and laser wavelength are discussed, as are data from enhanced vibrational spectra of fingerprint components. SERS and Raman chemical images of fingerprints and realistic contaminants are shown. To our knowledge, this represents the first SERS imaging of fingerprints. In conclusion, this work progresses toward the ultimate goal of vibrationally detecting latent prints that would otherwise remain undetected using traditional development methods.

  1. Imaging of plant cell walls by confocal Raman microscopy.

    PubMed

    Gierlinger, Notburga; Keplinger, Tobias; Harrington, Michael

    2012-09-01

    Raman imaging of plant cell walls represents a nondestructive technique that can provide insights into chemical composition in context with structure at the micrometer level (<0.5 μm). The major steps of the experimental procedure are described: sample preparation (embedding and microcutting), setting the mapping parameters, and finally the calculation of chemical images on the basis of the acquired Raman spectra. Every Raman image is based on thousands of spectra, each being a spatially resolved molecular 'fingerprint' of the cell wall. Multiple components are analyzed within the native cell walls, and insights into polymer composition as well as the orientation of the cellulose microfibrils can be gained. The most labor-intensive step of this process is often the sample preparation, as the imaging approach requires a flat surface of the plant tissue with intact cell walls. After finishing the map (acquisition time is ∼10 min to 10 h, depending on the size of the region of interest and scanning parameters), many possibilities exist for the analysis of spectral data and image generation.

  2. Gold Nano-Popcorn Based Targeted Diagonosis, Nanotherapy Treatment and In-Situ Monitoring of Photothermal Therapy Response of Prostate Cancer Cells Using Surface Enhanced Raman Spectroscopy

    PubMed Central

    Lu, Wentong; Singh, Anant Kumar; Khan, Sadia Afrin; Senapati, Dulal; Yu, Hongtao; Ray, Paresh Chandra

    2010-01-01

    Prostate cancer is the second leading cause of cancer-related death among the American male population and the cost of treating prostate cancer patients is about $10 billion/year in the US. Current treatments are mostly ineffective against advanced stage prostate cancer disease and are often associated with severe side effects. Driven by the need, in this manuscript, we report multifunctional nanotechnology-driven gold nano-popcorn based surface enhanced Raman scattering (SERS) assay for targeted sensing, nanotherapy treatment and in-situ monitoring of photothermal nanotherapy response during the therapy process. Our experimental data show that in the presence of LNCaP human prostate cancer cell, multifunctional popcorn shape gold nanoparticle forms several hot spots and provides a significant enhancement of the Raman signal intensity by several orders of magnitude (2.5 × 109). As a result, it can recognize human prostate cancer cell in 50 cells level. Our results indicate that the localized heating that occurs during NIR irradiation is able to cause irreparable cellular damage of the prostate cancer cell. Our in-situ time dependent results demonstrates for the first time that by monitoring SERS intensity change, one can monitor photo thermal nanotherapy response during therapy process. Possible mechanisms and operating principle of our SERS assay have been discussed. Ultimately, this nanotechnology driven assay could have enormous potential applications in rapid, on-site targeted sensing, nanotherapy treatment and monitoring of nanotherapy process which is critical to providing effective treatment of cancer disease. PMID:21128627

  3. Hyperspectral image analysis for CARS, SRS, and Raman data

    PubMed Central

    Karuna, Arnica; Borri, Paola; Langbein, Wolfgang

    2015-01-01

    In this work, we have significantly enhanced the capabilities of the hyperspectral image analysis (HIA) first developed by Masia et al. 1 The HIA introduced a method to factorize the hyperspectral data into the product of component concentrations and spectra for quantitative analysis of the chemical composition of the sample. The enhancements shown here comprise (1) a spatial weighting to reduce the spatial variation of the spectral error, which improves the retrieval of the chemical components with significant local but small global concentrations; (2) a new selection criterion for the spectra used when applying sparse sampling2 to speed up sequential hyperspectral imaging; and (3) a filter for outliers in the data using singular value decomposition, suited e.g. to suppress motion artifacts. We demonstrate the enhancements on coherent anti‐Stokes Raman scattering, stimulated Raman scattering, and spontaneous Raman data. We provide the HIA software as executable for public use. © 2015 The Authors. Journal of Raman Spectroscopy published by John Wiley & Sons, Ltd. PMID:27478301

  4. Alkyne-Functionalized Superstable Graphitic Silver Nanoparticles for Raman Imaging

    PubMed Central

    2015-01-01

    Noble metals, especially gold, have been widely used in plasmon resonance applications. Although silver has a larger optical cross section and lower cost than gold, it has attracted much less attention because of its easy corrosion, thereby degrading plasmonic signals and limiting its applications. To circumvent this problem, we report the facile synthesis of superstable AgCu@graphene (ACG) nanoparticles (NPs). The growth of several layers of graphene onto the surface of AgCu alloy NPs effectively protects the Ag surface from contamination, even in the presence of hydrogen peroxide, hydrogen sulfide, and nitric acid. The ACG NPs have been utilized to enhance the unique Raman signals from the graphitic shell, making ACG an ideal candidate for cell labeling, rapid Raman imaging, and SERS detection. ACG is further functionalized with alkyne-polyethylene glycol, which has strong Raman vibrations in the Raman-silent region of the cell, leading to more accurate colocalization inside cells. In sum, this work provides a simple approach to fabricate corrosion-resistant, water-soluble, and graphene-protected AgCu NPs having a strong surface plasmon resonance effect suitable for sensing and imaging. PMID:25233109

  5. Raman imaging of the diverse states of the filamentous cyanobacteria

    NASA Astrophysics Data System (ADS)

    Ishihara, J.; Tachikawa, M.; Mochizuki, A.; Sako, Y.; Iwasaki, H.; Morita, S.

    2013-05-01

    The objective of our research was to predict cell fates of a multicellular system, accompanied by cellular differentiation. To fulfill this objective, we sought to distinguish the differentiated and undifferentiated cells of filamentous cyanobacteria (Anabaena sp. PCC 7120) using Raman imaging. This technique indicated Raman bands of the cellular system, in which several bands were assigned to vibrations of β-carotene and scytonemin. We applied principal component analysis (PCA) to the Raman spectra to determine the PC1 and PC2 loading plots and their scores. The data points obtained for heterocyst tended to converge along the bottom of the scatterplot whereas those for vegetative cells were more widely distributed in the PC plane. This indicates that the chemical compositions of a heterocyst were relatively stable. As vegetative cells are capable of proliferation or differentiation, they may transit and exist in several states including the pseudo-differentiated state. The results suggest that the chemical compositions of a vegetative cell fluctuated according to its cellular condition. In conclusion, the results of Raman imaging indicate that the diverse states of vegetative cells are localized in a specific state through differentiation.

  6. In situ Determination of Pore-water pH in Reducing Sediments near Methane Seeps and Vents by Laser Raman Spectroscopy

    NASA Astrophysics Data System (ADS)

    Peltzer, E. T.; Walz, P. M.; Luna, M.; Zhang, X.; Brewer, P. G.

    2015-12-01

    Sediments near methane vents and seeps are often anoxic in nature due to the microbial oxidation of organic matter. When the pore-water oxygen is consumed, the microbial population resorts to using sulfate as the terminal electron receptor. For the anaerobic oxidation of methane, the net reaction is: CH4 + SO42- = HCO3- + HS- + H2O. Hydrogen sulfide produced by this reaction dissociates into bisulfide in proportion to the pore-water pH. Since the first pK of H2S is about 7 and close to the in situ pore-water pH, it satisfies the criteria for a useful pH indicating dye. Although the two forms of hydrogen sulfide are not visually discernable by the human eye, these two forms have distinct Raman spectra and thus can be easily quantified using an in situ spectrometer. The relative Raman cross-sections of the hydrogen sulfide species were determined in the laboratory across a range of relevant pH values and at the approximate salinity (ionic strength) and temperature of deep-sea pore waters. With this calibration, it is simple to compute the pore-water pH from the relative abundance of the two sulfide species: pH = pK1 + log10([HS-]/[H2S]). Pore-water profiles were investigated at several sites in the Santa Monica basin around methane mounds, gas vents and cold seeps. A titanium pore-water probe with a stainless steel frit was used to filter and collect pore-water samples at 5-10 cm intervals in the top 50-60 cm of sediment. Filtration and collection of the pore-water samples was usually accomplished in 5-10 minutes, with acquisition of the laser Raman spectra requiring only 2-4 minutes additional time. Vertical profiles of sulfate, total sulfide (H2S + HS-), methane and pH were collected simultaneously using the laser Raman spectrometer and pore-water profile sampler. Sulfate was observed to decrease from seawater concentrations to below detection limits while both methane and total sulfide increased proportionally to the sulfate loss. Once total sulfide concentrations

  7. Denoising Stimulated Raman Spectroscopic Images by Total Variation Minimization

    PubMed Central

    Liao, Chien-Sheng; Choi, Joon Hee; Zhang, Delong; Chan, Stanley H.; Cheng, Ji-Xin

    2016-01-01

    High-speed coherent Raman scattering imaging is opening a new avenue to unveiling the cellular machinery by visualizing the spatio-temporal dynamics of target molecules or intracellular organelles. By extracting signals from the laser at MHz modulation frequency, current stimulated Raman scattering (SRS) microscopy has reached shot noise limited detection sensitivity. The laser-based local oscillator in SRS microscopy not only generates high levels of signal, but also delivers a large shot noise which degrades image quality and spectral fidelity. Here, we demonstrate a denoising algorithm that removes the noise in both spatial and spectral domains by total variation minimization. The signal-to-noise ratio of SRS spectroscopic images was improved by up to 57 times for diluted dimethyl sulfoxide solutions and by 15 times for biological tissues. Weak Raman peaks of target molecules originally buried in the noise were unraveled. Coupling the denoising algorithm with multivariate curve resolution allowed discrimination of fat stores from protein-rich organelles in C. elegans. Together, our method significantly improved detection sensitivity without frame averaging, which can be useful for in vivo spectroscopic imaging. PMID:26955400

  8. Detecting adulterants in milk powder using high-throughput Raman chemical imaging

    Technology Transfer Automated Retrieval System (TEKTRAN)

    This study used a line-scan high-throughput Raman imaging system to authenticate milk powder. A 5 W 785 nm line laser (240 mm long and 1 mm wide) was used as a Raman excitation source. The system was used to acquire hyperspectral Raman images in a wavenumber range of 103–2881 cm-1 from the skim milk...

  9. Understanding catalyst behavior during in situ heating through simultaneous secondary and transmitted electron imaging

    DOE PAGES

    Howe, Jane Y.; Allard, Jr., Lawrence Frederick; Demers, Hendrix; Bigelow, Wilbur C.; Steven H. Overbury

    2014-11-14

    In situ heating study via a simultaneous secondary electron (SE) and transmitted electron (TE) microscopy is extremely insightful because information from the surface (SE) and bulk (TE) can be readily obtained. The leached Au/Fe2O3 catalyst has voids on the surface of Fe2O3. Upon heating to 500 °C, voids shrank and disappeared, while internal Au species diffused to the surface to form new nanoparticles. Heating in vacuum reduced Fe2O3 to Fe3O4. Heating at 700 °C caused coalescence and growth of Au particles and formation of faceted Fe3O4 surfaces. We achieved 1.1 nm resolution in SE imaging during in situ heating.

  10. Raman Spectroscopy for Mineral Identification and Quantification for in situ Planetary Surface Analysis: A Point Count Method

    NASA Technical Reports Server (NTRS)

    Haskin, Larry A.; Wang, Alian; Rockow, Kaylynn M.; Jolliff, Bradley L.; Korotev, Randy L.; Viskupic, Karen M.

    1997-01-01

    Quantification of mineral proportions in rocks and soils by Raman spectroscopy on a planetary surface is best done by taking many narrow-beam spectra from different locations on the rock or soil, with each spectrum yielding peaks from only one or two minerals. The proportion of each mineral in the rock or soil can then be determined from the fraction of the spectra that contain its peaks, in analogy with the standard petrographic technique of point counting. The method can also be used for nondestructive laboratory characterization of rock samples. Although Raman peaks for different minerals seldom overlap each other, it is impractical to obtain proportions of constituent minerals by Raman spectroscopy through analysis of peak intensities in a spectrum obtained by broad-beam sensing of a representative area of the target material. That is because the Raman signal strength produced by a mineral in a rock or soil is not related in a simple way through the Raman scattering cross section of that mineral to its proportion in the rock, and the signal-to-noise ratio of a Raman spectrum is poor when a sample is stimulated by a low-power laser beam of broad diameter. Results obtained by the Raman point-count method are demonstrated for a lunar thin section (14161,7062) and a rock fragment (15273,7039). Major minerals (plagioclase and pyroxene), minor minerals (cristobalite and K-feldspar), and accessory minerals (whitlockite, apatite, and baddeleyite) were easily identified. Identification of the rock types, KREEP basalt or melt rock, from the 100-location spectra was straightforward.

  11. In situ imaging of the mouse cochlea using two-photon microscopy

    NASA Astrophysics Data System (ADS)

    Yang, Xin; Pu, Ye; Psaltis, Demetri; Stankovic, Konstantina M.

    2013-04-01

    Intracochlear imaging is of great interest clinically because cochlea is the central organ of hearing. However, intracochlear imaging is technologically challenging due to the cochlea's small size and encasement in bone. The state-of- the-art imaging techniques are not adequate for high resolution cellular imaging to establish diagnosis without destroying the cochlea. We report in situ imaging of intact mouse cochlea using endogenous two-photon excitation fluorescence (TPEF) as the contrast mechanism. TPEF eliminates the need for exogenous labeling and eradicating the staining-induced artifacts. We used a natural, membranous opening into the cochlea, the round window, as the optical access to reach the organ of Corti, requiring no additional slicing or opening. Our approach provides the maximum non-invasiveness in the imaging process. TPEF exhibits strong contrast allowing deep imaging of mouse cochlea with cellular and even subcellular resolution. Inner hair cell, outer hair cell and supporting cell are clearly identifiable in TPEF images. Distinct morphological differences are observed between healthy and noise-exposed cochleae, allowing detection of specific, noise-induced pathologic changes. The TPEF images taken through the round window are correlated with the whole mount sections, verifying their reliability. Compared with one-photon excitation fluorescence (OPEF) confocal microscope and wide-field transmission microscope images taken under the same magnification and resolution, TPEF images demonstrate clear advantages in terms of sharpness, signal to noise ratio and contrast. These capabilities provide a working foundation for microendoscopy-based clinical diagnostics of sensorineural hearing loss.

  12. The RAMANITA © method for non-destructive and in situ semi-quantitative chemical analysis of mineral solid-solutions by multidimensional calibration of Raman wavenumber shifts

    NASA Astrophysics Data System (ADS)

    Smith, David C.

    2005-08-01

    The "RAMANITA ©" method, for semi-quantitative chemical analysis of mineral solid-solutions by multidimensional calibration of Raman wavenumber shifts and mathematical calculation by simultaneous equations, is published here in detail in English for the first time. It was conceived by the present writer 20 years ago for binary and ternary pyroxene and garnet systems. The mathematical description was set out in 1989, but in an abstract in an obscure French special publication. Detailed "step-by-step" calibration of two garnet ternaries, followed by their linking, by M. Pinet and D.C. Smith in the early 1990s provided a hexary garnet database. Much later, using this garnet database, which forms part of his personal database called RAMANITA ©, the present writer began to develop the method by improving the terminology, automating the calculations, discussing problems and experimenting with different real chemical problems in archaeometry. Although this RAMANITA © method has been very briefly mentioned in two recent books, the necessary full mathematical explanation is given only here. The method will find application in any study which requires obtaining a non-destructive semi-quantitative chemical analysis from mineral solid solutions that cannot be analysed by any destructive analytical method, in particular for archaeological, geological or extraterrestrial research projects, e.g. from gemstones or other crystalline artworks of the cultural heritage (especially by Mobile Raman Microscopy (MRM)) in situ in museums or at archaeological sites, including under water for subaquatic archaeometry; from scientifically precious mineral microinclusions (such as garnet or pyroxene within diamond); from minerals in rocks analysed in situ on planetary bodies by a rover (especially "at distance" by telescopy). Recently some other workers have begun deducing chemical compositions from Raman wavenumber shifts in multivariate chemical space, but the philosophical approach is

  13. Light Sheet Tomography (LST) for in situ imaging of plant roots.

    PubMed

    Yang, Zhengyi; Downie, Helen; Rozbicki, Emil; Dupuy, Lionel X; MacDonald, Michael P

    2013-07-15

    The production of crops capable of efficient nutrient use is essential for addressing the problem of global food security. The ability of a plant's root system to interact with the soil micro-environment determines how effectively it can extract water and nutrients. In order to assess this ability and develop the fast and cost effective phenotyping techniques which are needed to establish efficient root systems, in situ imaging in soil is required. To date this has not been possible due to the high density of scatterers and absorbers in soil or because other growth substrates do not sufficiently model the heterogeneity of a soil's microenvironment. We present here a new form of light sheet imaging with novel transparent soil containing refractive index matched particles. This imaging method does not rely on fluorescence, but relies solely on scattering from root material. We term this form of imaging Light Sheet Tomography (LST). We have tested LST on a range of materials and plant roots in transparent soil and gel. Due to the low density of root structures, i.e. relatively large spaces between adjacent roots, long-term monitoring of lettuce root development in situ with subsequent quantitative analysis was achieved.

  14. The design and construction of a cell for the in situ monitoring of copolymerisation reactions using FT-Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Haigh, J.; Brookes, A.; Hendra, P. J.; Strawn, A.; Nicholas, C.; Purbrick, M.

    1997-01-01

    The copolymerisation of styrene and vinyl imidazole was studied online using a unique Raman cell. The copolymerisation parameters, r1 and r2, were obtained and compared with values obtained from NMR and elemental analysis. The problems associated with the technique and the data processing are discussed. Although there was poor correlation between techniques it was concluded that Raman has great potential as a much faster method therefore enabling much more data to be collected and giving information on the progress of copolymerisation reactions.

  15. Feasibility of the Simultaneous Determination of Monomer Concentrations and Particle Size in Emulsion Polymerization Using in Situ Raman Spectroscopy

    PubMed Central

    2015-01-01

    An immersion Raman probe was used in emulsion copolymerization reactions to measure monomer concentrations and particle sizes. Quantitative determination of monomer concentrations is feasible in two-monomer copolymerizations, but only the overall conversion could be measured by Raman spectroscopy in a four-monomer copolymerization. The feasibility of measuring monomer conversion and particle size was established using partial least-squares (PLS) calibration models. A simplified theoretical framework for the measurement of particle sizes based on photon scattering is presented, based on the elastic-sphere-vibration and surface-tension models. PMID:26900256

  16. Development of a Raman chemical image detection algorithm for authenticating dry milk

    NASA Astrophysics Data System (ADS)

    Qin, Jianwei; Chao, Kuanglin; Kim, Moon S.

    2013-05-01

    This research developed a Raman chemical imaging method for detecting multiple adulterants in skim milk powder. Ammonium sulfate, dicyandiamide, melamine, and urea were mixed into the milk powder as chemical adulterants in the concentration range of 0.1-5.0%. A Raman imaging system using a 785-nm laser acquired hyperspectral images in the wavenumber range of 102-2538 cm-1 for a 25×25 mm2 area of each mixture. A polynomial curve-fitting method was used to correct fluorescence background in the Raman images. An image classification method was developed based on single-band fluorescence-free images at unique Raman peaks of the adulterants. Raman chemical images were created to visualize identification and distribution of the multiple adulterant particles in the milk powder. Linear relationship was found between adulterant pixel number and adulterant concentration, demonstrating the potential of the Raman chemical imaging for quantitative analysis of the adulterants in the milk powder.

  17. In situ apparatus for the study of clathrate hydrates relevant to solar system bodies using synchrotron X-ray diffraction and Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Day, Sarah J.; Thompson, Stephen P.; Evans, Aneurin; Parker, Julia E.

    2015-02-01

    Context. Clathrate hydrates are believed to play a significant role in various solar system environments, e.g. comets, and the surfaces and interiors of icy satellites. However, the structural factors governing their formation and dissociation are poorly understood. Aims: We demonstrate the application of a high pressure gas cell, combined with variable temperature non-contact cooling and fast, time-resolved data collection, to the in situ study of clathrate hydrates under conditions relevant to solar system environments. Methods: Clathrates formed and processed within the sample cell are monitored in situ using time-resolved synchrotron X-ray powder diffraction and laser Raman spectroscopy. Results: X-ray diffraction allows the formation of clathrate hydrates to be observed as CO2 gas is applied to ice formed within the cell. Complete conversion is obtained by annealing at temperatures just below the ice melting point. A subsequent rise in the quantity of clathrate is observed as the cell is thermally cycled. Four regions between 100-5000 cm-1 are present in the in situ Raman spectra that carry features characteristic of both ice and clathrate formation. Conclusions: This novel experimental arrangement is well suited to studying clathrate hydrates over a wide range of temperature (80 -500 K) and pressure (1-100 bar) conditions relevant to solar system bodies and can be used with a variety of different gases and starting aqueous compositions (e.g. saline solutions). We propose the increase in clathrate formation observed during thermal cycling may be due to the formation of a quasi liquid-like phase that forms at temperatures below the ice melting point, but which allows either easier formation of new clathrate cages, or the retention and delocalisation of previously formed clathrate structures, possibly as amorphous clathrate. The structural similarities between hexagonal ice, the quasi liquid-like phase, and crystalline CO2 hydrate mean that differences in the

  18. Analysis of in-situ rock joint strength using digital borehole scanner images

    SciTech Connect

    Thapa, B.B.

    1994-09-01

    The availability of high resolution digital images of borehole walls using the Borehole Scanner System has made it possible to develop new methods of in-situ rock characterization. This thesis addresses particularly new approaches to the characterization of in-situ joint strength arising from surface roughness. An image processing technique is used to extract the roughness profile from joints in the unrolled image of the borehole wall. A method for estimating in-situ Rengers envelopes using this data is presented along with results from using the method on joints in a borehole in porphyritic granite. Next, an analysis of the joint dilation angle anisotropy is described and applied to the porphyritic granite joints. The results indicate that the dilation angle of the joints studied are anisotropic at small scales and tend to reflect joint waviness as scale increases. A procedure to unroll the opposing roughness profiles to obtain a two dimensional sample is presented. The measurement of apertures during this process is shown to produce an error which increases with the dip of the joint. The two dimensional sample of opposing profiles is used in a new kinematic analysis of the joint shear stress-shear deformation behavior. Examples of applying these methods on the porphyritic granite joints are presented. The unrolled opposing profiles were used in a numerical simulation of a direct shear test using Discontinuous Deformation Analysis. Results were compared to laboratory test results using core samples containing the same joints. The simulated dilatancy and shear stress-shear deformation curves were close to the laboratory curves in the case of a joint in porphyritic granite.

  19. An integrated on-line irradiation and in situ live cell imaging system

    NASA Astrophysics Data System (ADS)

    Liang, Ying; Fu, Qibin; Wang, Weikang; Liu, Yu; Liu, Feng; Yang, Gen; Wang, Yugang

    2015-09-01

    Ionizing radiation poses a threat to genome integrity by introducing DNA damages, particularly DNA double-strand breaks (DSB) in cells. Understanding how cells react to DSB and maintain genome integrity is of major importance, since increasing evidences indicate the links of DSB with genome instability and cancer predispositions. However, tracking the dynamics of DNA damages and repair response to ionizing radiation in individual cell is difficult. Here we describe the development of an on-line irradiation and in situ live cell imaging system based on isotopic sources at Institute of Heavy Ion Physics, Peking University. The system was designed to irradiate cells and in situ observe the cellular responses to ionizing radiation in real time. On-line irradiation was achieved by mounting a metal framework that hold an isotopic γ source above the cell culture dish for γ irradiation; or by integrating an isotopic α source to an objective lens under the specialized cell culture dish for α irradiation. Live cell imaging was performed on a confocal microscope with an environmental chamber installed on the microscope stage. Culture conditions in the environment chamber such as CO2, O2 concentration as well as temperature are adjustable, which further extends the capacity of the system and allows more flexible experimental design. We demonstrate the use of this system by tracking the DSB foci formation and disappearance in individual cells after exposure to irradiation. On-line irradiation together with in situ live cell imaging in adjustable culture conditions, the system overall provides a powerful tool for investigation of cellular and subcellular response to ionizing radiation under different physiological conditions such as hyperthermia or hypoxia.

  20. In situ loading of well-dispersed silver nanoparticles on nanocrystalline magnesium oxide for real-time monitoring of catalytic reactions by surface enhanced Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Zhang, Kaige; Li, Gongke; Hu, Yuling

    2015-10-01

    The surface-enhanced Raman spectroscopy (SERS) technique is of great importance for insight into the transient reaction intermediates and mechanistic pathways involved in heterogeneously catalyzed chemical reactions under actual reaction conditions, especially in water. Herein, we demonstrate a facile method for in situ synthesis of nanocrystalline magnesium oxide-Ag(0) (nano MgO-Ag(0)) hybrid nanomaterials with dispersed Ag nanoparticles (Ag NPs) on the surface of nanocrystalline magnesium oxide (nano MgO) via Sn2+ linkage and reduction. As a benefit from the synergy effect of nano MgO and Ag NPs, the nano MgO-Ag(0) exhibited both excellent SERS and catalytic activities for the reduction of 4-nitrothiophenol in the presence of NaBH4. The nano MgO-Ag(0) was used for real-time monitoring of the catalytic reaction process of 4-nitrothiophenol to 4-aminothiophenol in an aqueous medium by observing the SERS signals of the reactant, intermediate and final products. The intrinsic reaction kinetics and reaction mechanism of this reaction were also investigated. This SERS-based synergy technique provides a novel approach for quantitative in situ monitoring of catalytic chemical reaction processes.The surface-enhanced Raman spectroscopy (SERS) technique is of great importance for insight into the transient reaction intermediates and mechanistic pathways involved in heterogeneously catalyzed chemical reactions under actual reaction conditions, especially in water. Herein, we demonstrate a facile method for in situ synthesis of nanocrystalline magnesium oxide-Ag(0) (nano MgO-Ag(0)) hybrid nanomaterials with dispersed Ag nanoparticles (Ag NPs) on the surface of nanocrystalline magnesium oxide (nano MgO) via Sn2+ linkage and reduction. As a benefit from the synergy effect of nano MgO and Ag NPs, the nano MgO-Ag(0) exhibited both excellent SERS and catalytic activities for the reduction of 4-nitrothiophenol in the presence of NaBH4. The nano MgO-Ag(0) was used for real

  1. Optimized cobalt nanowires for domain wall manipulation imaged by in situ Lorentz microscopy

    SciTech Connect

    Rodriguez, L. A.; Magen, C.; Snoeck, E.; Gatel, C.; Serrano-Ramon, L.; and others

    2013-01-14

    Direct observation of domain wall (DW) nucleation and propagation in focused electron beam induced deposited Co nanowires as a function of their dimensions was carried out by Lorentz microscopy (LTEM) upon in situ application of magnetic field. Optimal dimensions favoring the unambiguous DW nucleation/propagation required for applications were found in 500-nm-wide and 13-nm-thick Co nanowires, with a maximum nucleation field and the largest gap between nucleation and propagation fields. The internal DW structures were resolved using the transport-of-intensity equation formalism in LTEM images and showed that the optimal nanowire dimensions correspond to the crossover between the nucleation of transverse and vortex walls.

  2. In vivo in situ en face optical coherence tomography imaging of chick embryos

    NASA Astrophysics Data System (ADS)

    Leitner, Michael; Castanheira, Joana; Ferreira, Luís; Ferreira, Mónica; Palmeirim, Isabel; Rosa, Carla C.; Podoleanu, Adrian G.

    2009-07-01

    Chick embryos are among the most studied species in development biology because they are easily obtained, highly accessible and present a similar development to that of humans. Normally morphological studies are carried out with confocal microscopy, however in-situ imaging is impossible and in- vivo imaging can only be performed with great difficulty. For confocal microscopy the embryo has to be studied outside the egg, what generally also means a short life expectancy of the embryo. Additionally, extracting the embryo of the egg precludes the possibility of studying its development in its natural environment. In this paper it is shown that en-face optical coherence tomography (en-face OCT) is a possible solution to overcome these difficulties allowing for an in-situ and in-vivo study over a timescale of several days. With en-face OCT it is possible to accompany the development of one single embryo over several days and to acquire high resolution and axially resolved images.

  3. In situ molecular imaging of hydrated biofilm in a microfluidic reactor by ToF-SIMS

    SciTech Connect

    Hua, Xin; Yu, Xiao-Ying; Wang, Zhaoying; Yang, Li; Liu, Bingwen; Zhu, Zihua; Tucker, Abigail E.; Chrisler, William B.; Hill, Eric A.; Thevuthasan, Suntharampillai; Lin, Yuehe; Liu, Songqin; Marshall, Matthew J.

    2014-02-26

    The first results of using a novel single channel microfluidic reactor to enable Shewanella biofilm growth and in situ characterization using time-of-flight secondary ion mass spectrometry (ToF-SIMS) in the hydrated environment are presented. The new microfluidic interface allows direct probing of the liquid surface using ToF-SIMS, a vacuum surface technique. The detection window is an aperture of 2 m in diameter on a thin silicon nitride (SiN) membrane and it allows direct detection of the liquid surface. Surface tension of the liquid flowing inside the microchannel holds the liquid within the aperture. ToF-SIMS depth profiling was used to drill through the SiN membrane and the biofilm grown on the substrate. In situ 2D imaging of the biofilm in hydrated state was acquired, providing spatial distribution of the chemical compounds in the biofilm system. This data was compared with a medium filled microfluidic reactor devoid of biofilm and dried biofilm samples deposited on clean silicon wafers. Principle Component Analysis (PCA) was used to investigate these observations. Our results show that imaging biofilms in the hydrated environment using ToF-SIMS is possible using the unique microfluidic reactor. Moreover, characteristic biofilm fatty acids fragments were observed in the hydrated biofilm grown in the microfluidic channel, illustrating the advantage of imaging biofilm in its native environment.

  4. In situ treatment of liver using catheter based therapeutic ultrasound with combined imaging and GPS tracking

    NASA Astrophysics Data System (ADS)

    Ghoshal, Goutam; Heffter, Tamas; Williams, Emery; Bromfield, Corinne; Salgaonkar, Vasant; Rund, Laurie; Ehrhardt, John M.; Diederich, Chris J.; Burdette, E. Clif

    2013-02-01

    Extensive surgical procedure or liver transplant still remains the gold standard for treating slow-growing tumors in liver. But only few candidates are suitable for such procedure due to poor liver function, tumors in unresectable locations or presence of other liver diseases. In such situations, minimally invasive surgery may be the best therapeutic procedure. The use of RF, laser and ultrasound ablation techniques has gained considerable interest over the past several years to treat liver diseases. The success of such minimally invasive procedure depends on accurately targeting the desired region and guiding the entire procedure. The purpose of this study is to use ultrasound imaging and GPS tracking system to accurately place a steerable acoustic ablator and multiple temperature sensors in porcine liver in situ. Temperature sensors were place at eight different locations to estimate thermal distribution in the three-dimensional treated volume. Acoustic ablator of center frequency of 7 MHz was used for the experiments. During therapy a maximum temperature of 60-65 °C was observed at a distance 8-10 mm from the center of the ablation transducer. The dose distribution was analyzed and compared with the gross pathology of the treated region. Accurate placement of the acoustic applicator and temperature sensors were achieved using the combined image-guidance and the tracking system. By combining ultrasound imaging and GPS tracking system accurate placement of catheter based acoustic ablation applicator can be achieved in livers in situ.

  5. In situ real-time imaging of self-sorted supramolecular nanofibres

    NASA Astrophysics Data System (ADS)

    Onogi, Shoji; Shigemitsu, Hajime; Yoshii, Tatsuyuki; Tanida, Tatsuya; Ikeda, Masato; Kubota, Ryou; Hamachi, Itaru

    2016-08-01

    Self-sorted supramolecular nanofibres—a multicomponent system that consists of several types of fibre, each composed of distinct building units—play a crucial role in complex, well-organized systems with sophisticated functions, such as living cells. Designing and controlling self-sorting events in synthetic materials and understanding their structures and dynamics in detail are important elements in developing functional artificial systems. Here, we describe the in situ real-time imaging of self-sorted supramolecular nanofibre hydrogels consisting of a peptide gelator and an amphiphilic phosphate. The use of appropriate fluorescent probes enabled the visualization of self-sorted fibres entangled in two and three dimensions through confocal laser scanning microscopy and super-resolution imaging, with 80 nm resolution. In situ time-lapse imaging showed that the two types of fibre have different formation rates and that their respective physicochemical properties remain intact in the gel. Moreover, we directly visualized stochastic non-synchronous fibre formation and observed a cooperative mechanism.

  6. In situ real-time imaging of self-sorted supramolecular nanofibres.

    PubMed

    Onogi, Shoji; Shigemitsu, Hajime; Yoshii, Tatsuyuki; Tanida, Tatsuya; Ikeda, Masato; Kubota, Ryou; Hamachi, Itaru

    2016-08-01

    Self-sorted supramolecular nanofibres-a multicomponent system that consists of several types of fibre, each composed of distinct building units-play a crucial role in complex, well-organized systems with sophisticated functions, such as living cells. Designing and controlling self-sorting events in synthetic materials and understanding their structures and dynamics in detail are important elements in developing functional artificial systems. Here, we describe the in situ real-time imaging of self-sorted supramolecular nanofibre hydrogels consisting of a peptide gelator and an amphiphilic phosphate. The use of appropriate fluorescent probes enabled the visualization of self-sorted fibres entangled in two and three dimensions through confocal laser scanning microscopy and super-resolution imaging, with 80 nm resolution. In situ time-lapse imaging showed that the two types of fibre have different formation rates and that their respective physicochemical properties remain intact in the gel. Moreover, we directly visualized stochastic non-synchronous fibre formation and observed a cooperative mechanism. PMID:27442279

  7. Spatiotemporal cellular imaging of polymer-pDNA nanocomplexes affords in situ morphology and trafficking trends.

    PubMed

    Ingle, Nilesh P; Xue, Lian; Reineke, Theresa M

    2013-11-01

    Synthetic polymers are ubiquitous in the development of drug and polynucleotide delivery vehicles, offering promise for personalized medicine. However, the polymer structure plays a central yet elusive role in dictating the efficacy, safety, mechanisms, and kinetics of therapeutic transport in a spatial and temporal manner. Here, we decipher the intracellular pathways pertaining to shape, size, location, and mechanism of four structurally divergent polymer vehicles (Tr455, Tr477, jetPEI, and Glycofect) that create colloidal nanoparticles (polyplexes) when complexed with fluorescently labeled plasmid DNA (pDNA). Multiple high resolution tomographic images of whole HeLa (human cervical adenocarcinoma) cells were captured via confocal microscopy at 4, 8, 12, and 24 h. The images were reconstructed to visualize and quantify trends in situ in a four-dimensional spatiotemporal manner. The data revealed heretofore-unseen images of polyplexes in situ and structure-function relationships, i.e., Glycofect polyplexes are trafficked as the smallest polyplex complexes and Tr455 polyplexes have expedited translocation to the perinuclear region. Also, all of the polyplex types appeared to be preferentially internalized and trafficked via early endosomes affiliated with caveolae, a Rab-5-dependent pathway, actin, and microtubules. PMID:24007201

  8. Coherent Raman spectro-imaging with laser frequency combs.

    PubMed

    Ideguchi, Takuro; Holzner, Simon; Bernhardt, Birgitta; Guelachvili, Guy; Picqué, Nathalie; Hänsch, Theodor W

    2013-10-17

    Advances in optical spectroscopy and microscopy have had a profound impact throughout the physical, chemical and biological sciences. One example is coherent Raman spectroscopy, a versatile technique interrogating vibrational transitions in molecules. It offers high spatial resolution and three-dimensional sectioning capabilities that make it a label-free tool for the non-destructive and chemically selective probing of complex systems. Indeed, single-colour Raman bands have been imaged in biological tissue at video rates by using ultra-short-pulse lasers. However, identifying multiple, and possibly unknown, molecules requires broad spectral bandwidth and high resolution. Moderate spectral spans combined with high-speed acquisition are now within reach using multichannel detection or frequency-swept laser beams. Laser frequency combs are finding increasing use for broadband molecular linear absorption spectroscopy. Here we show, by exploring their potential for nonlinear spectroscopy, that they can be harnessed for coherent anti-Stokes Raman spectroscopy and spectro-imaging. The method uses two combs and can simultaneously measure, on the microsecond timescale, all spectral elements over a wide bandwidth and with high resolution on a single photodetector. Although the overall measurement time in our proof-of-principle experiments is limited by the waiting times between successive spectral acquisitions, this limitation can be overcome with further system development. We therefore expect that our approach of using laser frequency combs will not only enable new applications for nonlinear microscopy but also benefit other nonlinear spectroscopic techniques.

  9. Experimental procedures to mitigate electron beam induced artifacts during in situ fluid imaging of nanomaterials.

    PubMed

    Woehl, Taylor J; Jungjohann, Katherine L; Evans, James E; Arslan, Ilke; Ristenpart, William D; Browning, Nigel D

    2013-04-01

    Scanning transmission electron microscopy of various fluid and hydrated nanomaterial samples has revealed multiple imaging artifacts and electron beam-fluid interactions. These phenomena include growth of crystals on the fluid stage windows, repulsion of particles from the irradiated area, bubble formation, and the loss of atomic information during prolonged imaging of individual nanoparticles. Here we provide a comprehensive review of these fluid stage artifacts, and we present new experimental evidence that sheds light on their origins in terms of experimental apparatus issues and indirect electron beam sample interactions with the fluid layer. A key finding is that many artifacts are a result of indirect electron beam interactions, such as production of reactive radicals in the water by radiolysis, and the associated crystal growth. The results presented here will provide a methodology for minimizing fluid stage imaging artifacts and acquiring quantitative in situ observations of nanomaterial behavior in a liquid environment.

  10. Matrix-Assisted Laser Desorption Ionization Imaging Mass Spectrometry: In Situ Molecular Mapping

    PubMed Central

    Angel, Peggi M.; Caprioli, Richard M.

    2013-01-01

    Matrix-assisted laser desorption ionization imaging mass spectrometry (IMS) is a relatively new imaging modality that allows mapping of a wide range of biomolecules within a thin tissue section. The technology uses a laser beam to directly desorb and ionize molecules from discrete locations on the tissue that are subsequently recorded in a mass spectrometer. IMS is distinguished by the ability to directly measure molecules in situ ranging from small metabolites to proteins, reporting hundreds to thousands of expression patterns from a single imaging experiment. This article reviews recent advances in IMS technology, applications, and experimental strategies that allow it to significantly aid in the discovery and understanding of molecular processes in biological and clinical samples. PMID:23259809

  11. Imaging microbial metal metabolism in situ under conditions of the deep-sea hydrothermal vents

    NASA Astrophysics Data System (ADS)

    Oger, P. M.; Daniel, I.; Simionovici, A.; Picard, A.

    2006-12-01

    High-pressure biotopes are the most widely spread biotopes on Earth. They represent one possible location for the origin of life. They also share striking similarities with extraterrestrial biotopes such as those postulated for Europe or Mars. In absence of light, dissimilatory reduction of metals (DMR) is fueling the ecosystem. Monitoring the metabolism of the deep-sea hydrothermal vent microbial fauna under P, T and chemical conditions relevant to their isolation environment can be difficult because of the confinement and because most spectroscopic probes do not sense metallic ions in solution. We demonstrated the possibility to use Xray spectroscopy to monitor the speciation of metallic species in solution. Experiments were performed at The ESRF using Selenium (Se) detoxification by Agrobacterium tumefaciens as an analog of DMR. The reduction of Se from selenite to the metal was monitored by a combiantion of two Xray spectroscopic techniques (XANES and μXRF). Cells were incubated in the low pressure DAC in growth medium supplemented with 5mM Selenite and incubated under pressures up to 60 Mpa at 30°C for 24h. The evolution of the speciation can be easily monitored and the concentration of each Se species determined from the Xray spectra by linear combinations of standard spectra. Selenite is transformed by the bacterium into a mixture of metal Se and methylated Se after 24 hours. Se detoxification is observed in situ up to at least 25 MPa. The technique, developped for Se can be adapted to monitor other elements more relevant to DMR such as As, Fe or S, which should allow to monitor in situ under controlled pressure and temperature the metabolism of vent organisms. It is also amenable to the monitoring of toxic metals. Xray spectroscopy and the lpDAC are compatible with other spectroscopic techniques, such as Raman, UV or IR spectroscopies, allowing to probe other metabolic activities. Hence, enlarging the range of metabolic information that can be obtained in

  12. A Raman-based endoscopic strategy for multiplexed molecular imaging.

    PubMed

    Zavaleta, Cristina L; Garai, Ellis; Liu, Jonathan T C; Sensarn, Steven; Mandella, Michael J; Van de Sompel, Dominique; Friedland, Shai; Van Dam, Jacques; Contag, Christopher H; Gambhir, Sanjiv S

    2013-06-18

    Endoscopic imaging is an invaluable diagnostic tool allowing minimally invasive access to tissues deep within the body. It has played a key role in screening colon cancer and is credited with preventing deaths through the detection and removal of precancerous polyps. However, conventional white-light endoscopy offers physicians structural information without the biochemical information that would be advantageous for early detection and is essential for molecular typing. To address this unmet need, we have developed a unique accessory, noncontact, fiber optic-based Raman spectroscopy device that has the potential to provide real-time, multiplexed functional information during routine endoscopy. This device is ideally suited for detection of functionalized surface-enhanced Raman scattering (SERS) nanoparticles as molecular imaging contrast agents. This device was designed for insertion through a clinical endoscope and has the potential to detect and quantify the presence of a multiplexed panel of tumor-targeting SERS nanoparticles. Characterization of the Raman instrument was performed with SERS particles on excised human tissue samples, and it has shown unsurpassed sensitivity and multiplexing capabilities, detecting 326-fM concentrations of SERS nanoparticles and unmixing 10 variations of colocalized SERS nanoparticles. Another unique feature of our noncontact Raman endoscope is that it has been designed for efficient use over a wide range of working distances from 1 to 10 mm. This is necessary to accommodate for imperfect centering during endoscopy and the nonuniform surface topology of human tissue. Using this endoscope as a key part of a multiplexed detection approach could allow endoscopists to distinguish between normal and precancerous tissues rapidly and to identify flat lesions that are otherwise missed.

  13. Study of the corrosion products formed on a multiphase CuAlBe alloy in a sodium chloride solution by micro-Raman and in situ AFM measurements

    NASA Astrophysics Data System (ADS)

    Montecinos, S.; Simison, S. N.

    2011-06-01

    The corrosion products formed on a multiphase Cu-11.40Al-0.55Be (wt.%) alloy in 3.5% NaCl at open circuit potential, and their evolution with immersion time were studied mainly by micro-Raman and in situ AFM measurements. The aluminium content of each phase affects the formation of the corrosion products on them. After 1 day of immersion, γ 2 precipitates were more susceptible to dealuminization, while α' phase exhibited a high corrosion stability. The corrosion products evolved with immersion time, and CuCl 2 and a Cu 2O/CuO double layer film were the stable products formed on all the phases after long times.

  14. Transparent, flexible surface enhanced Raman scattering substrates based on Ag-coated structured PET (polyethylene terephthalate) for in-situ detection

    NASA Astrophysics Data System (ADS)

    Zuo, Zewen; Zhu, Kai; Gu, Chuan; Wen, Yibing; Cui, Guanglei; Qu, Jun

    2016-08-01

    Transparent, flexible surface-enhanced Raman scattering (SERS) substrates were fabricated by metalization of structured polyethylene terephthalate (PET) sheets. The resultant Ag-coated structured PET SERS substrates were revealed to be highly sensitive with good reproducibility and stability, an enhancement factor of 3 × 106 was acquired, which can be attributed mainly to the presence of plentiful multiple-type hot spots within the quasi-three-dimensional surface of the structured PET obtained by oxygen plasma etching. In addition, detections of model molecules on fruit skin were also carried out, demonstrating the great potential of the Ag-coated structured PET in in-situ detection of analyte on irregular objects. Importantly, the technique used for the preparation of such substrate is completely compatible with well-established silicon device technologies, and large-area fabrication with low cost can be readily realized.

  15. In situ Raman and synchrotron X-ray diffraction study on crystallization of Choline chloride/Urea deep eutectic solvent under high pressure

    NASA Astrophysics Data System (ADS)

    Yuan, Chaosheng; Chu, Kunkun; Li, Haining; Su, Lei; Yang, Kun; Wang, Yongqiang; Li, Xiaodong

    2016-09-01

    Pressure-induced crystallization of Choline chloride/Urea (ChCl/Urea) deep eutectic solvent (DES) has been investigated by in-situ Raman spectroscopy and synchrotron X-ray diffraction. The results indicated that high pressure crystals appeared at around 2.6 GPa, and the crystalline structure was different from that formed at ambient pressure. Upon increasing the pressure, the Nsbnd H stretching modes of Urea underwent dramatic change after liquid-solid transition. It appears that high pressures may enhance the hydrogen bonds formed between ChCl and Urea. P versus T phase diagram of ChCl/Urea DES was constructed, and the crystallization mechanism of ChCl/Urea DES was discussed in view of hydrogen bonds.

  16. Spectroscopy of low and intermediate Z elements at extreme conditions: in situ studies of Earth materials at pressure and temperature via X-ray Raman scattering

    NASA Astrophysics Data System (ADS)

    Sternemann, C.; Wilke, M.

    2016-07-01

    X-ray Raman scattering spectroscopy is an emerging method in the study of low and intermediate Z elements' core-electron excitations at extreme conditions in order to reveal information on local structure and electronic state of matter in situ. We discuss the capabilities of this method to address questions in Earth materials' science and demonstrate its sensitivity to detect changes in the oxidation state, electronic structure, coordination, and spin state. Examples are presented for the study of the oxygen K-, silicon L- and iron M-edges. We assess the application of both temperature and pressure in such investigations exploiting diamond anvil cells in combination with resistive or laser heating which is required to achieve realistic conditions of the Earth's crust, mantle, and core.

  17. A suitable for large scale production, flexible and transparent surface-enhanced Raman scattering substrate for in situ ultrasensitive analysis of chemistry reagents

    NASA Astrophysics Data System (ADS)

    Chen, P. X.; Shang, S. B.; Hu, L. T.; Liu, X. Y.; Qiu, H. W.; Li, C. H.; Huo, Y. Y.; Jiang, S. Z.; Yang, C.

    2016-09-01

    In this paper, a high cost-performance surface-enhanced Raman scattering (SERS) flexible substrate is demonstrated, which endowed with excellent optical transparency, high SERS activity and large scale. This SERS flexible substrate of Ag/Cu/Polyethylene Terephthalate (PET) was prepared by replacing Cu atoms with Ag atoms in situ on Cu nano-film. The Ag/Cu/PET flexible substrate shows high sensitivity in SERS detection and the minimum detected concentration of R6G can reach 10-10 M. In addition, the residual methylene blue (MB) on a fish surface was selected as the analyte, the results no doubt shows the potential of SERS technology application in food detection.

  18. Phase transitions of cesium azide at pressures up to 30 GPa studied using in situ Raman spectroscopy

    SciTech Connect

    Medvedev, S. A. Felser, C.; Barkalov, O. I.; Naumov, P.; Palasyuk, T.

    2015-04-28

    Cesium azide has been studied by Raman spectroscopy at pressures up to ≈30 GPa at room temperature. The sequence of phase transitions to Phase III (at 0.5 GPa), Phase IV (at 4.3 GPa), and Phase V (at ≈19 GPa) has been observed in agreement with recent X-ray diffraction studies. Phase III has been found to adopt a monoclinic C2/m structure with two azide anions in nonequivalent positions, where one set of azide anions appears to be orientationally disordered according to the observed Raman spectra. The transition to Phase IV has been associated with orientational ordering of azide anions, while the transition to Phase V has been shown to proceed with a lowering of crystal symmetry. Moreover, spectroscopic features indicate a possible change of bonding in CsN{sub 3} toward formation of covalent bonds at high pressures.

  19. [In situ experimental study of phase transition of calcite by Raman spectroscopy at high temperature and high pressure].

    PubMed

    Liu, Chuan-jiang; Zheng, Hai-fei

    2012-02-01

    The phase transitions of calcite at high temperature and high pressure were investigated by using hydrothermal diamond anvil cell combined with Raman spectroscopy. The result showed that the Raman peak of 155 cm(-1) disappeared, the peak of 1 087 cm(-1) splited into 1083 and 1 090 cm(-1) peaks and the peak of 282 cm(-1) abruptly reduced to 231 cm(-1) at ambient temperature when the system pressure increased to 1 666 and 2 127 MPa respectively, which proved that calcite transformed to calcite-II and calcite-III. In the heating process at the initial pressure of 2 761 MPa and below 171 degrees C, there was no change in Raman characteristic peaks of calcite-III. As the temperature increased to 171 degrees C, the color of calcite crystal became opaque completely and the symmetric stretching vibration peak of 1 087 cm(-1), in-plane bending vibration peak of 713 cm(-1) and lattice vibration peaks of 155 and 282 cm(-1) began to mutate, showing that the calcite-III transformed to a new phase of calcium carbonate at the moment. When the temperature dropped to room temperature, this new phase remained stable all along. It also indicated that the process of phase transformation from calcite to the new phase of calcium carbonate was irreversible. The equation of phase transition between calcite-III and new phase of calcium carbonate can be determined by P(MPa) = 9.09T x (degrees C) +1 880. The slopes of the Raman peak (v1 087) of symmetrical stretching vibration depending on pressure and temperature are dv/dP = 5.1 (cm(-1) x GPa(-1)) and dv/dT = -0.055 3(cm(-1) x degrees C(-1)), respectively. PMID:22512172

  20. Monitoring plasmon-driven surface catalyzed reactions in situ using time-dependent surface-enhanced Raman spectroscopy on single particles of hierarchical peony-like silver microflowers

    NASA Astrophysics Data System (ADS)

    Tang, Xianghu; Cai, Wenya; Yang, Liangbao; Liu, Jinhuai

    2014-07-01

    Investigating the kinetics of catalytic reactions with surface-enhanced Raman scattering (SERS) on a single particle remains a significant challenge. In this study, the single particle of the constructed hierarchical peony-like silver microflowers (SMFs) with highly roughened surface led to the coupling of high catalytic activity with a strong SERS effect, which acts as an excellent bifunctional platform for in situ monitoring of surface catalytic reactions. The kinetics of the reaction of 4-nitrothiophenol (4-NTP) dimerizing into 4,4'-dimercaptoazobenzene (DMAB) was investigated and comparatively studied by using the SERS technique on a single particle of different morphologies of SMFs. The results indicate that a fully developed nanostructure of a hierarchical SMF has both larger SERS enhancement and apparent reaction rate constant k, which may be useful for monitoring and understanding the mechanism of plasmon-driven surface catalyzed reactions.Investigating the kinetics of catalytic reactions with surface-enhanced Raman scattering (SERS) on a single particle remains a significant challenge. In this study, the single particle of the constructed hierarchical peony-like silver microflowers (SMFs) with highly roughened surface led to the coupling of high catalytic activity with a strong SERS effect, which acts as an excellent bifunctional platform for in situ monitoring of surface catalytic reactions. The kinetics of the reaction of 4-nitrothiophenol (4-NTP) dimerizing into 4,4'-dimercaptoazobenzene (DMAB) was investigated and comparatively studied by using the SERS technique on a single particle of different morphologies of SMFs. The results indicate that a fully developed nanostructure of a hierarchical SMF has both larger SERS enhancement and apparent reaction rate constant k, which may be useful for monitoring and understanding the mechanism of plasmon-driven surface catalyzed reactions. Electronic supplementary information (ESI) available: Fig. S1-S12. See DOI

  1. Determination of methane concentrations in water in equilibrium with sI methane hydrate in the absence of a vapor phase by in situ Raman spectroscopy

    USGS Publications Warehouse

    Lu, W.; Chou, I.-Ming; Burruss, R.C.

    2008-01-01

    Most submarine gas hydrates are located within the two-phase equilibrium region of hydrate and interstitial water with pressures (P) ranging from 8 to 60 MPa and temperatures (T) from 275 to 293 K. However, current measurements of solubilities of methane in equilibrium with hydrate in the absence of a vapor phase are limited below 20 MPa and 283.15 K, and the differences among these data are up to 30%. When these data were extrapolated to other P-T conditions, it leads to large and poorly known uncertainties. In this study, in situ Raman spectroscopy was used to measure methane concentrations in pure water in equilibrium with sI (structure one) methane hydrate, in the absence of a vapor phase, at temperatures from 276.6 to 294.6 (??0.3) K and pressures at 10, 20, 30 and 40 (??0.4%) MPa. The relationship among concentration of methane in water in equilibrium with hydrate, in mole fraction [X(CH4)], the temperature in K, and pressure in MPa was derived as: X(CH4) = exp [11.0464 + 0.023267 P - (4886.0 + 8.0158 P)/T]. Both the standard enthalpy and entropy of hydrate dissolution at the studied T-P conditions increase slightly with increasing pressure, ranging from 41.29 to 43.29 kJ/mol and from 0.1272 to 0.1330 kJ/K ?? mol, respectively. When compared with traditional sampling and analytical methods, the advantages of our method include: (1) the use of in situ Raman signals for methane concentration measurements eliminates possible uncertainty caused by sampling and ex situ analysis, (2) it is simple and efficient, and (3) high-pressure data can be obtained safely. ?? 2007 Elsevier Ltd. All rights reserved.

  2. A hot tip: imaging phenomena using in situ multi-stimulus probes at high temperatures.

    PubMed

    Nonnenmann, Stephen S

    2016-02-14

    Accurate high temperature characterization of materials remains a critical challenge to the continued advancement of various important energy, nuclear, electronic, and aerospace applications. Future experimental studies must assist these communities to progress past empiricism and derive deliberate, predictable designs of material classes functioning within active, extreme environments. Successful realization of systems ranging from fuel cells and batteries to electromechanical nanogenerators and turbines requires a dynamic understanding of the excitation, surface-mediated, and charge transfer phenomena which occur at heterophase interfaces (i.e. vapor-solid, liquid-solid, solid-solid) and impact overall performance. Advancing these frontiers therefore necessitates in situ (operando) characterization methods capable of resolving, both spatially and functionally, the coherence between these complex, collective excitations, and their respective response dynamics, through studies within the operating regime. This review highlights recent developments in scanning probe microscopy in performing in situ imaging at high elevated temperatures. The influence of and evolution from vacuum-based electron and tunneling microscopy are briefly summarized and discussed. The scope includes the use of high temperature imaging to directly observe critical phase transition, electronic, and electrochemical behavior under dynamic temperature settings, thus providing key physical parameters. Finally, both challenges and directions in combined instrumentation are proposed and discussed towards the end.

  3. A hot tip: imaging phenomena using in situ multi-stimulus probes at high temperatures

    NASA Astrophysics Data System (ADS)

    Nonnenmann, Stephen S.

    2016-02-01

    Accurate high temperature characterization of materials remains a critical challenge to the continued advancement of various important energy, nuclear, electronic, and aerospace applications. Future experimental studies must assist these communities to progress past empiricism and derive deliberate, predictable designs of material classes functioning within active, extreme environments. Successful realization of systems ranging from fuel cells and batteries to electromechanical nanogenerators and turbines requires a dynamic understanding of the excitation, surface-mediated, and charge transfer phenomena which occur at heterophase interfaces (i.e. vapor-solid, liquid-solid, solid-solid) and impact overall performance. Advancing these frontiers therefore necessitates in situ (operando) characterization methods capable of resolving, both spatially and functionally, the coherence between these complex, collective excitations, and their respective response dynamics, through studies within the operating regime. This review highlights recent developments in scanning probe microscopy in performing in situ imaging at high elevated temperatures. The influence of and evolution from vacuum-based electron and tunneling microscopy are briefly summarized and discussed. The scope includes the use of high temperature imaging to directly observe critical phase transition, electronic, and electrochemical behavior under dynamic temperature settings, thus providing key physical parameters. Finally, both challenges and directions in combined instrumentation are proposed and discussed towards the end.

  4. In situ imaging and control of layer-by-layer femtosecond laser thinning of graphene.

    PubMed

    Li, D W; Zhou, Y S; Huang, X; Jiang, L; Silvain, J-F; Lu, Y F

    2015-02-28

    Although existing methods (chemical vapor deposition, mechanical exfoliation, etc.) are available to produce graphene, the lack of thickness control limits further graphene applications. In this study, we demonstrate an approach to precisely thin graphene films to a specific thickness using femtosecond (fs) laser raster scanning. By using appropriate laser fluence and scanning times, graphene thinning with an atomic layer precision, namely layer-by-layer graphene removal, has been realized. The fs laser used was configured in a four-wave mixing (FWM) system which can be used to distinguish graphene layer thickness and count the number of layers using the linear relationship between the FWM signal intensity and the graphene thickness. Furthermore, FWM imaging has been successfully applied to achieve in situ, real-time monitoring of the fs laser graphene thinning process. This method can not only realize the large-scale thinning of graphene with atomic layer precision, but also provide in situ, rapid imaging capability of graphene for an accurate assessment of the number of layers.

  5. Image correlation method for measuring flow and diameter changes in contracting mesenteric microlymphatics in situ

    NASA Astrophysics Data System (ADS)

    Dixon, J. Brandon; Cote, Gerard; Gashev, Anatoly; Greiner, Steven; Moore, James; Zawieja, David

    2006-02-01

    Collecting microlymphatics play a vital role in promoting lymph flow from the initial lymphatics in the interstitial spaces to the large transport lymph ducts. In most tissues, the primary mechanism for producing this flow is the spontaneous contractions of the lymphatic wall. Individual units, known as lymphangion, are separated by valves that help prevent backflow when the vessel contracts, thus promoting flow through the lymphatic network. Lymphatic contractile activity is inhibited by flow in isolated lymphatics, however there are virtually no in situ measurements of lymph flow in these vessels. One of the difficulties associated with obtaining such measurements is the time consuming methods of manual particle tracking used previously by our group. Using an in situ preparation with mesenteric microlymphatics (~ 100 μm in diameter) and a high speed imaging system (500 fps), we have developed an image correlation method to measure lymphatic flow with a standard error of prediction of 0.3 mm/sec when compared with manual particle tracking.

  6. Investigating the regulation of stem and progenitor cell mitotic progression by in situ imaging.

    PubMed

    Gerhold, Abigail R; Ryan, Joël; Vallée-Trudeau, Julie-Nathalie; Dorn, Jonas F; Labbé, Jean-Claude; Maddox, Paul S

    2015-05-01

    Genome stability relies upon efficacious chromosome congression and regulation by the spindle assembly checkpoint (SAC). The study of these fundamental mitotic processes in adult stem and progenitor cells has been limited by the technical challenge of imaging mitosis in these cells in situ. Notably, how broader physiological changes, such as dietary intake or age, affect mitotic progression in stem and/or progenitor cells is largely unknown. Using in situ imaging of C. elegans adult germlines, we describe the mitotic parameters of an adult stem and progenitor cell population in an intact animal. We find that SAC regulation in germline stem and progenitor cells is distinct from that found in early embryonic divisions and is more similar to that of classical tissue culture models. We further show that changes in organismal physiology affect mitotic progression in germline stem and progenitor cells. Reducing dietary intake produces a checkpoint-dependent delay in anaphase onset, and inducing dietary restriction when the checkpoint is impaired increases the incidence of segregation errors in mitotic and meiotic cells. Similarly, developmental aging of the germline stem and progenitor cell population correlates with a decline in the rate of several mitotic processes. These results provide the first in vivo validation of models for SAC regulation developed in tissue culture systems and demonstrate that several fundamental features of mitotic progression in adult stem and progenitor cells are highly sensitive to organismal physiological changes.

  7. MALDI Mass Spectrometry Imaging for Visualizing In Situ Metabolism of Endogenous Metabolites and Dietary Phytochemicals

    PubMed Central

    Fujimura, Yoshinori; Miura, Daisuke

    2014-01-01

    Understanding the spatial distribution of bioactive small molecules is indispensable for elucidating their biological or pharmaceutical roles. Mass spectrometry imaging (MSI) enables determination of the distribution of ionizable molecules present in tissue sections of whole-body or single heterogeneous organ samples by direct ionization and detection. This emerging technique is now widely used for in situ label-free molecular imaging of endogenous or exogenous small molecules. MSI allows the simultaneous visualization of many types of molecules including a parent molecule and its metabolites. Thus, MSI has received much attention as a potential tool for pathological analysis, understanding pharmaceutical mechanisms, and biomarker discovery. On the other hand, several issues regarding the technical limitations of MSI are as of yet still unresolved. In this review, we describe the capabilities of the latest matrix-assisted laser desorption/ionization (MALDI)-MSI technology for visualizing in situ metabolism of endogenous metabolites or dietary phytochemicals (food factors), and also discuss the technical problems and new challenges, including MALDI matrix selection and metabolite identification, that need to be addressed for effective and widespread application of MSI in the diverse fields of biological, biomedical, and nutraceutical (food functionality) research. PMID:24957029

  8. A hot tip: imaging phenomena using in situ multi-stimulus probes at high temperatures.

    PubMed

    Nonnenmann, Stephen S

    2016-02-14

    Accurate high temperature characterization of materials remains a critical challenge to the continued advancement of various important energy, nuclear, electronic, and aerospace applications. Future experimental studies must assist these communities to progress past empiricism and derive deliberate, predictable designs of material classes functioning within active, extreme environments. Successful realization of systems ranging from fuel cells and batteries to electromechanical nanogenerators and turbines requires a dynamic understanding of the excitation, surface-mediated, and charge transfer phenomena which occur at heterophase interfaces (i.e. vapor-solid, liquid-solid, solid-solid) and impact overall performance. Advancing these frontiers therefore necessitates in situ (operando) characterization methods capable of resolving, both spatially and functionally, the coherence between these complex, collective excitations, and their respective response dynamics, through studies within the operating regime. This review highlights recent developments in scanning probe microscopy in performing in situ imaging at high elevated temperatures. The influence of and evolution from vacuum-based electron and tunneling microscopy are briefly summarized and discussed. The scope includes the use of high temperature imaging to directly observe critical phase transition, electronic, and electrochemical behavior under dynamic temperature settings, thus providing key physical parameters. Finally, both challenges and directions in combined instrumentation are proposed and discussed towards the end. PMID:26795921

  9. Comparison of optical and microphysical properties of pure Saharan mineral dust observed with AERONET Sun photometer, Raman lidar, and in situ instruments during SAMUM 2006

    NASA Astrophysics Data System (ADS)

    Müller, D.; Lee, K.-H.; Gasteiger, J.; Tesche, M.; Weinzierl, B.; Kandler, K.; Müller, T.; Toledano, C.; Otto, S.; Althausen, D.; Ansmann, A.

    2012-04-01

    The Saharan Mineral Dust Experiment (SAMUM) 2006, Morocco, aimed at the characterization of optical, physical, and radiative properties of Saharan dust. AERONET Sun photometer, several lidars (Raman and high-spectral-resolution instruments), and airborne and ground-based in situ instruments provided us with a comprehensive set of data on particle-shape dependent and particle-shape independent dust properties. We compare 4 measurement days in detail, and we carry out a statistical analysis for some of the inferred data products for the complete measurement period. Particle size distributions and complex refractive indices inferred from the Sun photometer observations and measured in situ aboard a research aircraft show systematic differences. We find differences in the wavelength-dependence of single-scattering albedo, compared to light-scattering computations that use data from SOAP (spectral optical absorption photometer). AERONET data products of particle size distribution, complex refractive index, and axis ratios were used to compute particle extinction-to-backscatter (lidar) ratios and linear particle depolarization ratios. We find differences for these parameters to lidar measurements of lidar ratio and particle depolarization ratio. Differences particularly exist at 355 nm, which may be the result of differences of the wavelength-dependent complex refractive index that is inferred by the methods employed in this field campaign. We discuss various error sources that may lead to the observed differences.

  10. In situ loading of well-dispersed silver nanoparticles on nanocrystalline magnesium oxide for real-time monitoring of catalytic reactions by surface enhanced Raman spectroscopy.

    PubMed

    Zhang, Kaige; Li, Gongke; Hu, Yuling

    2015-10-28

    The surface-enhanced Raman spectroscopy (SERS) technique is of great importance for insight into the transient reaction intermediates and mechanistic pathways involved in heterogeneously catalyzed chemical reactions under actual reaction conditions, especially in water. Herein, we demonstrate a facile method for in situ synthesis of nanocrystalline magnesium oxide-Ag(0) (nano MgO-Ag(0)) hybrid nanomaterials with dispersed Ag nanoparticles (Ag NPs) on the surface of nanocrystalline magnesium oxide (nano MgO) via Sn(2+) linkage and reduction. As a benefit from the synergy effect of nano MgO and Ag NPs, the nano MgO-Ag(0) exhibited both excellent SERS and catalytic activities for the reduction of 4-nitrothiophenol in the presence of NaBH4. The nano MgO-Ag(0) was used for real-time monitoring of the catalytic reaction process of 4-nitrothiophenol to 4-aminothiophenol in an aqueous medium by observing the SERS signals of the reactant, intermediate and final products. The intrinsic reaction kinetics and reaction mechanism of this reaction were also investigated. This SERS-based synergy technique provides a novel approach for quantitative in situ monitoring of catalytic chemical reaction processes.

  11. Three-dimensional Raman spectroscopic imaging of protein crystals deposited on a nanodroplet.

    PubMed

    Nitahara, Satoshi; Maeki, Masatoshi; Yamaguchi, Hiroshi; Yamashita, Kenichi; Miyazaki, Masaya; Maeda, Hideaki

    2012-12-21

    Confocal Raman spectroscopic imaging has been used to find the location of protein crystals deposited in a nanodroplet. The depth of the protein crystal has been clearly identified by comparing the three-dimensional Raman spectroscopic images of the protein with those of water. Additionally, the low concentration region around a growing protein crystal in the nanodroplet was visualized using two-dimensional Raman spectroscopic imaging.

  12. Potential clinical impact of three-dimensional visualization for fluorescent in situ hybridization image analysis

    NASA Astrophysics Data System (ADS)

    Li, Zheng; Li, Shibo; Bin, Zheng; Zhang, Roy; Li, Yuhua; Tian, Huimin; Chen, Wei; Liu, Hong

    2012-05-01

    Chromosomal translocation is strong indication of cancers. Fluorescent in situ hybridization (FISH) can effectively detect this translocation and achieve high accuracy in disease diagnosis and prognosis assessment. For this purpose, whole chromosome paint probes are utilized to image the configuration of DNA fragments. Although two-dimensional (2-D) microscopic images are typically used in FISH signal analysis, we present a case where the translocation occurs in the depth direction where two probed FISH signals are overlapped in the projected image plane. Thus, the translocation cannot be identified. However, when imaging the whole specimen with a confocal microscope at 27 focal planes with 0.5-μm step interval, the translocation can be clearly identified due to the free rotation capability by the three-dimensional (3-D) visualization. Such a translocation detection error of using 2-D images might be critical in detecting and diagnosing early or subtle disease cases where detecting a small number of abnormal cells can make diagnostic difference. Hence, the underlying implication of this report suggests that utilizing 3-D visualization may improve the overall accuracy of FISH analysis for some clinical cases. However, the clinical efficiency and cost of using 3-D versus 2-D imaging methods are also to be assessed carefully.

  13. X-ray Coherent Diffraction Imaging of Cellulose Fibrils in Situ

    SciTech Connect

    Lal, Jyotsana; Harder, Ross J.; Makowski, Lee

    2011-01-01

    Cellulose is the most abundant renewable source of organic molecules on earth[1]. As fossil fuel reserves become depleted, the use of cellulose as a feed stock for fuels and chemicals is being aggressively explored. Cellulose is a linear polymer of glucose that packs tightly into crystalline fibrils that make up a substantial proportion of plant cell walls. Extraction of the cellulose chains from these fibrils in a chemically benign process has proven to be a substantial challenge [2]. Monitoring the deconstruction of the fibrils in response to physical and chemical treatments would expedite the development of efficient processing methods. As a step towards achieving that goal, we here describe Bragg-coherent diffraction imaging (CDI) as an approach to producing images of cellulose fibrils in situ within vascular bundles from maize.

  14. Imaging in situ protein-DNA interactions in the cell nucleus using FRET-FLIM

    SciTech Connect

    Cremazy, Frederic G.E.; Manders, Erik M.M.; Bastiaens, Philippe I.H.; Kramer, Gertjan; Hager, Gordon L.; Munster, Erik B. van; Verschure, Pernette J.; Gadella, TheodorusW.J.; Driel, Roel van . E-mail: van.driel@science.uva.nl

    2005-10-01

    Although the distribution of DNA-binding proteins inside the cell nucleus can be analyzed by immunolabeling or by tagging proteins with GFP, we cannot establish whether the protein is bound to DNA or not. Here, we describe a novel approach that allows imaging of the in situ interaction between a GFP-fusion protein and DNA in the cell nucleus, using fluorescence resonance energy transfer (FRET). We used fluorescence lifetime imaging microscopy (FLIM) as a reliable tool to detect protein in contact with DNA. The method was successfully applied to the DNA-binding proteins histone H2B and the glucocorticoid receptor and to the heterochromatin-associated proteins HP1{alpha} and HP1{beta}.

  15. X-ray coherent diffraction imaging of cellulose fibrils in situ.

    PubMed

    Lal, Jyotsana; Harder, Ross; Makowski, Lee

    2011-01-01

    Cellulose is the most abundant renewable source of organic molecules on earth[1]. As fossil fuel reserves become depleted, the use of cellulose as a feed stock for fuels and chemicals is being aggressively explored. Cellulose is a linear polymer of glucose that packs tightly into crystalline fibrils that make up a substantial proportion of plant cell walls. Extraction of the cellulose chains from these fibrils in a chemically benign process has proven to be a substantial challenge [2]. Monitoring the deconstruction of the fibrils in response to physical and chemical treatments would expedite the development of efficient processing methods. As a step towards achieving that goal, we here describe Bragg-coherent diffraction imaging (CDI) as an approach to producing images of cellulose fibrils in situ within vascular bundles from maize. PMID:22254364

  16. In situ detection and identification of microorganisms at single-colony resolution by spectral imaging

    NASA Astrophysics Data System (ADS)

    Miyazawa, Kanae; Kobayashi, Ken-Ichi; Nakauchi, Shigeki; Hiraishi, Akira

    2008-11-01

    The in situ detection and identification of environmental microorganisms is important for general microbial ecology research. In addition, the rapid detection of microbial contamination in food-processing plants is essential. The current paper proposes a method for the rapid detection and identification of microorganisms using spectral imaging. Photosynthetic and non-photosynthetic bacterial colonies with different absorption spectra in the near-infrared wavelength region were measured directly from a Petri dish. The bacterial colonies were distinguished and subsequently typed using multiple discriminant analysis. The accuracy of the detection and identification of colonies of various sizes was evaluated. The results showed that colonies with diameters of 100 and 300 μm could be detected and identified, respectively, with adequate accuracy. Moreover, using our novel application of this spectral-imaging technique, the bacterial detection and identification times were reduced by more than half and by a few weeks, respectively, compared with conventional methods.

  17. The interaction of an amino-modified ZrO2 nanomaterial with macrophages-an in situ investigation by Raman microspectroscopy.

    PubMed

    Silge, Anja; Bocklitz, Thomas; Ossig, Rainer; Schnekenburger, Jürgen; Rösch, Petra; Popp, Jürgen

    2016-08-01

    Metal oxide nanoparticles (NP) are applied in the fields of biomedicine, pharmaceutics, and in consumer products as textiles, cosmetics, paints, or fuels. In this context, the functionalization of the NP surface is a common method to modify and modulate the product performance. A chemical surface modification of NP such as an amino-functionalization can be used to achieve a positively charged and hydrophobic surface. Surface functionalization is known to affect the interaction of nanomaterials (NM) with cellular macromolecules and the responses of tissues or cells, like the uptake of particles by phagocytic cells. Therefore, it is important to assess the possible risk of those modified NP for human health and environment. By applying Raman microspectroscopy, we verified in situ the interaction of amino-modified ZrO2 NP with cultivated macrophages. The results demonstrated strong adhesion properties of the NP to the cell membrane and internalization into the cells. The intracellular localization of the NP was visualized via Raman depth scans of single cells. After the cells were treated with sodium azide (NaN3) and 2-deoxy-glucose to inhibit the phagocytic activity, NP were still detected inside cells to comparable percentages. The observed tendency of amino-modified ZrO2 NP to interact with the cultivated macrophages may influence membrane integrity and cellular functions of alveolar macrophages in the respiratory system. Graphical abstract Detection of ZrO2 NM at subcellular level.

  18. In situ diagnostics of the crystal-growth process through neutron imaging: application to scintillators

    PubMed Central

    Tremsin, Anton S.; Makowska, Małgorzata G.; Perrodin, Didier; Shalapska, Tetiana; Khodyuk, Ivan V.; Trtik, Pavel; Boillat, Pierre; Vogel, Sven C.; Losko, Adrian S.; Strobl, Markus; Kuhn, L. Theil; Bizarri, Gregory A.; Bourret-Courchesne, Edith D.

    2016-01-01

    Neutrons are known to be unique probes in situations where other types of radiation fail to penetrate samples and their surrounding structures. In this paper it is demonstrated how thermal and cold neutron radiography can provide time-resolved imaging of materials while they are being processed (e.g. while growing single crystals). The processing equipment, in this case furnaces, and the scintillator materials are opaque to conventional X-ray interrogation techniques. The distribution of the europium activator within a BaBrCl:Eu scintillator (0.1 and 0.5% nominal doping concentrations per mole) is studied in situ during the melting and solidification processes with a temporal resolution of 5–7 s. The strong tendency of the Eu dopant to segregate during the solidification process is observed in repeated cycles, with Eu forming clusters on multiple length scales (only for clusters larger than ∼50 µm, as limited by the resolution of the present experiments). It is also demonstrated that the dopant concentration can be quantified even for very low concentration levels (∼0.1%) in 10 mm thick samples. The interface between the solid and liquid phases can also be imaged, provided there is a sufficient change in concentration of one of the elements with a sufficient neutron attenuation cross section. Tomographic imaging of the BaBrCl:0.1%Eu sample reveals a strong correlation between crystal fractures and Eu-deficient clusters. The results of these experiments demonstrate the unique capabilities of neutron imaging for in situ diagnostics and the optimization of crystal-growth procedures. PMID:27275133

  19. Fiber optic direct Raman imaging system based on a hollow-core fiber bundle

    NASA Astrophysics Data System (ADS)

    Inoue, S.; Katagiri, T.; Matsuura, Y.

    2015-03-01

    A Raman imaging system which combined a hollow fiber bundle and a direct imaging technique was constructed for high-speed endoscopic Raman imaging. The hollow fiber bundle is fabricated by depositing a silver thin film on the inner surface of pre-drawn glass capillary bundle. It performs as a fiber optic probe which transmits a Raman image with high signal-to-noise ratio because the propagating light is confined into the air core inducing little light scattering. The field of view on the sample is uniformly irradiated by the excitation laser light via the probe. The back-scattered image is collected by the probe and captured directly by an image sensor. A pair of thin film tunable filters is used to select target Raman band. This imaging system enables flexible and high-speed Raman imaging of biological tissues.

  20. Line-scan Raman spectroscopy for detection and imaging of explosives traces by a compact Raman spectrometer

    NASA Astrophysics Data System (ADS)

    Malka, Itamar; Bar, Ilana

    2016-02-01

    Measurements of Raman scattering spectra and of Raman maps of particles of explosives and related compounds [potassium nitrate, 2,4-dinitrotoluene (DNT), 2,4,6-trinitrotoluene (TNT) and 1,3,5-trinitro-1,3,5-triazacyclohexane (RDX)] were performed by a homebuilt compact Raman system, functioning with a 532-nm laser beam, focused as a point or line, along with full vertical binning or image readout of an intensified charge-coupled device camera. High specificity and sensitivity were obtained by line-excitation, which allowed fast detection and mapping of explosive particles with a relatively simple system.

  1. Raman imaging in geomicrobiology: endolithic phototrophic microorganisms in gypsum from the extreme sun irradiation area in the Atacama Desert.

    PubMed

    Vítek, Petr; Ascaso, Carmen; Artieda, Octavio; Wierzchos, Jacek

    2016-06-01

    The Raman imaging method was successfully applied for mapping the distribution of biomolecules (e.g., pigments) associated with cryptoendolithic and hypoendolithic microorganisms, as well as the inorganic host mineral matrix that forms the habitat for the biota. To the best of our knowledge, this is the first comprehensive study in the field of geomicrobiology based on this technique. The studied microbial ecosystem was located nearly 3000 m above sea level within the driest desert on Earth, the Atacama in Chile. Enhancement of carotenoid Raman signal intensity close to the surface was registered at different areas of endolithic colonization dominated by algae, with cyanobacteria present as well. This is interpreted as an adaptation mechanism to the excessive solar irradiation. On the other hand, cyanobacteria synthesize scytonemin as a passive UV-screening pigment (found at both the hypoendolithic and cryptoendolithic positions). The distribution of the scytonemin Raman signal was mapped simultaneously with the surrounding mineral matrix. Thus, mapping was done of the phototrophic microorganisms in their original microhabitat together with the host rock environment. Important information which was resolved from the Raman imaging dataset of the host rock is about the hydration state of Ca-sulfate, demonstrated on the presence of gypsum (CaSO4·2H2O) and the absence of both anhydrite (CaSO4) and bassanite (CaSO4·1/2H2O). Obtaining combined "in situ" simultaneous information from the geological matrix (inorganic) together with the microbial biomolecules (organic) is discussed and concluded as an important advantage of this technique. We discuss how selection of the laser wavelength (785 and 514.5-nm) influences the Raman imaging results. PMID:27055886

  2. Raman imaging in geomicrobiology: endolithic phototrophic microorganisms in gypsum from the extreme sun irradiation area in the Atacama Desert.

    PubMed

    Vítek, Petr; Ascaso, Carmen; Artieda, Octavio; Wierzchos, Jacek

    2016-06-01

    The Raman imaging method was successfully applied for mapping the distribution of biomolecules (e.g., pigments) associated with cryptoendolithic and hypoendolithic microorganisms, as well as the inorganic host mineral matrix that forms the habitat for the biota. To the best of our knowledge, this is the first comprehensive study in the field of geomicrobiology based on this technique. The studied microbial ecosystem was located nearly 3000 m above sea level within the driest desert on Earth, the Atacama in Chile. Enhancement of carotenoid Raman signal intensity close to the surface was registered at different areas of endolithic colonization dominated by algae, with cyanobacteria present as well. This is interpreted as an adaptation mechanism to the excessive solar irradiation. On the other hand, cyanobacteria synthesize scytonemin as a passive UV-screening pigment (found at both the hypoendolithic and cryptoendolithic positions). The distribution of the scytonemin Raman signal was mapped simultaneously with the surrounding mineral matrix. Thus, mapping was done of the phototrophic microorganisms in their original microhabitat together with the host rock environment. Important information which was resolved from the Raman imaging dataset of the host rock is about the hydration state of Ca-sulfate, demonstrated on the presence of gypsum (CaSO4·2H2O) and the absence of both anhydrite (CaSO4) and bassanite (CaSO4·1/2H2O). Obtaining combined "in situ" simultaneous information from the geological matrix (inorganic) together with the microbial biomolecules (organic) is discussed and concluded as an important advantage of this technique. We discuss how selection of the laser wavelength (785 and 514.5-nm) influences the Raman imaging results.

  3. Improving spatial resolution of confocal Raman microscopy by super-resolution image restoration.

    PubMed

    Cui, Han; Zhao, Weiqian; Wang, Yun; Fan, Ying; Qiu, Lirong; Zhu, Ke

    2016-05-16

    A new super-resolution image restoration confocal Raman microscopy method (SRIR-RAMAN) is proposed for improving the spatial resolution of confocal Raman microscopy. This method can recover the lost high spatial frequency of the confocal Raman microscopy by using Poisson-MAP super-resolution imaging restoration, thereby improving the spatial resolution of confocal Raman microscopy and realizing its super-resolution imaging. Simulation analyses and experimental results indicate that the spatial resolution of SRIR-RAMAN can be improved by 65% to achieve 200 nm with the same confocal Raman microscopy system. This method can provide a new tool for high spatial resolution micro-probe structure detection in physical chemistry, materials science, biomedical science and other areas.

  4. Label-free chemically specific imaging in planta with stimulated Raman scattering microscopy.

    PubMed

    Mansfield, Jessica C; Littlejohn, George R; Seymour, Mark P; Lind, Rob J; Perfect, Sarah; Moger, Julian

    2013-05-21

    The growing world population puts ever-increasing demands on the agricultural and agrochemical industries to increase agricultural yields. This can only be achieved by investing in fundamental plant and agrochemical research and in the development of improved analytical tools to support research in these areas. There is currently a lack of analytical tools that provide noninvasive structural and chemical analysis of plant tissues at the cellular scale. Imaging techniques such as coherent anti-Stokes Raman scattering (CARS) and stimulated Raman scattering (SRS) microscopy provide label-free chemically specific image contrast based on vibrational spectroscopy. Over the past decade, these techniques have been shown to offer clear advantages for a vast range of biomedical research applications. The intrinsic vibrational contrast provides label-free quantitative functional analysis, it does not suffer from photobleaching, and it allows near real-time imaging in 3D with submicrometer spatial resolution. However, due to the susceptibility of current detection schemes to optical absorption and fluorescence from pigments (such as chlorophyll), the plant science and agrochemical research communities have not been able to benefit from these techniques and their application in plant research has remained virtually unexplored. In this paper, we explore the effect of chlorophyll fluorescence and absorption in CARS and SRS microscopy. We show that with the latter it is possible to use phase-sensitive detection to separate the vibrational signal from the (electronic) absorption processes. Finally, we demonstrate the potential of SRS for a range of in planta applications by presenting in situ chemical analysis of plant cell wall components, epicuticular waxes, and the deposition of agrochemical formulations onto the leaf surface.

  5. Automated evaluation of Her-2/neu status in breast tissue from fluorescent in situ hybridization images.

    PubMed

    Raimondo, Francesco; Gavrielides, Marios A; Karayannopoulou, Georgia; Lyroudia, Kleoniki; Pitas, Ioannis; Kostopoulos, Ioannis

    2005-09-01

    The evaluation of fluorescent in situ hybridization (FISH) images is one of the most widely used methods to determine Her-2/neu status of breast samples, a valuable prognostic indicator. Conventional evaluation is a difficult task since it involves manual counting of dots in multiple images. In this paper, we present a multistage algorithm for the automated classification of FISH images from breast carcinomas. The algorithm focuses not only on the detection of FISH dots per image, but also on combining results from multiple images taken from a slice for overall case classification. The algorithm includes mainly two stages for nuclei and dot detection respectively. The dot segmentation consists of a top-hat filtering stage followed by template matching to separate real signals from noise. Nuclei segmentation includes a nonlinearity correction step, global thresholding to identify candidate regions, and a geometric rule to distinguish between holes within a nucleus and holes between nuclei. Finally, the marked watershed transform is used to segment cell nuclei with markers detected as regional maxima of the distance transform. Combining the two stages allows the measurement of FISH signals ratio per cell nucleus and the collective classification of cases as positive or negative. The system was evaluated with receiver operating characteristic analysis and the results were encouraging for the further development of this method. PMID:16190465

  6. Use of In Situ Data to Test a Raman Lidar-Based Cloud Condensation Nuclei Remote Sensing Method

    SciTech Connect

    Ghan, Steven J.; Collins, Donald R.

    2004-02-01

    A method of retrieving vertical profiles of cloud condensation nuclei (CCN) concentration from surface measurements is proposed. Surface measurements of the CCN concentration are scaled by the ratio of the backscatter (or extinction) vertical profile to the backscatter (or extinction) at or near the surface. The backscatter (or extinction) profile is measured by Raman lidar, and is corrected to dry conditions using the vertical profile of relative humidity (also measured by Raman lidar) and surface measurements of the dependence of backscatter (or extinction) on relative humidity. The method assumes the surface aerosol size distribution and composition are representative of the vertical column. Aircraft measurements of aerosol size distribution are used to test the dependence of the retrieval on the uniformity of aerosol size distribution. The retrieval is found to be robust for supersaturations less than 0.02%, but breaks down at higher supersaturations if the vertical profile of aerosol size distribution differs markedly from the distribution at the surface. Such conditions can be detected from the extinction/backscatter ratio.

  7. A new combined nuclear magnetic resonance and Raman spectroscopic probe applied to in situ investigations of catalysts and catalytic processes

    SciTech Connect

    Camp, Jules C. J.; Mantle, Michael D.; York, Andrew P. E.; McGregor, James

    2014-06-15

    Both Raman and nuclear magnetic resonance (NMR) spectroscopies are valuable analytical techniques capable of providing mechanistic information and thereby providing insights into chemical processes, including catalytic reactions. Since both techniques are chemically sensitive, they yield not only structural information but also quantitative analysis. In this work, for the first time, the combination of the two techniques in a single experimental apparatus is reported. This entailed the design of a new experimental probe capable of recording simultaneous measurements on the same sample and/or system of interest. The individual datasets acquired by each spectroscopic method are compared to their unmodified, stand-alone equivalents on a single sample as a means to benchmark this novel piece of equipment. The application towards monitoring reaction progress is demonstrated through the evolution of the homogeneous catalysed metathesis of 1‑hexene, with both experimental techniques able to detect reactant consumption and product evolution. This is extended by inclusion of magic angle spinning (MAS) NMR capabilities with a custom made MAS 7 mm rotor capable of spinning speeds up to 1600 Hz, quantified by analysis of the spinning sidebands of a sample of KBr. The value of this is demonstrated through an application involving heterogeneous catalysis, namely the metathesis of 2-pentene and ethene. This provides the added benefit of being able to monitor both the reaction progress (by NMR spectroscopy) and also the structure of the catalyst (by Raman spectroscopy) on the very same sample, facilitating the development of structure-performance relationships.

  8. A new combined nuclear magnetic resonance and Raman spectroscopic probe applied to in situ investigations of catalysts and catalytic processes.

    PubMed

    Camp, Jules C J; Mantle, Michael D; York, Andrew P E; McGregor, James

    2014-06-01

    Both Raman and nuclear magnetic resonance (NMR) spectroscopies are valuable analytical techniques capable of providing mechanistic information and thereby providing insights into chemical processes, including catalytic reactions. Since both techniques are chemically sensitive, they yield not only structural information but also quantitative analysis. In this work, for the first time, the combination of the two techniques in a single experimental apparatus is reported. This entailed the design of a new experimental probe capable of recording simultaneous measurements on the same sample and/or system of interest. The individual datasets acquired by each spectroscopic method are compared to their unmodified, stand-alone equivalents on a single sample as a means to benchmark this novel piece of equipment. The application towards monitoring reaction progress is demonstrated through the evolution of the homogeneous catalysed metathesis of 1‑hexene, with both experimental techniques able to detect reactant consumption and product evolution. This is extended by inclusion of magic angle spinning (MAS) NMR capabilities with a custom made MAS 7 mm rotor capable of spinning speeds up to 1600 Hz, quantified by analysis of the spinning sidebands of a sample of KBr. The value of this is demonstrated through an application involving heterogeneous catalysis, namely the metathesis of 2-pentene and ethene. This provides the added benefit of being able to monitor both the reaction progress (by NMR spectroscopy) and also the structure of the catalyst (by Raman spectroscopy) on the very same sample, facilitating the development of structure-performance relationships.

  9. Discrete magic angle turning system, apparatus, and process for in situ magnetic resonance spectroscopy and imaging

    DOEpatents

    Hu, Jian Zhi; Sears, Jr., Jesse A.; Hoyt, David W.; Wind, Robert A.

    2009-05-19

    Described are a "Discrete Magic Angle Turning" (DMAT) system, devices, and processes that combine advantages of both magic angle turning (MAT) and magic angle hopping (MAH) suitable, e.g., for in situ magnetic resonance spectroscopy and/or imaging. In an exemplary system, device, and process, samples are rotated in a clockwise direction followed by an anticlockwise direction of exactly the same amount. Rotation proceeds through an angle that is typically greater than about 240 degrees but less than or equal to about 360 degrees at constant speed for a time applicable to the evolution dimension. Back and forth rotation can be synchronized and repeated with a special radio frequency (RF) pulse sequence to produce an isotropic-anisotropic shift 2D correlation spectrum. The design permits tubes to be inserted into the sample container without introducing plumbing interferences, further allowing control over such conditions as temperature, pressure, flow conditions, and feed compositions, thus permitting true in-situ investigations to be carried out.

  10. Programmable oligonucleotide probes design and applications for in situ and in vivo RNA imaging in cells

    NASA Astrophysics Data System (ADS)

    Cheglakov, Zoya

    Unequal spreading of mRNA is a frequent experience observed in varied cell lines. The study of cellular processes dynamics and precise localization of mRNAs offers a vital toolbox to target specific proteins in precise cytoplasmic areas and provides a convenient instrument to uncover their mechanisms and functions. Latest methodological innovations have allowed imaging of a single mRNA molecule in situ and in vivo. Today, Fluorescent In Situ Hybridization (FISH) methods allow the studying of mRNA expression and offer a vital toolbox for accurate biological models. Studies enable analysis of the dynamics of an individual mRNA, have uncovered the multiplex RNA transport systems. With all current approaches, a single mRNA tracking in the mammalian cells is still challenging. This thesis describes mRNA detection methods based on programmable fluorophore-labeled DNA structures complimentary to native targets providing an accurate mRNA imaging in mammalian cells. First method represents beta-actin (ACTB) transcripts in situ detection in human cells, the technique strategy is based on programmable DNA probes, amplified by rolling circle amplification (RCA). The method reports precise localization of molecule of interest with an accuracy of a single-cell. Visualization and localization of specific endogenous mRNA molecules in real-time in vivo has the promising to innovate cellular biology studies, medical analysis and to provide a vital toolbox in drugs invention area. Second method described in this thesis represents miR-21 miRNA detection within a single live-cell resolution. The method using fluorophore-labeled short synthetic DNAs probes forming a stem-loop shape and generating Fluorescent Resonance Energy Transfer (FRET) as a result of target-probes hybridization. Catalytic nucleic acid (DNAzymes) probes are cooperative tool for precise detection of different mRNA targets. With assistance of a complementary fluorophore-quencher labeled substrate, the DNAzymes provide

  11. Tip-enhanced Raman spectroscopic imaging of patterned thiol monolayers

    PubMed Central

    Stadler, Johannes; Schmid, Thomas; Opilik, Lothar; Kuhn, Phillip; Dittrich, Petra S

    2011-01-01

    Summary Full spectroscopic imaging by means of tip-enhanced Raman spectroscopy (TERS) was used to measure the distribution of two isomeric thiols (2-mercaptopyridine (2-PySH) and 4-mercaptopyridine (4-PySH)) in a self-assembled monolayer (SAM) on a gold surface. From a patterned sample created by microcontact printing, an image with full spectral information in every pixel was acquired. The spectroscopic data is in good agreement with the expected molecular distribution on the sample surface due to the microcontact printing process. Using specific marker bands at 1000 cm−1 for 2-PySH and 1100 cm−1 for 4-PySH, both isomers could be localized on the surface and semi-quantitative information was deduced from the band intensities. Even though nanometer size resolution information was not required, the large signal enhancement of TERS was employed here to detect a monolayer coverage of weakly scattering analytes that were not detectable with normal Raman spectroscopy, emphasizing the usefulness of TERS. PMID:22003457

  12. Coherent Raman dual-comb spectroscopy and imaging

    NASA Astrophysics Data System (ADS)

    Ideguchi, Takuro; Holzner, Simon; Bernhardt, Birgitta; Guelachvili, Guy; Hänsch, Theodor W.; Picqué, Nathalie

    2014-11-01

    The invention of the optical frequency comb technique has revolutionized the field of precision spectroscopy, providing a way to measure the absolute frequency of any optical transition. Since, frequency combs have become common equipment for frequency metrology. In the last decade, novel applications for the optical frequency comb have been demonstrated beyond its original purpose. Broadband molecular spectroscopy is one of those. One such technique of molecular spectroscopy with frequency combs, dual-comb Fourier transform spectroscopy provides short measurement times with resolution and accuracy. Two laser frequency combs with slightly different repetition frequencies generate pairs of pulses with a linearly-scanned delay between pulses in a pair. The system without moving parts mimics a fast scanning Fourier transform interferometer. The measurement speed may be several orders of magnitude faster than that of a Michelson-based Fourier transform spectrometer, which opens up new opportunities for broadband molecular spectroscopy. Recently, dual-comb spectroscopy has been extended to nonlinear phenomena. A broadband Raman spectrum of molecular fingerprints may be measured within a few tens of microseconds with coherent Raman dual-comb spectroscopy. Raster scanning the sample leads to hyperspectral images. This rapid and broadband label-free vibrational spectroscopy and imaging technique might provide new diagnostic methods in a variety of scientific and industrial fields.

  13. In-Situ Imaging and Quantification of Tritium Surface Contamination via Coherent Fiber Bundle

    SciTech Connect

    Charles A. Gentile; John J. Parker; Stewart J. Zweben

    2001-11-12

    Princeton Plasma Physics Laboratory (PPPL) has developed a method of imaging tritium on in-situ surfaces for the purpose of real-time data collection. This method expands upon a previous tritium imaging concept, also developed at PPPL. Enhancements include an objective lens coupled to the entry aperture of a coherent fiber optic (CFO) bundle, and a relay lens connecting the exit aperture of the fiber bundle to an intensifier tube and a charge-coupled device (CCD) camera. The system has been specifically fabricated for use in determining tritium concentrations on first wall materials. One potential complication associated with the development of D-T [deuterium-tritium] fueled fusion reactors is the deposition of tritium (i.e., co-deposited layer) on the surface of the primary wall of the vacuum vessel. It would be advantageous to implement a process to accurately determine tritium distribution on these inner surfaces. This fiber optic imaging device provides a highly practical method for determining the location, concentration, and activity of surface tritium deposition. In addition, it can be employed for detection of tritium ''hot-spots'' and ''hide-out'' regions present on the surfaces being imaged.

  14. In-situ, sunphotometer and Raman lidar observations of aerosol transport events in the western Mediterranean during the June 2013 ChArMEx campaign

    NASA Astrophysics Data System (ADS)

    Totems, Julien; Sicard, Michael; Bertolin, Santi; Boytard, Mai-Lan; Chazette, Patrick; Comeron, Adolfo; Dulac, Francois; Hassanzadeh, Sahar; Lange, Diego; Marnas, Fabien; Munoz, Constantino; Shang, Xiaoxia

    2014-05-01

    We present a preliminary analysis of aerosol observations performed in June 2013 in the western Mediterranean at two stations set up in Barcelona and Menorca (Spain) in the framework of the ChArMEx (Chemistry Aerosol Mediterranean Experiment) project. The Barcelona station was equipped with the following fixed instruments belonging to the Universitat Politècnica de Catalunya (UPC): an AERONET (Aerosol Robotic Network) sun-photometer, an MPL (Micro Pulse Lidar) lidar and the UPC multi-wavelength lidar. The MPL lidar works at 532 nm and has a depolarization channel, while the UPC lidar works at 355, 532 and 1064 nm, and also includes two N2- (at 387 and 607 nm) and one H2O-Raman (at 407 nm) channels. The MPL system works continuously 24 hour/day. The UPC system was operated on alert in coordination with the research aircrafts plans involved in the campaign. In Cap d'en Font, Menorca, the mobile laboratory of the Laboratoire des Sciences du Climat et de l'Environnement hosted an automated (AERONET) and a manual (Microtops) 5-lambda sunphotometer, a 3-lambda nephelometer, a 7-lambda aethalometer, as well as the LSCE Water vapor Aerosol LIdar (WALI). This mini Raman lidar, first developed and validated for the HyMEX (Hydrological cycle in the Mediterranean eXperiment) campaign in 2012, works at 355 nm for eye safety and is designed with a short overlap distance (<300m) to probe the lower troposphere. It includes depolarization, N2- and H2O-Raman channels. H2O observations have been calibrated on-site by different methods and show good agreement with balloon measurements. Observations at Cap d'en Font were quasi-continuous from June 10th to July 3rd, 2013. The lidar data at both stations helped direct the research aircrafts and balloon launches to interesting plumes of particles in real time for in-situ measurements. Among some light pollution background from the European continent, a typical Saharan dust event and an unusual American dust/biomass burning event are

  15. Understanding catalyst behavior during in situ heating through simultaneous secondary and transmitted electron imaging

    PubMed Central

    2014-01-01

    By coupling techniques of simultaneous secondary (SE) and transmitted electron (TE) imaging at high resolution in a modern scanning transmission electron microscope (STEM), with the ability to heat specimens using a highly stable MEMS-based heating platform, we obtained synergistic information to clarify the behavior of catalysts during in situ thermal treatments. Au/iron oxide catalyst 'leached' to remove surface Au was heated to temperatures as high as 700°C. The Fe2O3 support particle structure tended to reduce to Fe3O4 and formed surface terraces; the formation, coalescence, and mobility of 1- to 2-nm particles on the terraces were characterized in SE, STEM-ADF, and TEM-BF modes. If combined with simultaneous nanoprobe spectroscopy, this approach will open the door to a new way of studying the kinetics of nano-scaled phenomena. PMID:25419195

  16. In situ atomic force microscopy imaging of electrodeposition of mixed layers of copper/cuprous oxide

    SciTech Connect

    Bonnefont, A.; Kostecki, R.; McLarnon, F.; Arrayet, J.C.; Servant, L.; Argoul, F.

    1999-11-01

    In situ atomic force microscopy (AFM) was applied to the dynamic characterization of the growth of mixed Cu/Cu{sub 2}O layers obtained by galvanostatic electrodeposition from alkaline Cu(II) lactate solutions. The correlation of the cathode potential profile with the average topographic profiles computed from the AFM images provided evidence for two transitions in the deposit growth during which the average growth velocity underwent rapid accelerations, the first one corresponding to zero interfacial concentration (Sand's time) and the second one to the emergence of the oscillations by a smooth transition. Despite its temporal resolution, the AFM technique could not capture the details of a single oscillation, but it proved to be quite adequate for tracking the general evolution of the electrode surface.

  17. Study of SGD along the French Mediterranean coastline using airborne TIR images and in situ analyses

    NASA Astrophysics Data System (ADS)

    van Beek, Pieter; Stieglitz, Thomas; Souhaut, Marc

    2015-04-01

    Although submarine groundwater discharge (SGD) has been investigated in many places of the world, very few studies were conducted along the French coastline of the Mediterranean Sea. Almost no information is available on the fluxes of water and chemical elements associated with these SGD and on their potential impact on the geochemical cycling and ecosystems of the coastal zones. In this work, we combined the use of airborne thermal infrared (TIR) images with in situ analyses of salinity, temperature, radon and radium isotopes to study SGD at various sites along the French Mediterranean coastline and in coastal lagoons. These analyses allowed us to detect SGD sites and to quantify SGD fluxes (that include both the fluxes of fresh groundwater and recirculated seawater). In particular, we will show how the Ra isotopes determined in the La Palme lagoon were used to estimate i) the residence time of waters in the lagoon and ii) SGD fluxes.

  18. Multinuclear in situ magnetic resonance imaging of electrochemical double-layer capacitors.

    PubMed

    Ilott, Andrew J; Trease, Nicole M; Grey, Clare P; Jerschow, Alexej

    2014-08-01

    The last decade has seen an intensified interest in the development and use of electrochemical double-layer capacitors, fuelled by the availability of new electrode materials. The use of nanoporous carbons, in particular, with extremely high surface areas for ion adsorption has enabled the development of working devices with significantly increased capacitances that have become viable alternatives to lithium-ion batteries in certain applications. An understanding of the charge storage mechanism and the ion dynamics inside the nanopores is only just emerging, with the most compelling evidence coming from simulation. Here we present the first in situ magnetic resonance imaging experiments of electrochemical double-layer capacitors. These experiments overcome the limitations of other techniques and give spatially resolved chemical information about the electrolyte ions in real time for a working capacitor of standard geometry. The results provide insight into the predominant capacitive processes occurring at different states of charge and discharge.

  19. Interactions of arsenic with calcite surfaces revealed by in situ nanoscale imaging

    NASA Astrophysics Data System (ADS)

    Renard, François; Putnis, Christine V.; Montes-Hernandez, German; Ruiz-Agudo, Encarnacion; Hovelmann, Jörn; Sarret, Géraldine

    2015-06-01

    Arsenic dissolved in water represents a key environmental and health challenge because several million people are under the threat of contamination. In calcareous environments calcite may play an important role in arsenic solubility and transfer in water. Arsenic-calcite interactions remain controversial, especially for As(III) which was proposed to be either incorporated as such, or as As(V) after oxidation. Here, we provide the first time-lapse in situ study of the evolution of the (10-14) calcite cleavage surface morphology during dissolution and growth in the presence of solutions with various amounts of As(III) or As(V) at room temperature and pH range 6-11 using a flow-through cell connected to an atomic force microscope (AFM). Reaction products were then characterized by Raman spectroscopy. In parallel, co-precipitation experiments with either As(III) or As(V) were performed in batch reactors, and the speciation of arsenic in the resulting solids was studied by X-ray absorption spectroscopy (XAS). For As(V), AFM results showed that it interacts strongly with the calcite surface, and XAS results showed that As(V) was mostly incorporated in the calcite structure. For As(III), AFM results showed much less impact on calcite growth and dissolution and less incorporation was observed. This was confirmed by XAS results that indicate that As(III) was partly oxidized into As(V) before being incorporated into calcite and the resulting calcite contained 36% As(III) and 64% As(V). All these experimental results confirm that As(V) has a much stronger interaction with calcite than As(III) and that calcite may represent an important reservoir for arsenic in various geological environments.

  20. In situ quantitative analysis of individual H2O-CO2 fluid inclusions by laser Raman spectroscopy

    USGS Publications Warehouse

    Azbej, T.; Severs, M.J.; Rusk, B.G.; Bodnar, R.J.

    2007-01-01

    Raman spectral parameters for the Raman ??1 (1285??cm- 1) and 2??2 (1388??cm- 1) bands for CO2 and for the O-H stretching vibration band of H2O (3600??cm- 1) were determined in H2O-CO2 fluid inclusions. Synthetic fluid inclusions containing 2.5 to 50??mol% CO2 were analyzed at temperatures equal to or greater than the homogenization temperature. The results were used to develop an empirical relationship between composition and Raman spectral parameters. The linear peak intensity ratio (IR = ICO2/(ICO2 + IH2O)) is related to the CO2 concentration in the inclusion according to the relation:Mole % C O2 = e- 3.959 IR2 + 8.0734 IRwhere ICO2 is the intensity of the 1388 cm- 1 peak and IH2O is the intensity of the 3600 cm- 1 peak. The relationship between linear peak intensity and composition was established at 350????C for compositions ranging from 2.5 to 50??mol% CO2. The CO2-H2O linear peak intensity ratio (IR) varies with temperature and the relationship between composition and IR is strictly valid only if the inclusions are analyzed at 350????C. The peak area ratio is defined as AR = ACO2/(ACO2 + AH2O), where ACO2 is the integrated area under the 1388??cm- 1 peak and AH2O is the integrated area under the 3600??cm- 1 peak. The relationship between peak area ratio (AR) and the CO2 concentration in the inclusions is given as:Mole % C O2 = 312.5 AR. The equation relating peak area ratio and composition is valid up to 25??mol% CO2 and from 300 to 450????C. The relationship between linear peak intensity ratio and composition should be used for inclusions containing ??? 50??mol% CO2 and which can be analyzed at 350????C. The relationship between composition and peak area ratios should be used when analyzing inclusions at temperatures less than or greater than 350????C (300-450) but can only be used for compositions ??? 25??mol% CO2. Note that this latter relationship has a somewhat larger standard deviation compared to the intensity ratio relationship. Calibration

  1. Raman spectroscopy and imaging to detect contaminants for food safety applications

    Technology Transfer Automated Retrieval System (TEKTRAN)

    This study presents the use of Raman chemical imaging for the screening of dry milk powder for the presence of chemical contaminants and Raman spectroscopy for quantitative assessment of chemical contaminants in liquid milk. For image-based screening, melamine was mixed into dry milk at concentratio...

  2. Screening of adulterants in powdered foods and ingredients using line-scan Raman chemical imaging.

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A newly developed line-scan Raman imaging system using a 785 nm line laser was used to authenticate powdered foods and ingredients. The system was used to collect hyperspectral Raman images in the range of 102–2865 wavenumber from three representative food powders mixed with selected adulterants eac...

  3. In situ cell-by-cell imaging and analysis of small cell populations by mass spectrometry.

    PubMed

    Shrestha, Bindesh; Patt, Joseph M; Vertes, Akos

    2011-04-15

    Molecular imaging by mass spectrometry (MS) is emerging as a tool to determine the distribution of proteins, lipids, and metabolites in tissues. The existing imaging methods, however, mostly rely on predefined rectangular grids for sampling that ignore the natural cellular organization of the tissue. Here we demonstrate that laser ablation electrospray ionization (LAESI) MS can be utilized for in situ cell-by-cell imaging of plant tissues. The cell-by-cell molecular image of the metabolite cyanidin, the ion responsible for purple pigmentation in onion (Allium cepa) epidermal cells, correlated well with the color of cells in the tissue. Chemical imaging using single-cells as voxels reflects the spatial distribution of biochemical differences within a tissue without the distortion stemming from sampling multiple cells within the laser focal spot. Microsampling by laser ablation also has the benefit of enabling the analysis of very small cell populations for biochemical heterogeneity. For example, with a ∼30 μm ablation spot we were able to analyze 3-4 achlorophyllous cells within an oil gland on a sour orange (Citrus aurantium) leaf. To explore cell-to-cell variations within and between tissues, multivariate statistical analysis on LAESI-MS data from epidermal cells of an A. cepa bulb and a C. aurantium leaf and from human buccal epithelial cell populations was performed using the method of orthogonal projections to latent structures discriminant analysis (OPLS-DA). The OPLS-DA analysis of mass spectra, containing over 300 peaks each, provided guidance in identifying a small number of metabolites most responsible for the variance between the cell populations. These metabolites can be viewed as promising candidates for biomarkers that, however, require further verification. PMID:21388149

  4. A high sampling rate digital holographic imager instrument for the in situ measurements of hydrometeors

    NASA Astrophysics Data System (ADS)

    Kaikkonen, Ville A.; Mäkynen, Anssi J.

    2016-06-01

    A novel digital in-line holographic imaging instrument designed for acquiring properties of individual hydrometeors in situ is presented. The instrument has a large measurement volume of 670 cm3. This combined with fast frame rate imaging and software controlled multi-exposure capabilities results in a representative sampling of rain and snowfall events. Hydrometeors are measured and analyzed from the in-focus images with microscopic resolution, and their 3D locations inside the measurement volume are determined. The instrument is designed to operate in cold climates and to produce reliable measurements also during strong winds. The imaging rate of the instrument was designed to be adequately high to observe the dynamic nature of rain and snow falls. By recording multi-exposure holograms, the effective frame rate can be increased. This allows the measurements of the velocities of the fast-falling hydrometeors. The instrument and the hologram processing are described; as well as results from laboratory tests and the first field measurements are shown. As a result, the resolving power of the instrument was measured to vary between 11 and 18 microns inside the measurement volume near the center of the field-of-view. Velocity vectors were measured both from multi-exposure and high frame rate holograms. The measured velocities ranged from 0.1 to 4 m/s. In addition, the projections of a flat-shaped and rotating snowflake imaged at different locations inside the measurement volume demonstrated the possibility to estimate the shape of the hydrometeor from multiple viewing angles.

  5. Characterization of conductive nanobiomaterials derived from viral assemblies by low-voltage STEM imaging and Raman scattering

    NASA Astrophysics Data System (ADS)

    Plascencia-Villa, Germán; Carreño-Fuentes, Liliana; Bahena, Daniel; José-Yacamán, Miguel; Palomares, Laura A.; Ramírez, Octavio T.

    2014-09-01

    New technologies require the development of novel nanomaterials that need to be fully characterized to achieve their potential. High-resolution low-voltage scanning transmission electron microscopy (STEM) has proven to be a very powerful technique in nanotechnology, but its use for the characterization of nanobiomaterials has been limited. Rotavirus VP6 self-assembles into nanotubular assemblies that possess an intrinsic affinity for Au ions. This property was exploited to produce hybrid nanobiomaterials by the in situ functionalization of recombinant VP6 nanotubes with gold nanoparticles. In this work, Raman spectroscopy and advanced analytical electron microscopy imaging with spherical aberration-corrected (Cs) STEM and nanodiffraction at low-voltage doses were employed to characterize nanobiomaterials. STEM imaging revealed the precise structure and arrangement of the protein templates, as well as the nanostructure and atomic arrangement of gold nanoparticles with high spatial sub-Angstrom resolution and avoided radiation damage. The imaging was coupled with backscattered electron imaging, ultra-high resolution scanning electron microscopy and x-ray spectroscopy. The hybrid nanobiomaterials that were obtained showed unique properties as bioelectronic conductive devices and showed enhanced Raman scattering by their precise arrangement into superlattices, displaying the utility of viral assemblies as functional integrative self-assembled nanomaterials for novel applications.

  6. [High definition Raman microscopic imaging]. Progress report, May 1, 1992--June 30, 1993

    SciTech Connect

    Morris, M.D.

    1993-11-01

    Confocal Raman microscopy was developed and used to study molecular sulfur inclusions in glass pellets. The Raman spectrum of water was used as a noninvasive temperature probe in operating electrophoresis capillaries. A macro-scale imager was used to image water Raman scattering using 30 mW 532 nm; it can be used to map boundaries, impurity distributions, and morphological changes in polymers and ceramics. A holographic beam splitter was obtained. Surface-enhanced Raman spectra was obtained from inside zebra fish embryos as a model system. Future research plans are given.

  7. Pulse-width considerations for nonlinear Raman brain imaging: whither the optimum?

    NASA Astrophysics Data System (ADS)

    Lanin, A. A.; Stepanov, E. A.; Tikhonov, R. A.; Sidorov-Biryukov, D. A.; Fedotov, A. B.; Zheltikov, A. M.

    2015-11-01

    We propose simple, yet efficient strategies of pulse-width optimization applicable for nonlinear Raman brain imaging. With the spectral bandwidth of laser pulses accurately matched against the bandwidth of molecular vibrations, the coherent Raman signal is shown to be radically enhanced, enabling higher sensitivities and higher frame rates in nonlinear Raman brain imaging. As a specific example, we show that subpicosecond pulses offer a powerful tool for the detection of brain tumors using stimulated Raman microscopy, as they provide a strong signal without compromising the molecular specificity.

  8. Mapping the intracellular distribution of carbon nanotubes after targeted delivery to carcinoma cells using confocal Raman imaging as a label-free technique

    NASA Astrophysics Data System (ADS)

    Lamprecht, C.; Gierlinger, N.; Heister, E.; Unterauer, B.; Plochberger, B.; Brameshuber, M.; Hinterdorfer, P.; Hild, S.; Ebner, A.

    2012-04-01

    The uptake of carbon nanotubes (CNTs) by mammalian cells and their distribution within cells is being widely studied in recent years due to their increasing use for biomedical purposes. The two main imaging techniques used are confocal fluorescence microscopy and transmission electron microscopy (TEM). The former, however, requires labeling of the CNTs with fluorescent dyes, while the latter is a work-intensive technique that is unsuitable for in situ bio-imaging. Raman spectroscopy, on the other hand, presents a direct, straightforward and label-free alternative. Confocal Raman microscopy can be used to image the CNTs inside cells, exploiting the strong Raman signal connected to different vibrational modes of the nanotubes. In addition, cellular components, such as the endoplasmic reticulum and the nucleus, can be mapped. We first validate our method by showing that only when using the CNTs’ G band for intracellular mapping accurate results can be obtained, as mapping of the radial breathing mode (RBM) only shows a small fraction of CNTs. We then take a closer look at the exact localization of the nanotubes inside cells after folate receptor-mediated endocytosis and show that, after 8-10 h incubation, the majority of CNTs are localized around the nucleus. In summary, Raman imaging has enormous potential for imaging CNTs inside cells, which is yet to be fully realized. The authors declare no conflict of interest.

  9. Characterization of fluor concentration and geometry in organic scintillators for in situ beta imaging

    SciTech Connect

    Tornai, M.P.; Hoffman, E.J.; MacDonald, L.R.; Levin, C.S.

    1996-12-01

    Development of a small area (1--2 cm{sup 2}) in situ beta imaging device includes optimization of the front end scintillation detector, which is fiber optically coupled to a remote photon detector. Thin plastic scintillation detectors, which are sensitive to charged particles, are the ideal detectors due to the low sensitivity to ambient gamma backgrounds. The light output of a new binary plastic scintillator was investigated with respect to increasing concentrations of the fluor (0.5--2.0% by weight) and varying thickness cylindrical configurations of the intended imaging detector. The fluor had an emission maximum increasing from 431 to 436 nm with increasing fluor concentration. The decay time(s) had two components (0.38 and 1.74 ns). There was an {approximately}20% increase in light output with increasing fluor concentration measured with both {sup 204}Tl betas and conversion electrons from {sup 207}Bi. The highest light output of this new scintillator was measured to be {approximately}30% lower than BC404. Simulations predicted the 1.5 mm scintillator thickness at which light output and energy absorption for {approximately}700 keV electrons (e.g., from {sup 204}Tl, {sup 18}F) were maximized, which corresponded with measurements. As beta continua are relatively featureless, energy calibration for the thin scintillators was investigated using Landau distributions, which appear as distinct peaks in the spectra. As the scintillators were made thinner, gamma backgrounds were shown to linearly decrease.

  10. Atomic-scale imaging and spectroscopy for in situ liquid scanning transmission electron microscopy.

    PubMed

    Jungjohann, Katherine L; Evans, James E; Aguiar, Jeffery A; Arslan, Ilke; Browning, Nigel D

    2012-06-01

    Observation of growth, synthesis, dynamics, and electrochemical reactions in the liquid state is an important yet largely unstudied aspect of nanotechnology. The only techniques that can potentially provide the insights necessary to advance our understanding of these mechanisms is simultaneous atomic-scale imaging and quantitative chemical analysis (through spectroscopy) under environmental conditions in the transmission electron microscope. In this study we describe the experimental and technical conditions necessary to obtain electron energy loss (EEL) spectra from a nanoparticle in colloidal suspension using aberration-corrected scanning transmission electron microscopy (STEM) combined with the environmental liquid stage. At a fluid path length below 400 nm, atomic resolution images can be obtained and simultaneous compositional analysis can be achieved. We show that EEL spectroscopy can be used to quantify the total fluid path length around the nanoparticle and demonstrate that characteristic core-loss signals from the suspended nanoparticles can be resolved and analyzed to provide information on the local interfacial chemistry with the surrounding environment. The combined approach using aberration-corrected STEM and EEL spectra with the in situ fluid stage demonstrates a plenary platform for detailed investigations of solution-based catalysis. PMID:22640968

  11. Atomic-Scale Imaging and Spectroscopy for In Situ Liquid Scanning Transmission Electron Microscopy

    SciTech Connect

    Jungjohann, K. L.; Evans, James E.; Aguiar, Jeff; Arslan, Ilke; Browning, Nigel D.

    2012-06-04

    Observation of growth, synthesis, dynamics and electrochemical reactions in the liquid state is an important yet largely unstudied aspect of nanotechnology. The only techniques that can potentially provide the insights necessary to advance our understanding of these mechanisms is simultaneous atomic-scale imaging and quantitative chemical analysis (through spectroscopy) under environmental conditions in the transmission electron microscope (TEM). In this study we describe the experimental and technical conditions necessary to obtain electron energy loss (EEL) spectra from a nanoparticle in colloidal suspension using aberration corrected scanning transmission electron microscopy (STEM) combined with the environmental liquid stage. At a fluid path length below 400 nm, atomic resolution images can be obtained and simultaneous compositional analysis can be achieved. We show that EEL spectroscopy can be used to quantify the total fluid path length around the nanoparticle, and demonstrate characteristic core-loss signals from the suspended nanoparticles can be resolved and analyzed to provide information on the local interfacial chemistry with the surrounding environment. The combined approach using aberration corrected STEM and EEL spectra with the in situ fluid stage demonstrates a plenary platform for detailed investigations of solution based catalysis and biological research.

  12. Atomic-scale imaging and spectroscopy for in situ liquid scanning transmission electron microscopy.

    PubMed

    Jungjohann, Katherine L; Evans, James E; Aguiar, Jeffery A; Arslan, Ilke; Browning, Nigel D

    2012-06-01

    Observation of growth, synthesis, dynamics, and electrochemical reactions in the liquid state is an important yet largely unstudied aspect of nanotechnology. The only techniques that can potentially provide the insights necessary to advance our understanding of these mechanisms is simultaneous atomic-scale imaging and quantitative chemical analysis (through spectroscopy) under environmental conditions in the transmission electron microscope. In this study we describe the experimental and technical conditions necessary to obtain electron energy loss (EEL) spectra from a nanoparticle in colloidal suspension using aberration-corrected scanning transmission electron microscopy (STEM) combined with the environmental liquid stage. At a fluid path length below 400 nm, atomic resolution images can be obtained and simultaneous compositional analysis can be achieved. We show that EEL spectroscopy can be used to quantify the total fluid path length around the nanoparticle and demonstrate that characteristic core-loss signals from the suspended nanoparticles can be resolved and analyzed to provide information on the local interfacial chemistry with the surrounding environment. The combined approach using aberration-corrected STEM and EEL spectra with the in situ fluid stage demonstrates a plenary platform for detailed investigations of solution-based catalysis.

  13. A semi-automated image analysis procedure for in situ plankton imaging systems.

    PubMed

    Bi, Hongsheng; Guo, Zhenhua; Benfield, Mark C; Fan, Chunlei; Ford, Michael; Shahrestani, Suzan; Sieracki, Jeffery M

    2015-01-01

    Plankton imaging systems are capable of providing fine-scale observations that enhance our understanding of key physical and biological processes. However, processing the large volumes of data collected by imaging systems remains a major obstacle for their employment, and existing approaches are designed either for images acquired under laboratory controlled conditions or within clear waters. In the present study, we developed a semi-automated approach to analyze plankton taxa from images acquired by the ZOOplankton VISualization (ZOOVIS) system within turbid estuarine waters, in Chesapeake Bay. When compared to images under laboratory controlled conditions or clear waters, images from highly turbid waters are often of relatively low quality and more variable, due to the large amount of objects and nonlinear illumination within each image. We first customized a segmentation procedure to locate objects within each image and extracted them for classification. A maximally stable extremal regions algorithm was applied to segment large gelatinous zooplankton and an adaptive threshold approach was developed to segment small organisms, such as copepods. Unlike the existing approaches for images acquired from laboratory, controlled conditions or clear waters, the target objects are often the majority class, and the classification can be treated as a multi-class classification problem. We customized a two-level hierarchical classification procedure using support vector machines to classify the target objects (< 5%), and remove the non-target objects (> 95%). First, histograms of oriented gradients feature descriptors were constructed for the segmented objects. In the first step all non-target and target objects were classified into different groups: arrow-like, copepod-like, and gelatinous zooplankton. Each object was passed to a group-specific classifier to remove most non-target objects. After the object was classified, an expert or non-expert then manually removed the

  14. Abnormal cubic-tetragonal phase transition of barium strontium titanate nanoparticles studied by in situ Raman spectroscopy and transmission electron microscopy heating experiments

    SciTech Connect

    Zhang, Yin; Chen, Chen; Gao, Ran; Xia, Feng; Li, YueSheng; Che, Renchao

    2015-11-02

    Phase stability of the ferroelectric materials at high temperature is extremely important to their device performance. Ba{sub x}Sr{sub 1−x}TiO{sub 3} (BST) nanoparticles with different Sr contents (x = 1, 0.91, 0.65, 0.4, and 0) are prepared by a facile hydrothermal method. Using Raman spectroscopy and transmission electron microscopy (TEM) analyses under in situ heating conditions (up to 300 °C), the phase transitions of BST nanoparticles between 25 °C and 280 °C are comprehensively investigated. The original Curie temperature of BST nanoparticles decreases abruptly with the increase in Sr content, which is more obvious than in the bulk or film material. Besides, an abnormal phase transition from cubic to tetragonal structure is observed from BST nanoparticles and the transition temperature rises along with the increase in Sr content. Direct TEM evidences including a slight lattice distortion have been provided. Differently, BaTiO{sub 3} nanoparticles remained in the tetragonal phase during the above temperature ranges.

  15. Incorporation of low energy activated nitrogen onto HOPG surface: Chemical states and thermal stability studies by in-situ XPS and Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Chandran, Maneesh; Shasha, Michal; Michaelson, Shaul; Hoffman, Alon

    2016-09-01

    In this paper we report the chemical states analysis of activated nitrogen incorporated highly oriented pyrolytic graphite (HOPG) surface under well-controlled conditions. Nitrogen incorporation is carried out by two different processes: an indirect RF nitrogen plasma and low energy (1 keV) N2+ implantation. Bonding configuration, concentration and thermal stability of the incorporated nitrogen species by aforesaid processes are systematically compared by in-situ X-ray photoelectron spectroscopy (XPS). Relatively large concentration of nitrogen is incorporated onto RF nitride HOPG surface (16.2 at.%), compared to N2+ implanted HOPG surface (7.7 at.%). The evolution of N 1s components (N1, N2, N3) with annealing temperature is comprehensively discussed, which indicates that the formation and reorganization of local chemical bonding states are determined by the process of nitridation and not by the prior chemical conditioning (i.e., amorphization or hydrogenation) of the HOPG surface. A combined XPS and Raman spectroscopy studies revealed that N2+ implantation process resulted in a high level of defects to the HOPG surface, which cannot be annealed-out by heat treatment up to 1000 °C. On the other hand, the RF nitrogen plasma process did not produce a high level of surface defects, while incorporating nearly the same amount of stable nitrogen species.

  16. Non-destructive in situ study of "Mad Meg" by Pieter Bruegel the Elder using mobile X-ray fluorescence, X-ray diffraction and Raman spectrometers

    NASA Astrophysics Data System (ADS)

    Van de Voorde, Lien; Van Pevenage, Jolien; De Langhe, Kaat; De Wolf, Robin; Vekemans, Bart; Vincze, Laszlo; Vandenabeele, Peter; Martens, Maximiliaan P. J.

    2014-07-01

    "Mad Meg", a figure of Flemish folklore, is the subject of a famous oil-on-panel painting by the Flemish renaissance artist Pieter Bruegel the Elder, exhibited in the Museum Mayer van den Bergh (Antwerp, Belgium). This article reports on the in situ chemical characterization of this masterpiece by using currently available state-of-the-art portable analytical instruments. The applied non-destructive analytical approach involved the use of a) handheld X-ray fluorescence instrumentation for retrieving elemental information and b) portable X-ray fluorescence/X-ray diffraction instrumentation and laser-based Raman spectrometers for obtaining structural/molecular information. Next to material characterization of the used pigments and of the different preparation layers of the painting, also the verification of two important historical iconographic hypotheses is performed concerning the economic way of painting by Brueghel, and whether or not he used blue smalt pigment for painting the boat that appears towards the top of the painting. The pigments identified are smalt pigment (65% SiO2 + 15% K2O + 10% CoO + 5% Al2O3) for the blue color present in all blue areas of the painting, probably copper resinate for the green colors, vermillion (HgS) as red pigment and lead white is used to form different colors. The comparison of blue pigments used on different areas of the painting gives no differences in the elemental fingerprint which confirms the existing hypothesis concerning the economic painting method by Bruegel.

  17. In situ DRIFT, Raman, and XRF implementation in a multianalytical methodology to diagnose the impact suffered by built heritage in urban atmospheres.

    PubMed

    Gómez-Laserna, Olivia; Arrizabalaga, Iker; Prieto-Taboada, Nagore; Olazabal, María Ángeles; Arana, Gorka; Madariaga, Juan Manuel

    2015-07-01

    This work addresses the evaluation of an innovative mutianalytical method to assess the conservation state of a fifteenth century palace house. With the goal of reducing the handicaps of field analysis, the in situ spectroscopic assessment, often based on the use of X-ray fluorescence and Raman spectrometers, was complemented by the use of diffuse reflectance infrared Fourier transform spectroscopy. In this manner, its usefulness as a diagnostic tool to discover the origin and mechanisms of the damage caused by atmospheric and infiltration water attacks were thoroughly examined. Moreover, the study was extended in the laboratory to increase the information obtained by nondestructive techniques. The results revealed a severe material loss caused by soluble salts. Thus, a noninvasive sampling method using cellulose patches was tested to study the amount and mobility of salts by means of ion chromatography. Finally, to establish the chemical degradation processes that are occurring in the palace, a chemometric analysis of the quantitative data as well as the construction of thermodynamic models was done to advise on the required restorative actions. Graphical Abstract The different phases of the multianalytical method to assess the conservation state of built heritage.

  18. In situ controlled growth of well-dispersed gold nanoparticles in TiO2 nanotube arrays as recyclable substrates for surface-enhanced Raman scattering.

    PubMed

    Chen, Yajie; Tian, Guohui; Pan, Kai; Tian, Chungui; Zhou, Juan; Zhou, Wei; Ren, Zhiyu; Fu, Honggang

    2012-01-21

    In this paper, well-aligned Au-decorated TiO(2) nanotube arrays with high surface-enhanced Raman scattering (SERS) enhancement were prepared using a facile in situ reduction and controlled growth approach. The gold nanoparticles are well-dispersed and assembled on the mouth surface and the inside of the TiO(2) nanotubes without clogging. The structure and optical properties of the Au-decorated TiO(2) nanotube arrays have been characterized. The Au-decorated TiO(2) nanotube arrays were employed as SERS-active substrates, which exhibit good performance due to long-range coupling between Au nanoparticles, and TiO(2)-assisted enhanced charge-transfer from Au to Rh6G. The SERS activity of the substrates strongly depends on the crystallite size and level of aggregation. The substrates display significant fluorescence quenching ability and uniform SERS responses throughout the whole surface area. Particularly, good recyclability is shown. The photocatalytic property of Au-decorated TiO(2) nanotube array was exploited to recycle the substrate through UV light photocatalytic purification. The experimental results showed that the substrate is featured by high reproducibility and can be used as a highly efficient SERS substrate for multiple detection of different chemical and biological molecules.

  19. In situ gap-mode Raman spectroscopy on single-crystal Au(100) electrodes: tuning the torsion angle of 4,4'-biphenyldithiols by an electrochemical gate field.

    PubMed

    Cui, Li; Liu, Bo; Vonlanthen, David; Mayor, Marcel; Fu, Yongchun; Li, Jian-Feng; Wandlowski, Thomas

    2011-05-18

    In situ gap-mode Raman spectra were acquired in an electrochemical environment on a single-crystal gold electrode employing a Au(100)|4,4'-biphenyldithiol (BPDT)|Au-NP(55 nm) sandwich assembly. This geometry enabled an investigation of the influence of an applied electrochemical gate field on the conformational changes in nanojunctions, such as the torsion angle (φ) of molecules. A linear correlation between the intensity ratio I(C═C)/I(C(ring)-S) and cos(2) φ in 4,4'-BPDT-type molecular junctions was established and subsequently utilized to estimate the potential dependence of the torsion angle of the "flexible" molecule M1 at different potentials. The latter decreases as the potential (charge) becomes more negative, resulting in better π-π coupling, which correlates with enhanced junction conductance. The demonstrated spectroelectrochemical strategy and the direct correlation of the spectroscopic results with (single) molecular conductance studies may guide the selection and elucidation of functional molecules for potential applications in novel nanodevices.

  20. Microfluidic electrochemical device and process for chemical imaging and electrochemical analysis at the electrode-liquid interface in-situ

    DOEpatents

    Yu, Xiao-Ying; Liu, Bingwen; Yang, Li; Zhu, Zihua; Marshall, Matthew J.

    2016-03-01

    A microfluidic electrochemical device and process are detailed that provide chemical imaging and electrochemical analysis under vacuum at the surface of the electrode-sample or electrode-liquid interface in-situ. The electrochemical device allows investigation of various surface layers including diffuse layers at selected depths populated with, e.g., adsorbed molecules in which chemical transformation in electrolyte solutions occurs.

  1. Acousto-optic Imaging System for In-situ Measurement of the High Temperature Distribution in Micron-size Specimens

    NASA Astrophysics Data System (ADS)

    Machikhin, Alexander S.; Zinin, Pavel V.; Shurygin, Alexander V.

    We developed a unique acousto-optic imaging system for in-situ measurement of high temperature distribution on micron-size specimens. The system was designed to measure temperature distribution inside minerals and functional material phases subjected to high pressure and high temperatures in a diamond anvil cell (DAC) heated by a high powered laser.

  2. In situ X-ray ptychography imaging of high-temperature CO{sub 2} acceptor particle agglomerates

    SciTech Connect

    Høydalsvik, Kristin; Bø Fløystad, Jostein; Esmaeili, Morteza; Mathiesen, Ragnvald H.; Breiby, Dag W.; Zhao, Tiejun; Rønning, Magnus; Diaz, Ana; Andreasen, Jens W.

    2014-06-16

    Imaging nanoparticles under relevant reaction conditions of high temperature and gas pressure is difficult because conventional imaging techniques, like transmission electron microscopy, cannot be used. Here we demonstrate that the coherent diffractive imaging technique of X-ray ptychography can be used for in situ phase contrast imaging in structure studies at atmospheric pressure and elevated temperatures. Lithium zirconate, a candidate CO{sub 2} capture material, was studied at a pressure of one atmosphere in air and in CO{sub 2}, at temperatures exceeding 600 °C. Images with a spatial resolution better than 200 nm were retrieved, and possibilities for improving the experiment are described.

  3. In-situ imaging of reacting single-particle zeolites by non-linear optical microscopy

    NASA Astrophysics Data System (ADS)

    Wrzesinski, Paul J.; Slipchenko, Mikhail N.; Zaman, Taslima A.; Rioux, Robert M.; Gord, James R.; Roy, Sukesh

    2015-03-01

    Zeolite catalysis has been exploited by the petrochemical industry since the 1940's for catalytic cracking reactions of long chain hydrocarbons. The selectivity of zeolites strongly depends on a pore size, which is controlled by the chosen structure-directing agent (SDA) and by the SDA decomposition/removal process. Although zeolites are composed of micron-sized crystals, studies of zeolite materials typically focus on bulk (i.e., ensemble) measurements to elucidate structure-function information or to optimize catalysts and/or process parameters. To examine these phenomena on the microscale, non-linear optical microscopy is used to provide real-time imaging of chemical reactions in zeolites at temperatures exceeding 400°C. The template decomposition mechanism is studied, as elucidation of the mechanism is critical to understanding the relationship between the decomposition chemistry and the nanoscale features of the zeolite (topology, Si/Al ratio, added dopants). Forward stimulated Raman scattering (SRS), forward coherent anti-Stokes Raman scattering (CARS) and epi two-photon fluorescence (TPF) modalities are acquired simultaneously providing video-rate structural and chemical information. A high-temperature cell with gas inlet system is used for the study of reactions under various temperatures and gas environments. Examining the decomposition process with single-particle resolution enables access to ensemble-level and spatially-resolved behavior. Parallel experiments on bulk zeolite powders are conducted to enable comparison of ensemble and single-particle behavior during template decomposition. Our multi-technique approach has high potential for gaining insight into the link between nanoscale structure and catalytic activity and selectivity of zeolitic materials.

  4. In-situ Damage Assessment of Collagen within Ancient Manuscripts Written on Parchment: A Polarized Raman Spectroscopy Approach

    NASA Astrophysics Data System (ADS)

    Schütz, R.; Rabin, I.; Hahn, O.; Fratzl, P.; Masic, A.

    2010-08-01

    The collection generally known as Qumran scrolls or Dead Sea Scrolls (DSS) comprises some 900 highly fragmented manuscripts (mainly written on parchment) from the Second Temple period. In the years since their manufacture the writing materials have undergone serious deterioration due to a combination of natural ageing and environmental effects. Therefore, understanding quantitatively state of conservation of such manuscripts is a challenging task and a deep knowledge of damage pathways on all hierarchical levels (from molecular up to macroscopic) results of fundamental importance for a correct protection and conservation strategy. However, the degradation of parchments is very complex and not well understood process. Parchment is a final product of processing of animal skin and consist mainly of type I collagen, which is the most abundant constituent of the dermal matrix. Collagen molecule is built by folding of three polypeptide α-chains into a right-handed triple helix. Every α-chain is made by a repetitive sequence of (Gly-X-Y)n, where X and Y are often proline and hydroxyproline. Parallel and staggered collagen triple helices associate into fibrils, which than assemble into fibers. Deterioration of parchment is caused by chemical changes due to gelatinization, oxidation and hydrolysis of the collagen chains, promoted by several factors, summarized as biological and microbiological (bacteria, fungi etc.), heat, light, humidity and pollutants (1, 2). In this work we have focused on studying the collagen within parchments on two different levels of organization (molecular and fibrilar) by applying polarized Raman spectroscopic technique. Beside spectral information related to chemical bonding, polarization anisotropy of some collagen bands (i.e. amide I) has been used to explore organization of collagen on higher levels (three-dimensional arrangement of the triple-helix molecules and their alignment within a fibril of collagen). To this aim we have compared

  5. A small animal Raman instrument for rapid, wide-area, spectroscopic imaging

    PubMed Central

    Bohndiek, Sarah E.; Wagadarikar, Ashwin; Zavaleta, Cristina L.; Van de Sompel, Dominique; Garai, Ellis; Jokerst, Jesse V.; Yazdanfar, Siavash; Gambhir, Sanjiv S.

    2013-01-01

    Raman spectroscopy, amplified by surface enhanced Raman scattering (SERS) nanoparticles, is a molecular imaging modality with ultra-high sensitivity and the unique ability to multiplex readouts from different molecular targets using a single wavelength of excitation. This approach holds exciting prospects for a range of applications in medicine, including identification and characterization of malignancy during endoscopy and intraoperative image guidance of surgical resection. The development of Raman molecular imaging with SERS nanoparticles is presently limited by long acquisition times, poor spatial resolution, small field of view, and difficulty in animal handling with existing Raman spectroscopy instruments. Our goal is to overcome these limitations by designing a bespoke instrument for Raman molecular imaging in small animals. Here, we present a unique and dedicated small-animal Raman imaging instrument that enables rapid, high-spatial resolution, spectroscopic imaging over a wide field of view (> 6 cm2), with simplified animal handling. Imaging of SERS nanoparticles in small animals demonstrated that this small animal Raman imaging system can detect multiplexed SERS signals in both superficial and deep tissue locations at least an order of magnitude faster than existing systems without compromising sensitivity. PMID:23821752

  6. In situ calibration of the foil detector for an infrared imaging video bolometer using a carbon evaporation technique

    NASA Astrophysics Data System (ADS)

    Mukai, K.; Peterson, B. J.; Takayama, S.; Sano, R.

    2016-11-01

    The InfraRed imaging Video Bolometer (IRVB) is a useful diagnostic for the multi-dimensional measurement of plasma radiation profiles. For the application of IRVB measurement to the neutron environment in fusion plasma devices such as the Large Helical Device (LHD), in situ calibration of the thermal characteristics of the foil detector is required. Laser irradiation tests of sample foils show that the reproducibility and uniformity of the carbon coating for the foil were improved using a vacuum evaporation method. Also, the principle of the in situ calibration system was justified.

  7. Characterization of propagation and scattering via wavefield imaging for improved in situ imaging of damage in composites

    NASA Astrophysics Data System (ADS)

    Williams, Westin B.; Michaels, Jennifer E.; Michaels, Thomas E.

    2016-04-01

    Detection, localization, and characterization of impact damage in composites using in situ transducers are important objectives for the aerospace industry to both reduce maintenance costs and prevent failures. A network of piezoelectric transducers spatially distributed over an area of interest is one practical configuration for utilizing guided waves to accomplish these objectives. Detecting and localizing barely visible impact damage with such a sparse array has been demonstrated in prior work, and improvements in localization were demonstrated by incorporating fairly crude estimates of scattering patterns in the imaging algorithms. Here we obtain more estimates of scattering patterns from a simulated defect by employing baseline subtraction of wavefield data recorded in a circle centered at the scatterer. Scattering patterns are estimated from the wavefield residual signals before and after simulated damage is introduced and the estimated scattering patterns are then incorporated into sparse array imaging via the minimum variance imaging method. Images created with different scattering patterns are compared and the efficacy of the methodology is assessed.

  8. Raman Spectroscopic Imaging of the Whole Ciona intestinalis Embryo during Development

    PubMed Central

    Nakamura, Mitsuru J.; Hotta, Kohji; Oka, Kotaro

    2013-01-01

    Intracellular composition and the distribution of bio-molecules play central roles in the specification of cell fates and morphogenesis during embryogenesis. Consequently, investigation of changes in the expression and distribution of bio-molecules, especially mRNAs and proteins, is an important challenge in developmental biology. Raman spectroscopic imaging, a non-invasive and label-free technique, allows simultaneous imaging of the intracellular composition and distribution of multiple bio-molecules. In this study, we explored the application of Raman spectroscopic imaging in the whole Ciona intestinalis embryo during development. Analysis of Raman spectra scattered from C. intestinalis embryos revealed a number of localized patterns of high Raman intensity within the embryo. Based on the observed distribution of bio-molecules, we succeeded in identifying the location and structure of differentiated muscle and endoderm within the whole embryo, up to the tailbud stage, in a label-free manner. Furthermore, during cell differentiation, we detected significant differences in cell state between muscle/endoderm daughter cells and daughter cells with other fates that had divided from the same mother cells; this was achieved by focusing on the Raman intensity of single Raman bands at 1002 or 1526 cm−1, respectively. This study reports the first application of Raman spectroscopic imaging to the study of identifying and characterizing differentiating tissues in a whole chordate embryo. Our results suggest that Raman spectroscopic imaging is a feasible label-free technique for investigating the developmental process of the whole embryo of C. intestinalis. PMID:23977129

  9. Raman mapping for kinetic analysis of crystallization of amorphous drug based on distributional images.

    PubMed

    Ueda, Hiroshi; Ida, Yasuo; Kadota, Kazunori; Tozuka, Yuichi

    2014-02-28

    The feasibility of Raman mapping for understanding the crystallization mechanism of an amorphous drug was investigated using described images. The crystallization tendency of amorphous indomethacin under dry condition at 30 °C was kinetically evaluated by means of Raman mapping and X-ray powder diffraction (XRPD) with change in the calculated crystallinities. Raman images directly revealed the occurrence of particle size-dependent non-uniform crystallization; slow crystallization of large particles, but fast crystallization of small particles. Kinetic analysis by fitting to the Kolmogorov-Johnson-Mehl-Avrami equation was performed for the crystallization profiles of both Raman mapping and XRPD data. For the Raman mapping data, the distribution of large particles was characterized and examined. The kinetic parameters calculated from the whole Raman image area agreed well with those of XRPD, suggesting accurate prediction of both techniques for the entire crystallization. Raman images revealed the change in the crystallization mechanism for the focused area; the large particles showed a reduced crystallization rate constant and an increase in the dimensional crystal growth exponent. Raman mapping is an attractive tool for quantitative and kinetic investigation of the crystallization mechanism with distributional images.

  10. In situ imaging reveals the biomass of giant protists in the global ocean.

    PubMed

    Biard, Tristan; Stemmann, Lars; Picheral, Marc; Mayot, Nicolas; Vandromme, Pieter; Hauss, Helena; Gorsky, Gabriel; Guidi, Lionel; Kiko, Rainer; Not, Fabrice

    2016-04-28

    Planktonic organisms play crucial roles in oceanic food webs and global biogeochemical cycles. Most of our knowledge about the ecological impact of large zooplankton stems from research on abundant and robust crustaceans, and in particular copepods. A number of the other organisms that comprise planktonic communities are fragile, and therefore hard to sample and quantify, meaning that their abundances and effects on oceanic ecosystems are poorly understood. Here, using data from a worldwide in situ imaging survey of plankton larger than 600 μm, we show that a substantial part of the biomass of this size fraction consists of giant protists belonging to the Rhizaria, a super-group of mostly fragile unicellular marine organisms that includes the taxa Phaeodaria and Radiolaria (for example, orders Collodaria and Acantharia). Globally, we estimate that rhizarians in the top 200 m of world oceans represent a standing stock of 0.089 Pg carbon, equivalent to 5.2% of the total oceanic biota carbon reservoir. In the vast oligotrophic intertropical open oceans, rhizarian biomass is estimated to be equivalent to that of all other mesozooplankton (plankton in the size range 0.2-20 mm). The photosymbiotic association of many rhizarians with microalgae may be an important factor in explaining their distribution. The previously overlooked importance of these giant protists across the widest ecosystem on the planet changes our understanding of marine planktonic ecosystems.

  11. In situ label-free static cytometry by monitoring spatiotemporal fluctuations of image gray values.

    PubMed

    Wohl, Ishay; Zurgil, Naomi; Hakuk, Yaron; Sobolev, Maria; Galmidi, Moti; Deutsch, Mordechai

    2015-10-01

    Spatiotemporal fluctuation of homogeneity and randomness of gray values within an image was explored and utilized as a label-free means for cell examination. This was done by utilizing a user-friendly combination of simple bright field microscope and Cytocapture dish, wherein cells are individually held, each within a picoliter optical chamber, forming an array of cells to be repeatedly measured over time and biomanipulated in situ at single-cell resolution. First, the measured gray level information entropy (GLIE) was used and, based on the fact that living cells are not in a state of thermodynamic equilibrium but rather in a metastable state, two fluctuation-sensitive measures were proposed and examined: ASDE—the spatial average of temporal standard deviation (SD) of GLIE, and AA—the average time autocorrelation of GLIE. System performance was validated on cell-free solutions. This was followed by examining the performance of the measures AGLIE, ASDE, and AA to distinguish among individual live-still, dead and live cells from various cell lines, as well as between cells which were and were not induced to differentiate. Results, which were obtained on four types of cells, indicate advantages of the proposed measures which are believed to be significant additions to the microscope-based probe-free toolbox. PMID:26506467

  12. In situ label-free static cytometry by monitoring spatiotemporal fluctuations of image gray values

    NASA Astrophysics Data System (ADS)

    Wohl, Ishay; Zurgil, Naomi; Hakuk, Yaron; Sobolev, Maria; Galmidi, Moti; Deutsch, Mordechai

    2015-10-01

    Spatiotemporal fluctuation of homogeneity and randomness of gray values within an image was explored and utilized as a label-free means for cell examination. This was done by utilizing a user-friendly combination of simple bright field microscope and Cytocapture dish, wherein cells are individually held, each within a picoliter optical chamber, forming an array of cells to be repeatedly measured over time and biomanipulated in situ at single-cell resolution. First, the measured gray level information entropy (GLIE) was used and, based on the fact that living cells are not in a state of thermodynamic equilibrium but rather in a metastable state, two fluctuation-sensitive measures were proposed and examined: ASDE-the spatial average of temporal standard deviation (SD) of GLIE, and AA-the average time autocorrelation of GLIE. System performance was validated on cell-free solutions. This was followed by examining the performance of the measures AGLIE, ASDE, and AA to distinguish among individual live-still, dead and live cells from various cell lines, as well as between cells which were and were not induced to differentiate. Results, which were obtained on four types of cells, indicate advantages of the proposed measures which are believed to be significant additions to the microscope-based probe-free toolbox.

  13. Optimal drug release schedule for in-situ radiosensitization of image guided permanent prostate implants

    NASA Astrophysics Data System (ADS)

    Cormack, Robert A.; Nguyen, Paul L.; D'Amico, Anthony V.; Sridhar, Sri; Makrigiorgos, Mike

    2011-03-01

    Planned in-situ radiosensitization may improve the therapeutic ratio of image guided 125I prostate brachytherapy. Spacers used in permanent implants may be manufactured from a radiosensitizer-releasing polymer to deliver protracted localized sensitization of the prostate. Such devices will have a limited drug-loading capacity, and the drug release schedule that optimizes outcome, under such a constraint, is not known. This work determines the optimal elution schedules for 125I prostate brachytherapy. The interaction between brachytherapy dose distributions and drug distribution around drug eluting spacers is modeled using a linear-quadratic (LQ) model of cell kill. Clinical brachytherapy plans were used to calculate the biologic effective dose (BED) for planned radiation dose distributions while adding the spatial distributions of radiosensitizer while varying the temporal release schedule subject to a constraint on the drug capacity of the eluting spacers. Results: The greatest increase in BED is achieved by schedules with the greatest sensitization early in the implant. Making brachytherapy spacers from radiosensitizer eluting polymer transforms inert parts of the implant process into a means of enhancing the effect of the brachytherapy radiation. Such an approach may increase the therapeutic ratio of prostate brachytherapy or offer a means of locally boosting the radiation effect without increasing the radiation dose to surrounding tissues.

  14. In situ imaging reveals the biomass of giant protists in the global ocean.

    PubMed

    Biard, Tristan; Stemmann, Lars; Picheral, Marc; Mayot, Nicolas; Vandromme, Pieter; Hauss, Helena; Gorsky, Gabriel; Guidi, Lionel; Kiko, Rainer; Not, Fabrice

    2016-04-28

    Planktonic organisms play crucial roles in oceanic food webs and global biogeochemical cycles. Most of our knowledge about the ecological impact of large zooplankton stems from research on abundant and robust crustaceans, and in particular copepods. A number of the other organisms that comprise planktonic communities are fragile, and therefore hard to sample and quantify, meaning that their abundances and effects on oceanic ecosystems are poorly understood. Here, using data from a worldwide in situ imaging survey of plankton larger than 600 μm, we show that a substantial part of the biomass of this size fraction consists of giant protists belonging to the Rhizaria, a super-group of mostly fragile unicellular marine organisms that includes the taxa Phaeodaria and Radiolaria (for example, orders Collodaria and Acantharia). Globally, we estimate that rhizarians in the top 200 m of world oceans represent a standing stock of 0.089 Pg carbon, equivalent to 5.2% of the total oceanic biota carbon reservoir. In the vast oligotrophic intertropical open oceans, rhizarian biomass is estimated to be equivalent to that of all other mesozooplankton (plankton in the size range 0.2-20 mm). The photosymbiotic association of many rhizarians with microalgae may be an important factor in explaining their distribution. The previously overlooked importance of these giant protists across the widest ecosystem on the planet changes our understanding of marine planktonic ecosystems. PMID:27096373

  15. Stacking sequence and interlayer coupling in few-layer graphene revealed by in situ imaging

    PubMed Central

    Wang, Zhu-Jun; Dong, Jichen; Cui, Yi; Eres, Gyula; Timpe, Olaf; Fu, Qiang; Ding, Feng; Schloegl, R.; Willinger, Marc-Georg

    2016-01-01

    In the transition from graphene to graphite, the addition of each individual graphene layer modifies the electronic structure and produces a different material with unique properties. Controlled growth of few-layer graphene is therefore of fundamental interest and will provide access to materials with engineered electronic structure. Here we combine isothermal growth and etching experiments with in situ scanning electron microscopy to reveal the stacking sequence and interlayer coupling strength in few-layer graphene. The observed layer-dependent etching rates reveal the relative strength of the graphene–graphene and graphene–substrate interaction and the resulting mode of adlayer growth. Scanning tunnelling microscopy and density functional theory calculations confirm a strong coupling between graphene edge atoms and platinum. Simulated etching confirms that etching can be viewed as reversed growth. This work demonstrates that real-time imaging under controlled atmosphere is a powerful method for designing synthesis protocols for sp2 carbon nanostructures in between graphene and graphite. PMID:27759024

  16. Elastic Wave Imaging of in-Situ Bio-Alterations in a Contaminated Aquifer

    NASA Astrophysics Data System (ADS)

    Jaiswal, P.; Raj, R.; Atekwana, E. A.; Briand, B.; Alam, I.

    2014-12-01

    We present a pioneering report on the utility of seismic methods in imaging bio-induced elastic property changes within a contaminated aquifer. To understand physical properties of contaminated soil, we acquired 48 meters long multichannel seismic profile over the Norman landfill leachate plume in Norman Oklahoma, USA. We estimated both the P- and S- wave velocities respectively using full-waveform inversion of the transmission and the ground-roll coda. The resulting S-wave model showed distinct velocity anomaly (~10% over background) within the water table fluctuation zone bounded by the historical minimum and maximum groundwater table. In comparison, the P-wave velocity anomaly within the same zone was negligible. The Environmental Scanning Electron Microscope (ESEM) images of samples from a core located along the seismic profile clearly shows presence of biofilms in the water table fluctuation zone and their absence both above and below the fluctuation zone. Elemental chemistry further indicates that the sediment composition throughout the core is fairly constant. We conclude that the velocity anomaly in S-wave is due to biofilms. As a next step, we develop mechanistic modeling to gain insights into the petro-physical behavior of biofilm-bearing sediments. Preliminary results suggest that a plausible model could be biofilms acting as contact cement between sediment grains. The biofilm cement can be placed in two ways - (i) superficial non-contact deposition on sediment grains, and (ii) deposition at grain contacts. Both models explain P- and S- wave velocity structure at reasonable (~5-10%) biofilm saturation and are equivocally supported by the ESEM images. Ongoing attenuation modeling from full-waveform inversion and its mechanistic realization, may be able to further discriminate between the two cement models. Our study strongly suggests that as opposed to the traditional P-wave seismic, S-wave acquisition and imaging can be a more powerful tool for in-situ

  17. Raman spectroscopy and coherent anti-Stokes Raman scattering imaging: prospective tools for monitoring skeletal cells and skeletal regeneration

    PubMed Central

    Moura, Catarina Costa; Tare, Rahul S.; Oreffo, Richard O. C.; Mahajan, Sumeet

    2016-01-01

    The use of skeletal stem cells (SSCs) for cell-based therapies is currently one of the most promising areas for skeletal disease treatment and skeletal tissue repair. The ability for controlled modification of SSCs could provide significant therapeutic potential in regenerative medicine, with the prospect to permanently repopulate a host with stem cells and their progeny. Currently, SSC differentiation into the stromal lineages of bone, fat and cartilage is assessed using different approaches that typically require cell fixation or lysis, which are invasive or even destructive. Raman spectroscopy and coherent anti-Stokes Raman scattering (CARS) microscopy present an exciting alternative for studying biological systems in their natural state, without any perturbation. Here we review the applications of Raman spectroscopy and CARS imaging in stem-cell research, and discuss the potential of these two techniques for evaluating SSCs, skeletal tissues and skeletal regeneration as an exemplar. PMID:27170652

  18. Seeing through Musculoskeletal Tissues: Improving In Situ Imaging of Bone and the Lacunar Canalicular System through Optical Clearing

    PubMed Central

    Berke, Ian M.; Miola, Joseph P.; David, Michael A.; Smith, Melanie K.; Price, Christopher

    2016-01-01

    In situ, cells of the musculoskeletal system reside within complex and often interconnected 3-D environments. Key to better understanding how 3-D tissue and cellular environments regulate musculoskeletal physiology, homeostasis, and health is the use of robust methodologies for directly visualizing cell-cell and cell-matrix architecture in situ. However, the use of standard optical imaging techniques is often of limited utility in deep imaging of intact musculoskeletal tissues due to the highly scattering nature of biological tissues. Drawing inspiration from recent developments in the deep-tissue imaging field, we describe the application of immersion based optical clearing techniques, which utilize the principle of refractive index (RI) matching between the clearing/mounting media and tissue under observation, to improve the deep, in situ imaging of musculoskeletal tissues. To date, few optical clearing techniques have been applied specifically to musculoskeletal tissues, and a systematic comparison of the clearing ability of optical clearing agents in musculoskeletal tissues has yet to be fully demonstrated. In this study we tested the ability of eight different aqueous and non-aqueous clearing agents, with RIs ranging from 1.45 to 1.56, to optically clear murine knee joints and cortical bone. We demonstrated and quantified the ability of these optical clearing agents to clear musculoskeletal tissues and improve both macro- and micro-scale imaging of musculoskeletal tissue across several imaging modalities (stereomicroscopy, spectroscopy, and one-, and two-photon confocal microscopy) and investigational techniques (dynamic bone labeling and en bloc tissue staining). Based upon these findings we believe that optical clearing, in combination with advanced imaging techniques, has the potential to complement classical musculoskeletal analysis techniques; opening the door for improved in situ investigation and quantification of musculoskeletal tissues. PMID:26930293

  19. Seeing through Musculoskeletal Tissues: Improving In Situ Imaging of Bone and the Lacunar Canalicular System through Optical Clearing.

    PubMed

    Berke, Ian M; Miola, Joseph P; David, Michael A; Smith, Melanie K; Price, Christopher

    2016-01-01

    In situ, cells of the musculoskeletal system reside within complex and often interconnected 3-D environments. Key to better understanding how 3-D tissue and cellular environments regulate musculoskeletal physiology, homeostasis, and health is the use of robust methodologies for directly visualizing cell-cell and cell-matrix architecture in situ. However, the use of standard optical imaging techniques is often of limited utility in deep imaging of intact musculoskeletal tissues due to the highly scattering nature of biological tissues. Drawing inspiration from recent developments in the deep-tissue imaging field, we describe the application of immersion based optical clearing techniques, which utilize the principle of refractive index (RI) matching between the clearing/mounting media and tissue under observation, to improve the deep, in situ imaging of musculoskeletal tissues. To date, few optical clearing techniques have been applied specifically to musculoskeletal tissues, and a systematic comparison of the clearing ability of optical clearing agents in musculoskeletal tissues has yet to be fully demonstrated. In this study we tested the ability of eight different aqueous and non-aqueous clearing agents, with RIs ranging from 1.45 to 1.56, to optically clear murine knee joints and cortical bone. We demonstrated and quantified the ability of these optical clearing agents to clear musculoskeletal tissues and improve both macro- and micro-scale imaging of musculoskeletal tissue across several imaging modalities (stereomicroscopy, spectroscopy, and one-, and two-photon confocal microscopy) and investigational techniques (dynamic bone labeling and en bloc tissue staining). Based upon these findings we believe that optical clearing, in combination with advanced imaging techniques, has the potential to complement classical musculoskeletal analysis techniques; opening the door for improved in situ investigation and quantification of musculoskeletal tissues.

  20. RECONSTRUCTING CORONAL MASS EJECTIONS WITH COORDINATED IMAGING AND IN SITU OBSERVATIONS: GLOBAL STRUCTURE, KINEMATICS, AND IMPLICATIONS FOR SPACE WEATHER FORECASTING

    SciTech Connect

    Liu Ying; Luhmann, Janet G.; Lin, Robert P.; Bale, Stuart D.; Thernisien, Arnaud; Vourlidas, Angelos; Davies, Jackie A.

    2010-10-20

    We reconstruct the global structure and kinematics of coronal mass ejections (CMEs) using coordinated imaging and in situ observations from multiple vantage points. A forward modeling technique, which assumes a rope-like morphology for CMEs, is used to determine the global structure (including orientation and propagation direction) from coronagraph observations. We reconstruct the corresponding structure from in situ measurements at 1 AU with the Grad-Shafranov method, which gives the flux-rope orientation, cross section, and a rough knowledge of the propagation direction. CME kinematics (propagation direction and radial distance) during the transit from the Sun to 1 AU are studied with a geometric triangulation technique, which provides an unambiguous association between solar observations and in situ signatures; a track fitting approach is invoked when data are available from only one spacecraft. We show how the results obtained from imaging and in situ data can be compared by applying these methods to the 2007 November 14-16 and 2008 December 12 CMEs. This merged imaging and in situ study shows important consequences and implications for CME research as well as space weather forecasting: (1) CME propagation directions can be determined to a relatively good precision as shown by the consistency between different methods; (2) the geometric triangulation technique shows a promising capability to link solar observations with corresponding in situ signatures at 1 AU and to predict CME arrival at the Earth; (3) the flux rope within CMEs, which has the most hazardous southward magnetic field, cannot be imaged at large distances due to expansion; (4) the flux-rope orientation derived from in situ measurements at 1 AU may have a large deviation from that determined by coronagraph image modeling; and (5) we find, for the first time, that CMEs undergo a westward migration with respect to the Sun-Earth line at their acceleration phase, which we suggest is a universal

  1. Investigation of drug distribution in tablets using surface enhanced Raman chemical imaging.

    PubMed

    Firkala, Tamás; Farkas, Attila; Vajna, Balázs; Farkas, István; Marosi, György

    2013-03-25

    This paper reports the first application of surface enhanced Raman chemical imaging on pharmaceutical tablets containing the active ingredient (API) in very low concentrations. Taking advantage of the extremely intensive Raman signals in the presence of silver colloids, image aquisition time was radically decreased. Moreover, the investigation of drug distribution below the detection limit of regular micro-Raman spectrometry was made feasible. The characteristics of different manufacturing technologies could be revealed at very low API concentrations by using chemometric methods for processing and evaluating the large number of varying spectra provided with this imaging method.

  2. Polarized Imaging Nephelometer for in situ airborne measurements of aerosol light scattering.

    PubMed

    Dolgos, Gergely; Martins, J Vanderlei

    2014-09-01

    Global satellite remote sensing of aerosols requires in situ measurements to enable the calibration and validation of algorithms. In order to improve our understanding of light scattering by aerosol particles, and to enable routine in situ airborne measurements of aerosol light scattering, we have developed an instrument, called the Polarized Imaging Nephelometer (PI-Neph). We designed and built the PI-Neph at the Laboratory for Aerosols, Clouds and Optics (LACO) of the University of Maryland, Baltimore County (UMBC). This portable instrument directly measures the ambient scattering coefficient and phase matrix elements of aerosols, in the field or onboard an aircraft. The measured phase matrix elements are the P(11), phase function, and P(12). Lasers illuminate the sampled ambient air and aerosol, and a wide field of view camera detects scattered light in a scattering angle range of 3° to 176°. The PI-Neph measures an ensemble of particles, supplying the relevant quantity for satellite remote sensing, as opposed to particle-by-particle measurements that have other applications. Comparisons with remote sensing measurements will have to consider aircraft inlet effects. The PI-Neph first measured at a laser wavelength of 532nm, and was first deployed successfully in 2011 aboard the B200 aircraft of NASA Langley during the Development and Evaluation of satellite ValidatiOn Tools by Experimenters (DEVOTE) project. In 2013, we upgraded the PI-Neph to measure at 473nm, 532nm, and 671nm nearly simultaneously. LACO has deployed the PI-Neph on a number of airborne field campaigns aboard three different NASA aircraft. This paper describes the PI-Neph measurement approach and validation by comparing measurements of artificial spherical aerosols with Mie theory. We provide estimates of calibration uncertainties, which show agreement with the small residuals between measurements of P(11) and -P(12)/P(11) and Mie theory. We demonstrate the capability of the PI-Neph to measure

  3. Polarized Imaging Nephelometer for in situ airborne measurements of aerosol light scattering.

    PubMed

    Dolgos, Gergely; Martins, J Vanderlei

    2014-09-01

    Global satellite remote sensing of aerosols requires in situ measurements to enable the calibration and validation of algorithms. In order to improve our understanding of light scattering by aerosol particles, and to enable routine in situ airborne measurements of aerosol light scattering, we have developed an instrument, called the Polarized Imaging Nephelometer (PI-Neph). We designed and built the PI-Neph at the Laboratory for Aerosols, Clouds and Optics (LACO) of the University of Maryland, Baltimore County (UMBC). This portable instrument directly measures the ambient scattering coefficient and phase matrix elements of aerosols, in the field or onboard an aircraft. The measured phase matrix elements are the P(11), phase function, and P(12). Lasers illuminate the sampled ambient air and aerosol, and a wide field of view camera detects scattered light in a scattering angle range of 3° to 176°. The PI-Neph measures an ensemble of particles, supplying the relevant quantity for satellite remote sensing, as opposed to particle-by-particle measurements that have other applications. Comparisons with remote sensing measurements will have to consider aircraft inlet effects. The PI-Neph first measured at a laser wavelength of 532nm, and was first deployed successfully in 2011 aboard the B200 aircraft of NASA Langley during the Development and Evaluation of satellite ValidatiOn Tools by Experimenters (DEVOTE) project. In 2013, we upgraded the PI-Neph to measure at 473nm, 532nm, and 671nm nearly simultaneously. LACO has deployed the PI-Neph on a number of airborne field campaigns aboard three different NASA aircraft. This paper describes the PI-Neph measurement approach and validation by comparing measurements of artificial spherical aerosols with Mie theory. We provide estimates of calibration uncertainties, which show agreement with the small residuals between measurements of P(11) and -P(12)/P(11) and Mie theory. We demonstrate the capability of the PI-Neph to measure

  4. Virtual spectral multiplexing for applications in in-situ imaging microscopy of transient phenomena

    NASA Astrophysics Data System (ADS)

    Deglint, Jason; Kazemzadeh, Farnoud; Shafiee, Mohammad Javad; Li, Edward; Khodadad, Iman; Saini, Simarjeet S.; Wong, Alexander; Clausi, David A.

    2015-09-01

    Multispectral sensing is specifically designed to provide quantitative spectral information about various materials or scenes. Using spectral information, various properties of objects can be measured and analysed. Microscopy, the observing and imaging of objects at the micron- or nano-scale, is one application where multispectral sensing can be advantageous, as many fields of science and research that use microscopy would benefit from observing a specimen in multiple wavelengths. Multispectral microscopy is available, but often requires the operator of the device to switch filters which is a labor intensive process. Furthermore, the need for filter switching makes such systems particularly limiting in cases where the sample contains live species that are constantly moving or exhibit transient phenomena. Direct methods for capturing multispectral data of a live sample simultaneously can also be challenging for microscopy applications as it requires an elaborate optical systems design which uses beamsplitters and a number of detectors proportional to the number of bands sought after. Such devices can therefore be quite costly to build and difficult to maintain, particularly for microscopy. In this paper, we present the concept of virtual spectral demultiplexing imaging (VSDI) microscopy for low-cost in-situ multispectral microscopy of transient phenomena. In VSDI microscopy, the spectral response of a color detector in the microscope is characterized and virtual spectral demultiplexing is performed on the simultaneously-acquired broadband detector measurements based on the developed spectral characterization model to produce microscopic imagery at multiple wavelengths. The proposed VSDI microscope was used to observe colorful nanowire arrays at various wavelengths simultaneously to illustrate its efficacy.

  5. Low-dose phase-based X-ray imaging techniques for in situ soft tissue engineering assessments.

    PubMed

    Izadifar, Zohreh; Honaramooz, Ali; Wiebe, Sheldon; Belev, George; Chen, Xiongbiao; Chapman, Dean

    2016-03-01

    In tissue engineering, non-invasive imaging of biomaterial scaffolds and tissues in living systems is essential to longitudinal animal studies for assessments without interrupting the repair process. Conventional X-ray imaging is inadequate for use in soft tissue engineering due to the limited absorption difference between the soft tissue and biomaterial scaffolds. X-ray phase-based imaging techniques that derive contrast from refraction or phase effects rather than absorption can provide the necessary contrast to see low-density biomaterial scaffolds and tissues in large living systems. This paper explores and compares three synchrotron phase-based X-ray imaging techniques-computed tomography (CT)-diffraction enhanced imaging (DEI), -analyzer based imaging (ABI), and -phase contrast imaging (PCI)-for visualization and characterization of low-density biomaterial scaffolds and tissues in situ for non-invasive soft tissue engineering assessments. Intact pig joints implanted with polycaprolactone scaffolds were used as the model to assess and compare the imaging techniques in terms of different qualitative and quantitative criteria. For long-term in vivo live animal imaging, different strategies for reducing the imaging radiation dose and scan time-reduced number of CT projections, region of interest, and low resolution imaging-were examined with the presented phase-based imaging techniques. The results demonstrated promising capabilities of the phase-based techniques for visualization of biomaterial scaffolds and soft tissues in situ. The low-dose imaging strategies were illustrated effective for reducing the radiation dose to levels appropriate for live animal imaging. The comparison among the imaging techniques suggested that CT-DEI has the highest efficiency in retaining image contrast at considerably low radiation doses.

  6. Ad-hoc surface-enhanced Raman spectroscopy methodologies for the detection of artist dyestuffs: thin layer chromatography-surface enhanced Raman spectroscopy and in situ on the fiber analysis.

    PubMed

    Brosseau, Christa L; Gambardella, Alessa; Casadio, Francesca; Grzywacz, Cecily M; Wouters, Jan; Van Duyne, Richard P

    2009-04-15

    Tailored ad-hoc methods must be developed for successful identification of minute amounts of natural dyes on works of art using Surface-Enhanced Raman Spectroscopy (SERS). This article details two of these successful approaches using silver film over nanosphere (AgFON) substrates and silica gel coupled with citrate-reduced Ag colloids. The latter substrate functions as the test system for the coupling of thin-layer chromatography and SERS (TLC-SERS), which has been used in the current research to separate and characterize a mixture of several artists' dyes. The poor limit of detection of TLC is overcome by coupling with SERS, and dyes which co-elute to nearly the same spot can be distinguished from each other. In addition, in situ extractionless non-hydrolysis SERS was used to analyze dyed reference fibers, as well as historical textile fibers. Colorants such as alizarin, purpurin, carminic acid, lac dye, crocin, and Cape jasmine were thus successfully identified. PMID:19317457

  7. In situ single molecule imaging of cell membranes: linking basic nanotechniques to cell biology, immunology and medicine.

    PubMed

    Pi, Jiang; Jin, Hua; Yang, Fen; Chen, Zheng W; Cai, Jiye

    2014-11-01

    The cell membrane, which consists of a viscous phospholipid bilayer, different kinds of proteins and various nano/micrometer-sized domains, plays a very important role in ensuring the stability of the intracellular environment and the order of cellular signal transductions. Exploring the precise cell membrane structure and detailed functions of the biomolecules in a cell membrane would be helpful to understand the underlying mechanisms involved in cell membrane signal transductions, which could further benefit research into cell biology, immunology and medicine. The detection of membrane biomolecules at the single molecule level can provide some subtle information about the molecular structure and the functions of the cell membrane. In particular, information obtained about the molecular mechanisms and other information at the single molecule level are significantly different from that detected from a large amount of biomolecules at the large-scale through traditional techniques, and can thus provide a novel perspective for the study of cell membrane structures and functions. However, the precise investigations of membrane biomolecules prompts researchers to explore cell membranes at the single molecule level by the use of in situ imaging methods, as the exact conformation and functions of biomolecules are highly controlled by the native cellular environment. Recently, the in situ single molecule imaging of cell membranes has attracted increasing attention from cell biologists and immunologists. The size of biomolecules and their clusters on the cell surface are set at the nanoscale, which makes it mandatory to use high- and super-resolution imaging techniques to realize the in situ single molecule imaging of cell membranes. In the past few decades, some amazing imaging techniques and instruments with super resolution have been widely developed for molecule imaging, which can also be further employed for the in situ single molecule imaging of cell membranes. In

  8. In situ single molecule imaging of cell membranes: linking basic nanotechniques to cell biology, immunology and medicine

    NASA Astrophysics Data System (ADS)

    Pi, Jiang; Jin, Hua; Yang, Fen; Chen, Zheng W.; Cai, Jiye

    2014-10-01

    The cell membrane, which consists of a viscous phospholipid bilayer, different kinds of proteins and various nano/micrometer-sized domains, plays a very important role in ensuring the stability of the intracellular environment and the order of cellular signal transductions. Exploring the precise cell membrane structure and detailed functions of the biomolecules in a cell membrane would be helpful to understand the underlying mechanisms involved in cell membrane signal transductions, which could further benefit research into cell biology, immunology and medicine. The detection of membrane biomolecules at the single molecule level can provide some subtle information about the molecular structure and the functions of the cell membrane. In particular, information obtained about the molecular mechanisms and other information at the single molecule level are significantly different from that detected from a large amount of biomolecules at the large-scale through traditional techniques, and can thus provide a novel perspective for the study of cell membrane structures and functions. However, the precise investigations of membrane biomolecules prompts researchers to explore cell membranes at the single molecule level by the use of in situ imaging methods, as the exact conformation and functions of biomolecules are highly controlled by the native cellular environment. Recently, the in situ single molecule imaging of cell membranes has attracted increasing attention from cell biologists and immunologists. The size of biomolecules and their clusters on the cell surface are set at the nanoscale, which makes it mandatory to use high- and super-resolution imaging techniques to realize the in situ single molecule imaging of cell membranes. In the past few decades, some amazing imaging techniques and instruments with super resolution have been widely developed for molecule imaging, which can also be further employed for the in situ single molecule imaging of cell membranes. In

  9. Novel probe for laser-induced breakdown spectroscopy and Raman measurements using an imaging optical fiber

    SciTech Connect

    Marquardt, B.J.; Stratis, D.N.; Angel, S.M.; Cremers, D.A.

    1998-09-01

    A fiber-optic probe designed for remote laser-induced breakdown spectroscopy (LIBS), Raman spectroscopy, and Raman imaging has been developed for the microanalysis of solid samples. The probe incorporates both single-strand optical fibers and an image guide and allows atomic emission and Raman analysis of any spot on a solid sample within a 5 mm diameter field of view. The real-time sample imaging aspects of the probe are demonstrated by measuring LIBS spectra from different regions of a granite sample and by measuring the Raman spectra of individual TiO{sub 2} and Sr(NO{sub 3}){sub 2} particles on a soil substrate. The ability to obtain remote Raman images of the TiO{sub 2} and Sr(NO{sub 3}){sub 2} particles on the soil substrate is also demonstrated. In this paper we discuss the design and implementation of the fiber-optic probe for obtaining LIBS spectra, Raman spectra, and Raman images. {copyright} {ital 1998} {ital Society for Applied Spectroscopy}

  10. Reaching millikelvin resolution in Raman distributed temperature sensing using image processing

    NASA Astrophysics Data System (ADS)

    Soto, Marcelo A.; Ramírez, Jaime A.; Thévenaz, Luc

    2016-05-01

    Image processing is proposed and experimentally demonstrated to improve the capabilities of Raman distributed optical fibre sensors. The here reported technique consists in stacking consecutive one-dimensional Raman Stokes and anti-Stokes traces in two-dimensional data arrays (one for each Raman component), which are then processed by an image denoising algorithm. Owing to the high level of correlation between consecutive measurements in conventional Raman sensing, it is experimentally demonstrated that this newly-proposed two-dimensional denoising approach provides a significant signal-to-noise ratio improvement, which in this case reaches 13.6 dB with no hardware modification to the conventional set-up. Experimental results demonstrate Raman distributed sensing with a remarkably enhanced temperature resolution of 4 mK at 9 km distance, which is obtained with 2 m spatial resolution and a short acquisition time of 35 s.

  11. Diagnostic Imaging in Flames with Instantaneous Planar Coherent Raman Spectroscopy.

    PubMed

    Bohlin, A; Kliewer, C J

    2014-04-01

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

  12. The replacement of Celestine (SrSO4) by Strontianite (SrCO3) studied in situ, spatially resolved, and real-time by Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Sulzbach, Michael; Geisler, Thorsten

    2015-04-01

    The replacement reaction of celestine (SrSO4) by strontianite (SrCO3) is one of the most common ways to obtain pure strontianite that is an important industrial reagent. Thus, the replacement reaction has been studied extensively over the past decades. In this work the replacement serves as a model system to study solid-fluid reactions in particular, the behavior of oxygen isotopes during the reaction. Measurements of isotopically enriched compounds using Raman spectroscopy showed that oxo-anion groups perform localized vibrations with distinct frequencies. These vibrations reflect the oxygen-based isotopologues of the oxo-anion molecule and the relative intensities of these bands are proportional to the isotopologue fractions in the molecule species that allows the precise quantification of its isotope composition. Therefore, Raman spectroscopy provides us with a tool to monitor the behavior of oxygen isotopes at reaction interfaces and in the fluid. Combining a confocal Raman spectrometer with an in-house-made Teflon© fluid cell even enables spatially resolved, in situ, and real-time measurements. Two different experimental setups were used to obtain general information about the replacement kinetics using isotopically natural solutions. The first experimental setup consisted of an in-house-made Teflon© fluid cell (with an internal heating system) filled with a 1M Na2CO3 solution and an equimolar amount of celestine powder. Grain sizes ranged between 63 and 125 μm and experimental temperatures were 35° C, 40° C, 45° C, and 50° C. At the start of the experiments the aqueous ν1(CO3) band could be observed at 1065 cm-1 that lost intensity over the course of the reaction. Complementary, the aqueous sulfate ν1(SO4) band at 981 cm-1grows in intensity. From the relative changes between these bands we derived the reaction rates and the activation energy. The second experimental setup also consisted of an in-house-made Teflon© fluid cell (without heating system

  13. Comparison of CME/Shock Propagation Models with Heliospheric Imaging and In Situ Observations

    NASA Astrophysics Data System (ADS)

    Zhao, Xinhua; Liu, Ying D.; Inhester, Bernd; Feng, Xueshang; Wiegelmann, Thomas; Lu, Lei

    2016-10-01

    The prediction of the arrival time for fast coronal mass ejections (CMEs) and their associated shocks is highly desirable in space weather studies. In this paper, we use two shock propagation models, i.e., Data Guided Shock Time Of Arrival (DGSTOA) and Data Guided Shock Propagation Model (DGSPM), to predict the kinematical evolution of interplanetary shocks associated with fast CMEs. DGSTOA is based on the similarity theory of shock waves in the solar wind reference frame, and DGSPM is based on the non-similarity theory in the stationary reference frame. The inputs are the kinematics of the CME front at the maximum speed moment obtained from the geometric triangulation method applied to STEREO imaging observations together with the Harmonic Mean approximation. The outputs provide the subsequent propagation of the associated shock. We apply these models to the CMEs on 2012 January 19, January 23, and March 7. We find that the shock models predict reasonably well the shock’s propagation after the impulsive acceleration. The shock’s arrival time and local propagation speed at Earth predicted by these models are consistent with in situ measurements of WIND. We also employ the Drag-Based Model (DBM) as a comparison, and find that it predicts a steeper deceleration than the shock models after the rapid deceleration phase. The predictions of DBM at 1 au agree with the following ICME or sheath structure, not the preceding shock. These results demonstrate the applicability of the shock models used here for future arrival time prediction of interplanetary shocks associated with fast CMEs.

  14. Imaging of multiple mRNA targets using quantum dot based in situ hybridization and spectral deconvolution in clinical biopsies

    SciTech Connect

    Tholouli, Eleni; Hoyland, Judith A.; Di Vizio, Dolores; O'Connell, Fionnuala; MacDermott, Sarah A.; Twomey, David; Levenson, Richard; Yin, John A. Liu; Golub, Todd R.; Loda, Massimo; Byers, Richard . E-mail: r.byers@manchester.ac.uk

    2006-09-22

    Gene expression mapping using microarray analysis has identified useful gene signatures for predicting outcome. However, little of this has been translated into clinically effective diagnostic tools as microarrays require high quality fresh-frozen tissue samples. We describe a methodology of multiplexed in situ hybridization (ISH) using a novel combination of quantum dot (QD)-labeled oligonucleotide probes and spectral imaging analysis in routinely processed, formalin-fixed paraffin embedded human biopsies. The conditions for QD-ISH were optimized using a poly d(T) oligonucleotide in decalcified bone marrow samples. Single and multiplex QD-ISH was performed in samples with acute leukemia and follicular lymphoma using oligonucleotide probes for myeloperoxidase, bcl-2, survivin, and XIAP. Spectral imaging was used for post hybridization tissue analysis, enabling separation of spatially colocalized signals. The method allows quantitative characterization of multiple gene expression using non-bleaching fluorochromes. This is expected to facilitate multiplex in situ transcript detection in routinely processed human clinical tissue.

  15. Subcellular chemical and morphological analysis by stimulated Raman scattering microscopy and image analysis techniques.

    PubMed

    D'Arco, Annalisa; Brancati, Nadia; Ferrara, Maria Antonietta; Indolfi, Maurizio; Frucci, Maria; Sirleto, Luigi

    2016-05-01

    The visualization of heterogeneous morphology, segmentation and quantification of image features is a crucial point for nonlinear optics microscopy applications, spanning from imaging of living cells or tissues to biomedical diagnostic. In this paper, a methodology combining stimulated Raman scattering microscopy and image analysis technique is presented. The basic idea is to join the potential of vibrational contrast of stimulated Raman scattering and the strength of imaging analysis technique in order to delineate subcellular morphology with chemical specificity. Validation tests on label free imaging of polystyrene-beads and of adipocyte cells are reported and discussed. PMID:27231626

  16. Subcellular chemical and morphological analysis by stimulated Raman scattering microscopy and image analysis techniques

    PubMed Central

    D’Arco, Annalisa; Brancati, Nadia; Ferrara, Maria Antonietta; Indolfi, Maurizio; Frucci, Maria; Sirleto, Luigi

    2016-01-01

    The visualization of heterogeneous morphology, segmentation and quantification of image features is a crucial point for nonlinear optics microscopy applications, spanning from imaging of living cells or tissues to biomedical diagnostic. In this paper, a methodology combining stimulated Raman scattering microscopy and image analysis technique is presented. The basic idea is to join the potential of vibrational contrast of stimulated Raman scattering and the strength of imaging analysis technique in order to delineate subcellular morphology with chemical specificity. Validation tests on label free imaging of polystyrene-beads and of adipocyte cells are reported and discussed. PMID:27231626

  17. Subcellular chemical and morphological analysis by stimulated Raman scattering microscopy and image analysis techniques.

    PubMed

    D'Arco, Annalisa; Brancati, Nadia; Ferrara, Maria Antonietta; Indolfi, Maurizio; Frucci, Maria; Sirleto, Luigi

    2016-05-01

    The visualization of heterogeneous morphology, segmentation and quantification of image features is a crucial point for nonlinear optics microscopy applications, spanning from imaging of living cells or tissues to biomedical diagnostic. In this paper, a methodology combining stimulated Raman scattering microscopy and image analysis technique is presented. The basic idea is to join the potential of vibrational contrast of stimulated Raman scattering and the strength of imaging analysis technique in order to delineate subcellular morphology with chemical specificity. Validation tests on label free imaging of polystyrene-beads and of adipocyte cells are reported and discussed.

  18. Alkyne-tag Raman imaging of bio-active small molecules in live cells

    NASA Astrophysics Data System (ADS)

    Ando, Jun; Palonpon, Almar F.; Yamakoshi, Hiroyuki; Dodo, Kosuke; Kawata, Satoshi; Sodeoka, Mikiko; Fujita, Katsumasa

    2015-12-01

    Raman microscopy is useful for molecular imaging and analysis of biological specimens. Here, we used alkyne containing a carbon-carbon triple bond as a Raman tag for observing small molecules in live cells. Alkyne tags can maintain original properties of target molecules with providing high chemical specificity owing to its distinct peak in a Raman-silent window of biomolecules. For demonstrations, alkyne-tagged thymidine and coenzyme Q analogue in live cells were visualized with high-spatial resolution. We extended the application of alkyne-tag imaging to visualize cell organelles and specific lipid components in artificial monolayer membranes.

  19. Remote and in situ detection of environmental and biological signatures: ground-truthing hyperspectral imaging for planetary exploration

    NASA Astrophysics Data System (ADS)

    Storrie-Lombardi, Michael C.; Brown, Adrian J.; Walter, Malcolm R.

    2004-11-01

    Proposed geochemical histories for the evolution of Mars offer the possibility that the planet may have experienced conditions remarkably similar to those faced by life on Earth during Archean and Proterozoic eons. For almost two billion years microbial mat communities dominated by photosynthetic cyanobacteria were the dominant life forms on Earth. Descendents of these complex communities and the fossil remnants of their ancestors can be found today in Northwestern Australia. These sites offer a unique testing ground for developing integrated remote and in situ methods for identifying sites of geobiological interest during exploration of Mars, the Jovian or Saturnian satellites, or neighboring extra-solar planetary systems. We are currently performing remote and in situ analyses of spectral and image data from the Trendall locality of NW Australia, an area rich in geobiological targets including hydrothermally altered basalts, fossil stromatolites and pillow basalts. We discuss the early results of employing cluster analysis, Bayesian probabilistic estimators, and complexity analysis techniques to analyze remote and in situ photographic and spectral data. The techniques presented offer a systematic methodology for both the remote selection of landing sites most likely to contain targets of geobiological interest and the in situ identification of aqueous or biologically altered samples.

  20. Quantitative vibrational imaging by hyperspectral stimulated Raman scattering microscopy and multivariate curve resolution analysis.

    PubMed

    Zhang, Delong; Wang, Ping; Slipchenko, Mikhail N; Ben-Amotz, Dor; Weiner, Andrew M; Cheng, Ji-Xin

    2013-01-01

    Spectroscopic imaging has been an increasingly critical approach for unveiling specific molecules in biological environments. Toward this goal, we demonstrate hyperspectral stimulated Raman loss (SRL) imaging by intrapulse spectral scanning through a femtosecond pulse shaper. The hyperspectral stack of SRL images is further analyzed by a multivariate curve resolution (MCR) method to reconstruct quantitative concentration images for each individual component and retrieve the corresponding vibrational Raman spectra. Using these methods, we demonstrate quantitative mapping of dimethyl sulfoxide concentration in aqueous solutions and in fat tissue. Moreover, MCR is performed on SRL images of breast cancer cells to generate maps of principal chemical components along with their respective vibrational spectra. These results show the great capability and potential of hyperspectral SRL microscopy for quantitative imaging of complicated biomolecule mixtures through resolving overlapped Raman bands.

  1. Raman imaging to study structural and chemical features of the dentin enamel junction

    NASA Astrophysics Data System (ADS)

    Alebrahim, M. Anwar; Krafft, C.; Popp, J.

    2015-10-01

    The structure and chemical features of the human dentin enamel junction (DEJ) were characterized using Raman spectroscopic imaging. Slices were prepared from 10 German, and 10 Turkish teeth. Raman images were collected at 785 nm excitation and the average Raman spectra were calculated for analysis. Univariate and multivariate spectral analysis were applied for investigation. Raman images were obtained based on the intensity ratios of CH at 1450 cm-1 (matrix) to phosphate at 960 cm-1 (mineral), and carbonate to phosphate (1070/960) ratios. Different algorithms (HCA, K-means cluster and VCA) also used to study the DEJ. The obtained results showed that the width of DEJ is about 5 pm related to univariate method while it varies from 6 to 12 μm based on multivariate spectral technique. Both spectral analyses showed increasing in carbonate content inside the DEJ compared to the dentin, and the amide I (collagen) peak in dentin spectra is higher than DEJ spectra peak.

  2. 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.

  3. Preclinical evaluation of Raman nanoparticle biodistribution for their potential use in clinical endoscopy imaging.

    PubMed

    Zavaleta, Cristina L; Hartman, Keith B; Miao, Zheng; James, Michelle L; Kempen, Paul; Thakor, Avnesh S; Nielsen, Carsten H; Sinclair, Robert; Cheng, Zhen; Gambhir, Sanjiv S

    2011-08-01

    Raman imaging offers unsurpassed sensitivity and multiplexing capabilities. However, its limited depth of light penetration makes direct clinical translation challenging. Therefore, a more suitable way to harness its attributes in a clinical setting would be to couple Raman spectroscopy with endoscopy. The use of an accessory Raman endoscope in conjunction with topically administered tumor-targeting Raman nanoparticles during a routine colonoscopy could offer a new way to sensitively detect dysplastic lesions while circumventing Raman's limited depth of penetration and avoiding systemic toxicity. In this study, the natural biodistribution of gold surface-enhanced Raman scattering (SERS) nanoparticles is evaluated by radiolabeling them with (64) Cu and imaging their localization over time using micropositron emission tomography (PET). Mice are injected either intravenously (IV) or intrarectally (IR) with approximately 100 microcuries (μCi) (3.7 megabecquerel (MBq)) of (64) Cu-SERS nanoparticles and imaged with microPET at various time points post injection. Quantitative biodistribution data are obtained as % injected dose per gram (%ID g(-1)) from each organ, and the results correlate well with the corresponding microPET images, revealing that IV-injected mice have significantly higher uptake (p < 0.05) in the liver (5 h = 8.96% ID g(-1); 24 h = 8.27% ID g(-1)) than IR-injected mice (5 h = 0.09% ID g(-1); 24 h = 0.08% ID g(-1)). IR-injected mice show localized uptake in the large intestine (5 h = 10.37% ID g(-1); 24 h = 0.42% ID g(-1)) with minimal uptake in other organs. Raman imaging of excised tissues correlate well with biodistribution data. These results suggest that the topical application of SERS nanoparticles in the mouse colon appears to minimize their systemic distribution, thus avoiding potential toxicity and supporting the clinical translation of Raman spectroscopy as an endoscopic imaging tool.

  4. The development of a wide-field, high-resolution UV Raman hyperspectral imager

    NASA Astrophysics Data System (ADS)

    Gomer, Nathaniel R.; Nelson, Matthew P.; Angel, S. M.

    2015-05-01

    Raman spectroscopy is a valuable tool for the investigation and analysis of explosive and biological analytes because it provides a unique molecular fingerprint that allows for unambiguous target identification. Raman can be advantageous when utilized with deep UV excitation, but typical deep UV Raman systems have numerous limitations that hinder their performance and make their potential integration onto a field portable platform difficult. These systems typically offer very low throughput, are physically large and heavy, and can only probe an area the size of a tightly focused laser, severely diminishing the ability of the system to investigate large areas efficiently. The majority of these limitations are directly related to a system's spectrometer, which is typically dispersive grating based and requires a very narrow slit width and long focal length optics to achieve high spectral resolution. To address these shortcomings, ChemImage Sensor Systems (CISS), teaming with the University of South Carolina, are developing a revolutionary wide-field Raman hyperspectral imaging system capable of providing wide-area, high resolution measurements with greatly increased throughput in a small form factor, which would revolutionize the way Raman is conducted and applied. The innovation couples a spatial heterodyne spectrometer (SHS), a novel slit-less spectrometer that operates similar to Michelson interferometer, with a fiber array spectral translator (FAST) fiber array, a two-dimensional imaging fiber for hyperspectral imagery. This combination of technologies creates a novel wide-field, high throughput Raman hyperspectral imager capable of yielding very high spectral resolution measurements using defocused excitation, giving the system a greater area coverage and faster search rate than traditional Raman systems. This paper will focus on the need for an innovative UV Raman system, provide an overview of spatial heterodyne Raman spectroscopy, and discuss the development

  5. Lock-in-detection-free line-scan stimulated Raman scattering microscopy for near video-rate Raman imaging.

    PubMed

    Wang, Zi; Zheng, Wei; Huang, Zhiwei

    2016-09-01

    We report on the development of a unique lock-in-detection-free line-scan stimulated Raman scattering microscopy technique based on a linear detector with a large full well capacity controlled by a field-programmable gate array (FPGA) for near video-rate Raman imaging. With the use of parallel excitation and detection scheme, the line-scan SRS imaging at 20 frames per second can be acquired with a ∼5-fold lower excitation power density, compared to conventional point-scan SRS imaging. The rapid data communication between the FPGA and the linear detector allows a high line-scanning rate to boost the SRS imaging speed without the need for lock-in detection. We demonstrate this lock-in-detection-free line-scan SRS imaging technique using the 0.5 μm polystyrene and 1.0 μm poly(methyl methacrylate) beads mixed in water, as well as living gastric cancer cells.

  6. Lock-in-detection-free line-scan stimulated Raman scattering microscopy for near video-rate Raman imaging.

    PubMed

    Wang, Zi; Zheng, Wei; Huang, Zhiwei

    2016-09-01

    We report on the development of a unique lock-in-detection-free line-scan stimulated Raman scattering microscopy technique based on a linear detector with a large full well capacity controlled by a field-programmable gate array (FPGA) for near video-rate Raman imaging. With the use of parallel excitation and detection scheme, the line-scan SRS imaging at 20 frames per second can be acquired with a ∼5-fold lower excitation power density, compared to conventional point-scan SRS imaging. The rapid data communication between the FPGA and the linear detector allows a high line-scanning rate to boost the SRS imaging speed without the need for lock-in detection. We demonstrate this lock-in-detection-free line-scan SRS imaging technique using the 0.5 μm polystyrene and 1.0 μm poly(methyl methacrylate) beads mixed in water, as well as living gastric cancer cells. PMID:27607947

  7. Quantitative Imaging and In Situ Concentration Measurements of Quantum Dot Nanomaterials in Variably Saturated Porous Media

    DOE PAGES

    Uyuşur, Burcu; Snee, Preston T.; Li, Chunyan; Darnault, Christophe J. G.

    2016-01-01

    Knowledge of the fate and transport of nanoparticles in the subsurface environment is limited, as techniques to monitor and visualize the transport and distribution of nanoparticles in porous media and measure their in situ concentrations are lacking. To address these issues, we have developed a light transmission and fluorescence method to visualize and measure in situ concentrations of quantum dot (QD) nanoparticles in variably saturated environments. Calibration cells filled with sand as porous medium and various known water saturation levels and QD concentrations were prepared. By measuring the intensity of the light transmitted through porous media exposed to fluorescent lightmore » and by measuring the hue of the light emitted by the QDs under UV light exposure, we obtained simultaneously in situ measurements of water saturation and QD nanoparticle concentrations with high spatial and temporal resolutions. Water saturation was directly proportional to the light intensity. A linear relationship was observed between hue-intensity ratio values and QD concentrations for constant water saturation levels. The advantages and limitations of the light transmission and fluorescence method as well as its implications for visualizing and measuring in situ concentrations of QDs nanoparticles in the subsurface environment are discussed.« less

  8. Dual-channel in-situ optical imaging system for quantifying lipid uptake and lymphatic pump function

    NASA Astrophysics Data System (ADS)

    Kassis, Timothy; Kohan, Alison B.; Weiler, Michael J.; Nipper, Matthew E.; Cornelius, Rachel; Tso, Patrick; Brandon Dixon, J.

    2012-08-01

    Nearly all dietary lipids are transported from the intestine to venous circulation through the lymphatic system, yet the mechanisms that regulate this process remain unclear. Elucidating the mechanisms involved in the functional response of lymphatics to changes in lipid load would provide valuable insight into recent implications of lymphatic dysfunction in lipid related diseases. Therefore, we sought to develop an in situ imaging system to quantify and correlate lymphatic function as it relates to lipid transport. The imaging platform provides the capability of dual-channel imaging of both high-speed bright-field video and fluorescence simultaneously. Utilizing post-acquisition image processing algorithms, we can quantify correlations between vessel pump function, lymph flow, and lipid concentration of mesenteric lymphatic vessels in situ. All image analysis is automated with customized LabVIEW virtual instruments; local flow is measured through lymphocyte velocity tracking, vessel contraction through measurements of the vessel wall displacement, and lipid uptake through fluorescence intensity tracking of an orally administered fluorescently labelled fatty acid analogue, BODIPY FL C16. This system will prove to be an invaluable tool for scientists studying intestinal lymphatic function in health and disease, and those investigating strategies for targeting the lymphatics with orally delivered drugs to avoid first pass metabolism.

  9. Dual-channel in-situ optical imaging system for quantifying lipid uptake and lymphatic pump function

    PubMed Central

    Kassis, Timothy; Kohan, Alison B.; Weiler, Michael J.; Nipper, Matthew E.; Cornelius, Rachel; Tso, Patrick

    2012-01-01

    Abstract. Nearly all dietary lipids are transported from the intestine to venous circulation through the lymphatic system, yet the mechanisms that regulate this process remain unclear. Elucidating the mechanisms involved in the functional response of lymphatics to changes in lipid load would provide valuable insight into recent implications of lymphatic dysfunction in lipid related diseases. Therefore, we sought to develop an in situ imaging system to quantify and correlate lymphatic function as it relates to lipid transport. The imaging platform provides the capability of dual-channel imaging of both high-speed bright-field video and fluorescence simultaneously. Utilizing post-acquisition image processing algorithms, we can quantify correlations between vessel pump function, lymph flow, and lipid concentration of mesenteric lymphatic vessels in situ. All image analysis is automated with customized LabVIEW virtual instruments; local flow is measured through lymphocyte velocity tracking, vessel contraction through measurements of the vessel wall displacement, and lipid uptake through fluorescence intensity tracking of an orally administered fluorescently labelled fatty acid analogue, BODIPY FL C16. This system will prove to be an invaluable tool for scientists studying intestinal lymphatic function in health and disease, and those investigating strategies for targeting the lymphatics with orally delivered drugs to avoid first pass metabolism. PMID:23224192

  10. Microstructural characterization of in situ MXCT images of high density foams under large strains

    SciTech Connect

    Patterson, Brian M; Gleiman, Seth; Marks, Trevor G; Milstein, Fredrick

    2009-01-01

    relative-density of the foam; however, there exists a gap in the understanding of how the foam microstructure affects the mechanical response of the foam. This is due in large part to the difficulty of characterizing foam structures in 3D, especially foams of high relative-density. Most elastomeric foams are manufactured by the introduction of a gas into a cross-linking polymer. The developing foam microstructure has a complex dependence on the polymer viscosity and rate of polymerization, resulting in a randomly arranged pore structure with a large distribution of pore sizes. One approach is to characterize foam microstructures solely in terms of the cross-sectional shape and vector arrangement of the strut matrix, since it is this matrix that supports the stresses upon loading of the foam; yet as the density of a foam is increased, the very definition of what constitutes a strut brakes down. Another, perhaps easier to visualize, characterization of foam microstructure can come from a description of the pore shape and arrangement. Given the random nature of the microstructures of blown foam, both approaches are useful and valid. This paper describes our work aimed at linking the mechanical response and microstructural evolution of high relative-density foam as it undergoes large deformation. This work consists of several inter-related parts, including (i) measuring the compressive stress-strain response, as illustrated in Fig. 1, (ii) obtaining in situ micro X-ray computed tomography (MXCT) images of high relative-density foams undergoing large strains, and (iii) developing mathematical, computer aided, methodologies to perform image analysis and calculations of parameters that characterize the pores and struts. By using MXCT, a non-invasive technique for imaging the internal structure of materials, we are able to observe, internally, individual struts and pores as they undergo large deformation. Here we describe our computer aided image analysis methodologies and present

  11. Understanding catalyst behavior during in situ heating through simultaneous secondary and transmitted electron imaging

    SciTech Connect

    Howe, Jane Y.; Allard, Jr., Lawrence Frederick; Demers, Hendrix; Bigelow, Wilbur C.; Steven H. Overbury

    2014-11-14

    In situ heating study via a simultaneous secondary electron (SE) and transmitted electron (TE) microscopy is extremely insightful because information from the surface (SE) and bulk (TE) can be readily obtained. The leached Au/Fe2O3 catalyst has voids on the surface of Fe2O3. Upon heating to 500 °C, voids shrank and disappeared, while internal Au species diffused to the surface to form new nanoparticles. Heating in vacuum reduced Fe2O3 to Fe3O4. Heating at 700 °C caused coalescence and growth of Au particles and formation of faceted Fe3O4 surfaces. We achieved 1.1 nm resolution in SE imaging during in situ heating.

  12. A novel non-imaging optics based Raman spectroscopy device for transdermal blood analyte measurement

    PubMed Central

    Kong, Chae-Ryon; Barman, Ishan; Dingari, Narahara Chari; Kang, Jeon Woong; Galindo, Luis; Dasari, Ramachandra R.; Feld, Michael S.

    2011-01-01

    Due to its high chemical specificity, Raman spectroscopy has been considered to be a promising technique for non-invasive disease diagnosis. However, during Raman excitation, less than one out of a million photons undergo spontaneous Raman scattering and such weakness in Raman scattered light often require highly efficient collection of Raman scattered light for the analysis of biological tissues. We present a novel non-imaging optics based portable Raman spectroscopy instrument designed for enhanced light collection. While the instrument was demonstrated on transdermal blood glucose measurement, it can also be used for detection of other clinically relevant blood analytes such as creatinine, urea and cholesterol, as well as other tissue diagnosis applications. For enhanced light collection, a non-imaging optical element called compound hyperbolic concentrator (CHC) converts the wide angular range of scattered photons (numerical aperture (NA) of 1.0) from the tissue into a limited range of angles accommodated by the acceptance angles of the collection system (e.g., an optical fiber with NA of 0.22). A CHC enables collimation of scattered light directions to within extremely narrow range of angles while also maintaining practical physical dimensions. Such a design allows for the development of a very efficient and compact spectroscopy system for analyzing highly scattering biological tissues. Using the CHC-based portable Raman instrument in a clinical research setting, we demonstrate successful transdermal blood glucose predictions in human subjects undergoing oral glucose tolerance tests. PMID:22125761

  13. Direct imaging of molecular symmetry by coherent anti-stokes Raman scattering

    PubMed Central

    Cleff, Carsten; Gasecka, Alicja; Ferrand, Patrick; Rigneault, Hervé; Brasselet, Sophie; Duboisset, Julien

    2016-01-01

    Nonlinear optical methods, such as coherent anti-Stokes Raman scattering and stimulated Raman scattering, are able to perform label-free imaging, with chemical bonds specificity. Here we demonstrate that the use of circularly polarized light allows to retrieve not only the chemical nature but also the symmetry of the probed sample, in a single measurement. Our symmetry-resolved scheme offers simple access to the local organization of vibrational bonds and as a result provides enhanced image contrast for anisotropic samples, as well as an improved chemical selectivity. We quantify the local organization of vibrational bonds on crystalline and biological samples, thus providing information not accessible by spontaneous Raman and stimulated Raman scattering techniques. This work stands for a symmetry-resolved contrast in vibrational microscopy, with potential application in biological diagnostic. PMID:27189667

  14. In situ nondestructive imaging of functional pigments in Micro-Tom tomato fruits by multi spectral imaging based on Wiener estimation method

    NASA Astrophysics Data System (ADS)

    Nishidate, Izumi; Ooe, Shintaro; Todoroki, Shinsuke; Asamizu, Erika

    2013-05-01

    To evaluate the functional pigments in the tomato fruits nondestructively, we propose a method based on the multispectral diffuse reflectance images estimated by the Wiener estimation for a digital RGB image. Each pixel of the multispectral image is converted to the absorbance spectrum and then analyzed by the multiple regression analysis to visualize the contents of chlorophyll a, lycopene and β-carotene. The result confirms the feasibility of the method for in situ imaging of chlorophyll a, β-carotene and lycopene in the tomato fruits.

  15. Simultaneous laser-induced fluorescence and Raman imaging inside a hydrogen engine.

    PubMed

    Engel, Sascha Ronald; Koch, Peter; Braeuer, Andreas; Leipertz, Alfred

    2009-12-10

    We report on the simultaneous and two-dimensional measurement of laser-induced fluorescence (LIF) and Raman scattering (Ramanography) applied inside a hydrogen internal combustion (IC) engine. Two different LIF tracer molecules, triethylamine (TEA) and trimethylamine (TMA), were used for the LIF experiments. The LIF and Raman results were found to be in very good agreement. The simultaneous application of Ramanography and LIF imaging indicated that TMA is the more suitable LIF tracer molecule, compared to TEA. PMID:20011004

  16. Simultaneous laser-induced fluorescence and Raman imaging inside a hydrogen engine.

    PubMed

    Engel, Sascha Ronald; Koch, Peter; Braeuer, Andreas; Leipertz, Alfred

    2009-12-10

    We report on the simultaneous and two-dimensional measurement of laser-induced fluorescence (LIF) and Raman scattering (Ramanography) applied inside a hydrogen internal combustion (IC) engine. Two different LIF tracer molecules, triethylamine (TEA) and trimethylamine (TMA), were used for the LIF experiments. The LIF and Raman results were found to be in very good agreement. The simultaneous application of Ramanography and LIF imaging indicated that TMA is the more suitable LIF tracer molecule, compared to TEA.

  17. Imaging of polysaccharides in the tomato cell wall with Raman microspectroscopy

    PubMed Central

    2014-01-01

    Background The primary cell wall of fruits and vegetables is a structure mainly composed of polysaccharides (pectins, hemicelluloses, cellulose). Polysaccharides are assembled into a network and linked together. It is thought that the percentage of components and of plant cell wall has an important influence on mechanical properties of fruits and vegetables. Results In this study the Raman microspectroscopy technique was introduced to the visualization of the distribution of polysaccharides in cell wall of fruit. The methodology of the sample preparation, the measurement using Raman microscope and multivariate image analysis are discussed. Single band imaging (for preliminary analysis) and multivariate image analysis methods (principal component analysis and multivariate curve resolution) were used for the identification and localization of the components in the primary cell wall. Conclusions Raman microspectroscopy supported by multivariate image analysis methods is useful in distinguishing cellulose and pectins in the cell wall in tomatoes. It presents how the localization of biopolymers was possible with minimally prepared samples. PMID:24917885

  18. Coherent anti-Stokes Raman scattering hyperspectral tissue imaging with a wavelength-swept system.

    PubMed

    Bégin, Steve; Burgoyne, Bryan; Mercier, Vincent; Villeneuve, Alain; Vallée, Réal; Côté, Daniel

    2011-01-01

    We present a wavelength-swept coherent anti-Stokes Raman scattering (WS-CARS) spectroscopy system for hyperspectral imaging in thick tissue. We use a strategy where the Raman lines are excited sequentially, circumventing the need for a spectrometer. This fibre laser system, consisting of a pump laser synchronized with a rapidly tunable programmable laser (PL), can access Raman lines over a significant fraction of the high wavenumber region (2700-2950 cm(-1)) at rates of up to 10,000 spectral points per second. To demonstrate its capabilities, we have acquired WS-CARS spectra of several samples as well as images and hyperspectral images (HSI) of thick tissue both in forward and epi-detection. This instrument should be especially useful in providing local biochemical information with surrounding context supplied by imaging. PMID:21559141

  19. Coherent anti-Stokes Raman scattering hyperspectral tissue imaging with a wavelength-swept system

    PubMed Central

    Bégin, Steve; Burgoyne, Bryan; Mercier, Vincent; Villeneuve, Alain; Vallée, Réal; Côté, Daniel

    2011-01-01

    We present a wavelength-swept coherent anti-Stokes Raman scattering (WS-CARS) spectroscopy system for hyperspectral imaging in thick tissue. We use a strategy where the Raman lines are excited sequentially, circumventing the need for a spectrometer. This fibre laser system, consisting of a pump laser synchronized with a rapidly tunable programmable laser (PL), can access Raman lines over a significant fraction of the high wavenumber region (2700–2950 cm−1) at rates of up to 10,000 spectral points per second. To demonstrate its capabilities, we have acquired WS-CARS spectra of several samples as well as images and hyperspectral images (HSI) of thick tissue both in forward and epi-detection. This instrument should be especially useful in providing local biochemical information with surrounding context supplied by imaging. PMID:21559141

  20. In Situ Raman Spectroscopic Study of Gypsum (CaSO4·2H2O) and Epsomite (MgSO4·7H2O) Dehydration Utilizing an Ultrasonic Levitator.

    PubMed

    Brotton, Stephen J; Kaiser, Ralf I

    2013-02-21

    We present an original apparatus combining an acoustic levitator and a pressure-compatible process chamber. To characterize in situ the chemical and physical modifications of a levitated, single particle while heated to well-defined temperatures using a carbon dioxide laser, the chamber is interfaced to a Raman spectroscopic probe. As a proof-of-concept study, by gradually increasing the heating temperature, we observed the variations in the Raman spectra as 150 μg of crystals of gypsum and epsomite were dehydrated in anhydrous nitrogen gas. We display spectra showing the decreasing intensities of the ν1 symmetric and ν3 asymmetric stretching modes of water with time and the simultaneous shift of the ν1(SO4(2-)) symmetric stretch mode to higher wavenumbers. Our results demonstrate that the new apparatus is well suited to study the dehydration of levitated species such as minerals and offers potential advantages compared with previous experiments on bulk samples. PMID:26281883

  1. Watching embryonic development in a new light: elasticity specific imaging with dual Brillouin/Raman microspectroscopy

    NASA Astrophysics Data System (ADS)

    Meng, Zhaokai; Hanson, Jessica A.; Yakovlev, Vladislav V.

    2016-03-01

    Mechanical properties of tissues play an important role in biological development. However, the current elasticity-specific imaging techniques are either destructive / invasive, or have a limited spatial and/or temporal resolution. Recently, we introduced Brillouin microscopy imaging as a local non-invasive probe of microscopic viscoelasticity in cells and tissues. In this study, by taking advantage of Brillouin spectroscopy, we imaged the viscoelasticity properties of different compartments of living zebrafish embryos, including yolk-sac, skin, spine and heart. Brillouin and Raman spectra were collected simultaneously at each location using a recently developed Brillouin/Raman microscope.

  2. New UK in-situ stress orientation for northern England and controls on borehole wall deformation identified using borehole imaging

    NASA Astrophysics Data System (ADS)

    Kingdon, Andrew; Fellgett, Mark W.; Waters, Colin N.

    2016-04-01

    The nascent development of a UK shale gas industry has highlighted the inadequacies of previous in-situ stress mapping which is fundamental to the efficacy and safety of potential fracturing operations. The limited number of stress inversions from earthquake focal plane mechanisms and overcoring measurements of in-situ stress in prospective areas increases the need for an up-to-date stress map. Borehole breakout results from 36 wells with newly interpreted borehole imaging data are presented. Across northern England these demonstrate a consistent maximum horizontal stress orientation (SHmax) orientation of 150.9° and circular standard deviation of 13.1°. These form a new and quality assured evidence base for both industry and its regulators. Widespread use of high-resolution borehole imaging tools has facilitated investigation of micro-scale relationships between stress and lithology, facilitating identification of breakouts as short as 25 cm. This is significantly shorter than those identified by older dual-caliper logging (typically 1-10+ m). Higher wall coverage (90%+ using the highest resolution tools) and decreasing pixel size (down to 4mm vertically by 2° of circumference) also facilitates identification of otherwise undetectable sub-centimetre width Drilling Induced Tensile Fractures (DIFs). Examination of borehole imaging from wells in North Yorkshire within the Carboniferous Pennine Coal Measures Group has showed that even though the stress field is uniform, complex micro-stress relationships exist. Different stress field indicators (SFI) are significantly affected by geology with differing failure responses from adjacent lithologies, highlighted by borehole imaging on sub-metre scales. Core-log-borehole imaging integration over intervals where both breakouts and DIFs have been identified allows accurate depth matching and thus allows a synthesis of failure for differing lithology and micro-structures under common in-situ conditions. Understanding these

  3. Constrained Kinematics of ICMEs from Multi-point in Situ and Heliospheric Imaging Data

    NASA Astrophysics Data System (ADS)

    Rollett, T.; Temmer, M.; Moestl, C.; Veronig, A. M.; Lugaz, N.; Vrsnak, B.; Farrugia, C. J.; Amerstorfer, U.

    2013-12-01

    The constrained harmonic mean (CHM) method is used to calculate the direction of motion of ICMEs and their kinematical profiles. Combining single spacecraft white-light observations from STEREO/HI with supplementary in situ data, it is possible to derive the propagation speed varying with heliocentric distance. This is a big advantage against other single-viewpoint methods, i.e. fitting methods, which assume a constant propagation speed. We show two different applications for the CHM method: first, an analysis of the interaction between the solar wind and ICMEs, and second, the interaction between two ICMEs. For analyzing interaction processes it is crucial to use a method that has the ability to investigate the corresponding effects on ICME kinematics. Additionally, we show the analysis of an outstanding fast ICME event of March 2012, which was detected in situ by Venus Express, Messenger and Wind and also observed by STEREO-A/HI. Due to these multiple in situ measurements it was possible to constrain the ICME kinematics by three different boundary values. These studies are fundamental in order to deepen the understanding of ICME evolution and to enhance existing forecasting methods. This work has received funding from the European Commission FP7 Project COMESEP (263252).

  4. Fusion FISH Imaging: Single-Molecule Detection of Gene Fusion Transcripts In Situ

    PubMed Central

    Markey, Fatu Badiane; Ruezinsky, William; Tyagi, Sanjay; Batish, Mona

    2014-01-01

    Double-stranded DNA breaks occur on a regular basis in the human genome as a consequence of genotoxic stress and errors during replication. Usually these breaks are rapidly and faithfully repaired, but occasionally different chromosomes, or different regions of the same chromosome, are fused to each other. Some of these aberrant chromosomal translocations yield functional recombinant genes, which have been implicated as the cause of a number of lymphomas, leukemias, sarcomas, and solid tumors. Reliable methods are needed for the in situ detection of the transcripts encoded by these recombinant genes. We have developed just such a method, utilizing single-molecule fluorescence in situ hybridization (sm-FISH), in which approximately 50 short fluorescent probes bind to adjacent sites on the same mRNA molecule, rendering each target mRNA molecule visible as a diffraction-limited spot in a fluorescence microscope. Utilizing this method, gene fusion transcripts are detected with two differently colored probe sets, each specific for one of the two recombinant segments of a target mRNA; enabling the fusion transcripts to be seen in the microscope as distinct spots that fluoresce in both colors. We demonstrate this method by detecting the BCR-ABL fusion transcripts that occur in chronic myeloid leukemia cells, and by detecting the EWSR1-FLI1 fusion transcripts that occur in Ewing's sarcoma cells. This technology should pave the way for accurate in situ typing of many cancers that are associated with, or caused by, fusion transcripts. PMID:24675777

  5. Raman spectroscopy and imaging to detect contaminants for food safety applications

    NASA Astrophysics Data System (ADS)

    Chao, Kuanglin; Qin, Jianwei; Kim, Moon S.; Peng, Yankun; Chan, Diane; Cheng, Yu-Che

    2013-05-01

    This study presents the use of Raman chemical imaging for the screening of dry milk powder for the presence of chemical contaminants and Raman spectroscopy for quantitative assessment of chemical contaminants in liquid milk. For image-based screening, melamine was mixed into dry milk at concentrations (w/w) between 0.2% and 10.0%, and images of the mixtures were analyzed by a spectral information divergence algorithm. Ammonium sulfate, dicyandiamide, and urea were each separately mixed into dry milk at concentrations (w/w) between 0.5% and 5.0%, and an algorithm based on self-modeling mixture analysis was applied to these sample images. The contaminants were successfully detected and the spatial distribution of the contaminants within the sample mixtures was visualized using these algorithms. Liquid milk mixtures were prepared with melamine at concentrations between 0.04% and 0.30%, with ammonium sulfate and with urea at concentrations between 0.1% and 10.0%, and with dicyandiamide at concentrations between 0.1% and 4.0%. Analysis of the Raman spectra from the liquid mixtures showed linear relationships between the Raman intensities and the chemical concentrations. Although further studies are necessary, Raman chemical imaging and spectroscopy show promise for use in detecting and evaluating contaminants in food ingredients.

  6. Label-Free Cellular Imaging by Broadband Coherent Anti-Stokes Raman Scattering Microscopy

    PubMed Central

    Parekh, Sapun H.; Lee, Young Jong; Aamer, Khaled A.; Cicerone, Marcus T.

    2010-01-01

    Raman microspectroscopy can provide the chemical contrast needed to characterize the complex intracellular environment and macromolecular organization in cells without exogenous labels. It has shown a remarkable ability to detect chemical changes underlying cell differentiation and pathology-related chemical changes in tissues but has not been widely adopted for imaging, largely due to low signal levels. Broadband coherent anti-Stokes Raman scattering (B-CARS) offers the same inherent chemical contrast as spontaneous Raman but with increased acquisition rates. To date, however, only spectrally resolved signals from the strong CH-related vibrations have been used for CARS imaging. Here, we obtain Raman spectral images of single cells with a spectral range of 600–3200 cm−1, including signatures from weakly scattering modes as well as CH vibrations. We also show that B-CARS imaging can be used to measure spectral signatures of individual cells at least fivefold faster than spontaneous Raman microspectroscopy and can be used to generate maps of biochemical species in cells. This improved spectral range and signal intensity opens the door for more widespread use of vibrational spectroscopic imaging in biology and clinical diagnostics. PMID:20959111

  7. Development of a Raman chemical imaging detection method for authenticating skim milk powder

    Technology Transfer Automated Retrieval System (TEKTRAN)

    This research demonstrated that Raman chemical imaging coupled with a simple image classification algorithm can be used to detect multiple chemical adulterants in skim milk powder. Ammonium sulfate, dicyandiamide, melamine, and urea were mixed into the milk powder as chemical adulterants in the conc...

  8. A Raman chemical imaging system for detection of contaminants in food

    Technology Transfer Automated Retrieval System (TEKTRAN)

    This study presented a preliminary investigation into the use of macro-scale Raman chemical imaging for the screening of dry milk powder for the prescence of chemical contaminants. Melamine was mixed into dry milk at concentrations (w/w) of 0.2%, 0.5%, 1.0%, 2.0%, 5.0%, and 10.0% and images of the ...

  9. Two-dimensional imaging of sprays with fluorescence, lasing, and stimulated Raman scattering

    SciTech Connect

    Acker, W.P. ); Serpenguezel, A.; Swindal, J.C.; Chang, R.K. )

    1992-06-20

    Two-dimensional fluorescence, lasing, and stimulated Raman scattering images of a hollow-cone nozzle spray are observed. The various constituents of the spray, such as vapor, liquid ligaments, small droplets, and large droplets, are distinguished by selectively imaging different colors associated with the inelastic light-scattering processes.

  10. The Multispectral Microscopic Imager: Integrating Microimaging with Spectroscopy for the In-Situ Exploration of the Moon

    NASA Technical Reports Server (NTRS)

    Nunez, J. I.; Farmer, J. D.; Sellar, R. G.; Allen, Carlton C.

    2010-01-01

    To maximize the scientific return, future robotic and human missions to the Moon will need to have in-situ capabilities to enable the selection of the highest value samples for returning to Earth, or a lunar base for analysis. In order to accomplish this task efficiently, samples will need to be characterized using a suite of robotic instruments that can provide crucial information about elemental composition, mineralogy, volatiles and ices. Such spatially-correlated data sets, which place mineralogy into a microtextural context, are considered crucial for correct petrogenetic interpretations. . Combining microscopic imaging with visible= nearinfrared reflectance spectroscopy, provides a powerful in-situ approach for obtaining mineralogy within a microtextural context. The approach is non-destructive and requires minimal mechanical sample preparation. This approach provides data sets that are comparable to what geologists routinely acquire in the field, using a hand lens and in the lab using thin section petrography, and provide essential information for interpreting the primary formational processes in rocks and soils as well as the effects of secondary (diagenetic) alteration processes. Such observations lay a foundation for inferring geologic histories and provide "ground truth" for similar instruments on orbiting satellites; they support astronaut EVA activities and provide basic information about the physical properties of soils required for assessing associated health risks, and are basic tools in the exploration for in-situ resources to support human exploration of the Moon.

  11. In Situ Ptychography of Heterogeneous Catalysts using Hard X-Rays: High Resolution Imaging at Ambient Pressure and Elevated Temperature.

    PubMed

    Baier, Sina; Damsgaard, Christian D; Scholz, Maria; Benzi, Federico; Rochet, Amélie; Hoppe, Robert; Scherer, Torsten; Shi, Junjie; Wittstock, Arne; Weinhausen, Britta; Wagner, Jakob B; Schroer, Christian G; Grunwaldt, Jan-Dierk

    2016-02-01

    A new closed cell is presented for in situ X-ray ptychography which allows studies under gas flow and at elevated temperature. In order to gain complementary information by transmission and scanning electron microscopy, the cell makes use of a Protochips E-chipTM which contains a small, thin electron transparent window and allows heating. Two gold-based systems, 50 nm gold particles and nanoporous gold as a relevant catalyst sample, were used for studying the feasibility of the cell. Measurements showing a resolution around 40 nm have been achieved under a flow of synthetic air and during heating up to temperatures of 933 K. An elevated temperature exhibited little influence on image quality and resolution. With this study, the potential of in situ hard X-ray ptychography for investigating annealing processes of real catalyst samples is demonstrated. Furthermore, the possibility to use the same sample holder for ex situ electron microscopy before and after the in situ study underlines the unique possibilities available with this combination of electron microscopy and X-ray microscopy on the same sample.

  12. In Situ Balloon-Borne Ice Particle Imaging in High-Latitude Cirrus

    NASA Astrophysics Data System (ADS)

    Kuhn, Thomas; Heymsfield, Andrew J.

    2016-09-01

    Cirrus clouds reflect incoming solar radiation, creating a cooling effect. At the same time, these clouds absorb the infrared radiation from the Earth, creating a greenhouse effect. The net effect, crucial for radiative transfer, depends on the cirrus microphysical properties, such as particle size distributions and particle shapes. Knowledge of these cloud properties is also needed for calibrating and validating passive and active remote sensors. Ice particles of sizes below 100 µm are inherently difficult to measure with aircraft-mounted probes due to issues with resolution, sizing, and size-dependent sampling volume. Furthermore, artefacts are produced by shattering of particles on the leading surfaces of the aircraft probes when particles several hundred microns or larger are present. Here, we report on a series of balloon-borne in situ measurements that were carried out at a high-latitude location, Kiruna in northern Sweden (68N 21E). The method used here avoids these issues experienced with the aircraft probes. Furthermore, with a balloon-borne instrument, data are collected as vertical profiles, more useful for calibrating or evaluating remote sensing measurements than data collected along horizontal traverses. Particles are collected on an oil-coated film at a sampling speed given directly by the ascending rate of the balloon, 4 m s-1. The collecting film is advanced uniformly inside the instrument so that an always unused section of the film is exposed to ice particles, which are measured by imaging shortly after sampling. The high optical resolution of about 4 µm together with a pixel resolution of 1.65 µm allows particle detection at sizes of 10 µm and larger. For particles that are 20 µm (12 pixel) in size or larger, the shape can be recognized. The sampling volume, 130 cm3 s-1, is well defined and independent of particle size. With the encountered number concentrations of between 4 and 400 L-1, this required about 90- to 4-s sampling times to

  13. In Situ Balloon-Borne Ice Particle Imaging in High-Latitude Cirrus

    NASA Astrophysics Data System (ADS)

    Kuhn, Thomas; Heymsfield, Andrew J.

    2016-06-01

    Cirrus clouds reflect incoming solar radiation, creating a cooling effect. At the same time, these clouds absorb the infrared radiation from the Earth, creating a greenhouse effect. The net effect, crucial for radiative transfer, depends on the cirrus microphysical properties, such as particle size distributions and particle shapes. Knowledge of these cloud properties is also needed for calibrating and validating passive and active remote sensors. Ice particles of sizes below 100 µm are inherently difficult to measure with aircraft-mounted probes due to issues with resolution, sizing, and size-dependent sampling volume. Furthermore, artefacts are produced by shattering of particles on the leading surfaces of the aircraft probes when particles several hundred microns or larger are present. Here, we report on a series of balloon-borne in situ measurements that were carried out at a high-latitude location, Kiruna in northern Sweden (68N 21E). The method used here avoids these issues experienced with the aircraft probes. Furthermore, with a balloon-borne instrument, data are collected as vertical profiles, more useful for calibrating or evaluating remote sensing measurements than data collected along horizontal traverses. Particles are collected on an oil-coated film at a sampling speed given directly by the ascending rate of the balloon, 4 m s-1. The collecting film is advanced uniformly inside the instrument so that an always unused section of the film is exposed to ice particles, which are measured by imaging shortly after sampling. The high optical resolution of about 4 µm together with a pixel resolution of 1.65 µm allows particle detection at sizes of 10 µm and larger. For particles that are 20 µm (12 pixel) in size or larger, the shape can be recognized. The sampling volume, 130 cm3 s-1, is well defined and independent of particle size. With the encountered number concentrations of between 4 and 400 L-1, this required about 90- to 4-s sampling times to

  14. Method for automatically identifying spectra of different wood cell wall layers in Raman imaging data set.

    PubMed

    Zhang, Xun; Ji, Zhe; Zhou, Xia; Ma, Jian-Feng; Hu, Ya-Hong; Xu, Feng

    2015-01-20

    The technique of Raman spectroscopic imaging is finding ever-increasing applications in the field of wood science for its ability to provide spatial and spectral information about the sample. On the basis of the acquired Raman imaging data set, it is possible to determine the distribution of chemical components in various wood cell wall layers. However, the Raman imaging data set often contains thousands of spectra measured at hundreds or even thousands of individual frequencies, which results in difficulties accurately and quickly extracting all of the spectra within a specific morphological region of wood cell walls. To address this issue, the authors propose a new method to automatically identify Raman spectra of different cell wall layers on the basis of principal component analysis (PCA) and cluster analysis. A Raman imaging data set collected from a 55.5 μm × 47.5 μm cross-section of poplar tension wood was analyzed. Several thousand spectra were successfully classified into five groups in accordance with different morphological regions, namely, cell corner (CC), compound middle lamella (CML), secondary wall (SW), gelatinous layer (G-layer), and cell lumen. Their corresponding average spectra were also calculated. In addition, the relationship between different characteristic peaks in the obtained Raman spectra was estimated and it was found that the peak at 1331 cm(-1) is more related to lignin rather than cellulose. Not only can this novel method provide a convenient and accurate procedure for identifying the spectra of different cell wall layers in a Raman imaging data set, but it also can bring new insights into studying the morphology and topochemistry in wood cell walls.

  15. An in situ optical imaging system for measuring lipid uptake, vessel contraction, and lymph flow in small animal lymphatic vessels

    NASA Astrophysics Data System (ADS)

    Kassis, Timothy; Weiler, Michael J.; Dixon, J. Brandon

    2012-03-01

    All dietary lipids are transported to venous circulation through the lymphatic system, yet the underlying mechanisms that regulate this process remain unclear. Understanding how the lymphatics functionally respond to changes in lipid load is important in the diagnosis and treatment of lipid and lymphatic related diseases such as obesity, hypercholesterolemia, and lymphedema. Therefore, we sought to develop an in situ imaging system to quantify and correlate lymphatic function as it relates to lipid transport. A custom-built optical set-up provides us with the capability of dual-channel imaging of both high-speed bright-field video and fluorescence simultaneously. This is achieved by dividing the light path into two optical bands. Utilizing high-speed and back-illuminated CCD cameras and post-acquisition image processing algorithms, we have the potential quantify correlations between vessel contraction, lymph flow and lipid concentration of mesenteric lymphatic vessels in situ. Local flow velocity is measured through lymphocyte tracking, vessel contraction through measurements of the vessel walls and lipid uptake through fluorescence intensity tracking of a fluorescent long chain fatty acid analogue, Bodipy FL C16. This system will prove to be an invaluable tool for both scientists studying lymphatic function in health and disease, and those investigating strategies for targeting the lymphatic system with orally delivered drugs.

  16. Spatio-Temporal Cellular Imaging of Polymer-pDNA Nanocomplexes Affords In Situ Morphology and Trafficking Trends

    PubMed Central

    Ingle, Nilesh P.; Lian, Xue; Reineke, Theresa M.

    2013-01-01

    Synthetic polymers are ubiquitous in the development of drug and polynucleotide delivery vehicles, offering promise for personalized medicine. However, the polymer structure plays a central yet elusive role in dictating the efficacy, safety, mechanisms, and kinetics of therapeutic transport in a spatial and temporal manner. Here, we decipher the intracellular evolutionary pathways pertaining to shape, size, location, and mechanism of four structurally-divergent polymer vehicles (Tr455, Tr477, jetPEI™ and Glycofect™) that create colloidal nanoparticles (polyplexes) when complexed with fluorescently-labeled plasmid DNA (pDNA). Multiple high resolution tomographic images of whole HeLa (human cervical adenocarcinoma) cells were captured via confocal microscopy at 4, 8, 12 and 24 hours. The images were reconstructed to visualize and quantify trends in situ in a four-dimensional spatio-temporal manner. The data revealed heretofore-unseen images of polyplexes in situ and structure-function relationships, i.e., Glycofect™ polyplexes are trafficked as the smallest polyplex complexes and Tr455 polyplexes have expedited translocation to the perinuclear region. Also, all of the polyplex types appeared to be preferentially internalized and trafficked via early endosomes affiliated with caveolae, a Rab-5-dependent pathway, actin, and microtubules. PMID:24007201

  17. Application and Miniaturization of Linear and Nonlinear Raman Microscopy for Biomedical Imaging

    NASA Astrophysics Data System (ADS)

    Mittal, Richa

    Current diagnostics for several disorders rely on surgical biopsy or evaluation of ex vivo bodily fluids, which have numerous drawbacks. We evaluated the potential for vibrational techniques (both linear and nonlinear Raman) as a reliable and noninvasive diagnostic tool. Raman spectroscopy is an optical technique for molecular analysis that has been used extensively in various biomedical applications. Based on demonstrated capabilities of Raman spectroscopy we evaluated the potential of the technique for providing a noninvasive diagnosis of mucopolysaccharidosis (MPS). These studies show that Raman spectroscopy can detect subtle changes in tissue biochemistry. In applications where sub-micrometer visualization of tissue compositional change is required, a transition from spectroscopy to high quality imaging is necessary. Nonlinear vibrational microscopy is sensitive to the same molecular vibrations as linear Raman, but features fast imaging capabilities. Coherent Raman scattering when combined with other nonlinear optical (NLO) techniques (like two-photon excited fluorescence and second harmonic generation) forms a collection of advanced optical techniques that provide noninvasive chemical contrast at submicron resolution. This capability to examine tissues without external molecular agents is driving the NLO approach towards clinical applications. However, the unique imaging capabilities of NLO microscopy are accompanied by complex instrument requirements. Clinical examination requires portable imaging systems for rapid inspection of tissues. Optical components utilized in NLO microscopy would then need substantial miniaturization and optimization to enable in vivo use. The challenges in designing compact microscope objective lenses and laser beam scanning mechanisms are discussed. The development of multimodal NLO probes for imaging oral cavity tissue is presented. Our prototype has been examined for ex vivo tissue imaging based on intrinsic fluorescence and SHG

  18. The design and implementation of a high-fidelity Raman imaging microscope.

    PubMed

    Goldstein, S R; Kidder, L H; Herne, T M; Levin, I W; Lewis, E N

    1996-10-01

    We describe a Raman imaging microscope that produces high-fidelity, large format Raman images and Raman spectra from samples as small as 1 micron in size. Laser illumination is delivered to the object by means of an infinity corrected microscope objective, either by a galvanometer scanning system or a widefield fibre optic. Wavelength selection of Raman scattered emission is achieved by an acousto-optic tunable filter (AOTF), which maintains image fidelity and provides either continuous or random wavelength selection. The collimated AOTF output is imaged first by a tube lens and then by a projection lens onto a cooled silicon CCD array. Instrument features, including factors that determine the system's spatial and spectral resolution, and design considerations are discussed in detail. Images and spectra of test objects and samples that demonstrate the capability of this imaging spectrometer are presented. The potential of intrinsic chemical imaging is discussed in terms of its use in the analyses of a variety of chemical and biological samples. PMID:8923757

  19. Picosecond spectral coherent anti-Stokes Raman scattering imaging with principal component analysis of meibomian glands

    NASA Astrophysics Data System (ADS)

    Lin, Chia-Yu; Suhalim, Jeffrey L.; Nien, Chyong Ly; Miljković, Miloš D.; Diem, Max; Jester, James V.; Potma, Eric. O.

    2011-02-01

    The lipid distribution in the mouse meibomian gland was examined with picosecond spectral anti-Stokes Raman scattering (CARS) imaging. Spectral CARS data sets were generated by imaging specific localized regions of the gland within tissue sections at consecutive Raman shifts in the CH2 stretching vibrational range. Spectral differences between the location specific CARS spectra obtained in the lipid-rich regions of the acinus and the central duct were observed, which were confirmed with a Raman microspectroscopic analysis, and attributed to meibum lipid modifications within the gland. A principal component analysis of the spectral data set reveals changes in the CARS spectrum when transitioning from the acini to the central duct. These results demonstrate the utility of picosecond spectral CARS imaging combined with multivariate analysis for assessing differences in the distribution and composition of lipids in tissues.

  20. Giant Raman scattering from J-aggregated dyes inside carbon nanotubes for multispectral imaging

    NASA Astrophysics Data System (ADS)

    Gaufrès, E.; Tang, N. Y.-Wa; Lapointe, F.; Cabana, J.; Nadon, M.-A.; Cottenye, N.; Raymond, F.; Szkopek, T.; Martel, R.

    2014-01-01

    Raman spectroscopy uses visible light to acquire vibrational fingerprints of molecules, thus making it a powerful tool for chemical analysis in a wide range of media. However, its potential for optical imaging at high resolution is severely limited by the fact that the Raman effect is weak. Here, we report the discovery of a giant Raman scattering effect from encapsulated and aggregated dye molecules inside single-walled carbon nanotubes. Measurements performed on rod-like dyes such as α-sexithiophene and β-carotene, assembled inside single-walled carbon nanotubes as highly polarizable J-aggregates, indicate a resonant Raman cross-section of (3 +/- 2) × 10-21 cm2 sr-1, which is well above the cross-section required for detecting individual aggregates at the highest optical resolution. Free from fluorescence background and photobleaching, this giant Raman effect allows the realization of a library of functionalized nanoprobe labels for Raman imaging with robust detection using multispectral analysis.

  1. Development of a fiber based Raman probe compatible with interventional magnetic resonance imaging

    NASA Astrophysics Data System (ADS)

    Ashok, Praveen C.; Praveen, Bavishna B.; Rube, Martin; Cox, Benjamin; Melzer, Andreas; Dholakia, Kishan

    2014-02-01

    Raman spectroscopy has proven to be a powerful tool for discriminating between normal and abnormal tissue types. Fiber based Raman probes have demonstrated its potential for in vivo disease diagnostics. Combining Raman spectroscopy with Magnetic Resonance Imaging (MRI) opens up new avenues for MR guided minimally invasive optical biopsy. Although Raman probes are commercially available, they are not compatible with a MRI environment due to the metallic components which are used to align the micro-optic components such as filters and lenses at the probe head. Additionally they are not mechanically compatible with a typical surgical environment as factors such as sterility and length of the probe are not addressed in those designs. We have developed an MRI compatible fiber Raman probe with a disposable probe head hence maintaining sterility. The probe head was specially designed to avoid any material that would cause MR imaging artefacts. The probe head that goes into patient's body had a diameter <1.5 mm so that it is compatible with biopsy needles and catheters. The probe has been tested in MR environment and has been proven to be capable of obtaining Raman signal while the probe is under real-time MR guidance.

  2. Lean Raman imaging for rapid assessment of homogeneity in pharmaceutical formulations.

    PubMed

    Brown, Stephanie C; Claybourn, Mike; Sievwright, Dawn; Fearnside, Vicki; Ashman, Chris

    2010-04-01

    Solid dispersion formulations and drug in polymer matrices are increasingly being used by the pharmaceutical industry to enhance the solubility, or bio-availability, of active pharmaceutical ingredients (APIs). The degree of solubility or bio-availability enhancement, as well as properties such as chemical stability and physical characteristics, will be dependent on the homogeneity of the drug in polymer matrix. The use of Raman spectroscopy to assess homogeneity has traditionally been limited by the time required to acquire images from a statistically representative sample area. This may be overcome by employing a more rapid one-dimensional Raman line-mapping approach and using a statistical analysis to extract the critical information. This approach has been termed "lean" Raman imaging and allows a large area of sample to be probed in a relatively short space of time. This paper discusses the use of "lean" Raman imaging to assess two performance-indicating parameters of a drug in polymer formulation, sedimentation of the API within a capsule formulation and phase separation of the individual components. The development of a screening method, using Raman line mapping to allow rapid measurement of sedimentation of the API, is discussed. This method requires less than half an hour per capsule for data collection and processing. In addition, the development of a "lean" Raman mapping technique, using single line scans to assess drug and polymer domain sizes, is detailed. This technique employs a simple peak ratio approach coupled with statistical analysis to provide a measure of the degree of drug and polymer segregation without the need for acquisition of high pixel density images or multivariate analysis. The Raman mapping data is compared with both the dissolution profiles and processing parameters of the samples tested and a strong correlation is shown between formulation homogeneity and dissolution behavior.

  3. Dual Raman-Brillouin Microscope for Chemical and Mechanical Characterization and Imaging.

    PubMed

    Traverso, Andrew J; Thompson, Jonathan V; Steelman, Zachary A; Meng, Zhaokai; Scully, Marlan O; Yakovlev, Vladislav V

    2015-08-01

    We present a unique confocal microscope capable of measuring the Raman and Brillouin spectra simultaneously from a single spatial location. Raman and Brillouin scattering offer complementary information about a material's chemical and mechanical structure, respectively, and concurrent monitoring of both of these spectra would set a new standard for material characterization. We achieve this by applying recent innovations in Brillouin spectroscopy that reduce the necessary acquisition times to durations comparable to conventional Raman spectroscopy while attaining a high level of spectral accuracy. To demonstrate the potential of the system, we map the Raman and Brillouin spectra of a molded poly(ethylene glycol) diacrylate (PEGDA) hydrogel sample in cyclohexane to create two-dimensional images with high contrast at microscale resolutions. This powerful tool has the potential for very diverse analytical applications in basic science, industry, and medicine.

  4. Tissue diagnosis using power-sharing multifocal Raman micro-spectroscopy and auto-fluorescence imaging.

    PubMed

    Sinjab, Faris; Kong, Kenny; Gibson, Graham; Varma, Sandeep; Williams, Hywel; Padgett, Miles; Notingher, Ioan

    2016-08-01

    We describe a multifocal Raman micro-spectroscopy detection method based on a digital micromirror device, which allows for simultaneous "power-sharing" acquisition of Raman spectra from ad hoc sampling points. As the locations of the points can be rapidly updated in real-time via software control of a liquid-crystal spatial light modulator (LC-SLM), this technique is compatible with automated adaptive- and selective-sampling Raman spectroscopy techniques, the latter of which has previously been demonstrated for fast diagnosis of skin cancer tissue resections. We describe the performance of this instrument and show examples of multiplexed measurements on a range of test samples. Following this, we show the feasibility of reducing measurement time for power-shared multifocal Raman measurements combined with confocal auto-fluorescence imaging to provide guided diagnosis of tumours in human skin samples. PMID:27570692

  5. Tissue diagnosis using power-sharing multifocal Raman micro-spectroscopy and auto-fluorescence imaging

    PubMed Central

    Sinjab, Faris; Kong, Kenny; Gibson, Graham; Varma, Sandeep; Williams, Hywel; Padgett, Miles; Notingher, Ioan

    2016-01-01

    We describe a multifocal Raman micro-spectroscopy detection method based on a digital micromirror device, which allows for simultaneous “power-sharing” acquisition of Raman spectra from ad hoc sampling points. As the locations of the points can be rapidly updated in real-time via software control of a liquid-crystal spatial light modulator (LC-SLM), this technique is compatible with automated adaptive- and selective-sampling Raman spectroscopy techniques, the latter of which has previously been demonstrated for fast diagnosis of skin cancer tissue resections. We describe the performance of this instrument and show examples of multiplexed measurements on a range of test samples. Following this, we show the feasibility of reducing measurement time for power-shared multifocal Raman measurements combined with confocal auto-fluorescence imaging to provide guided diagnosis of tumours in human skin samples. PMID:27570692

  6. Direct measurement of CO2 solubility and pH in NaCl hydrothermal solutions by combining in-situ potentiometry and Raman spectroscopy up to 280 °C and 150 bar

    NASA Astrophysics Data System (ADS)

    Truche, Laurent; Bazarkina, Elena F.; Berger, Gilles; Caumon, Marie-Camille; Bessaque, Gilles; Dubessy, Jean

    2016-03-01

    The in-situ monitoring of aqueous solution chemistry at elevated temperatures and pressures is a major challenge in geochemistry. Here, we combined for the first time in-situ Raman spectroscopy for concentration measurements and potentiometry for pH measurement in a single hydrothermal cell equipped with sampling systems and operating under controlled conditions of temperature and pressure. Dissolved CO2 concentration and pH were measured at temperatures up to 280 °C and pressures up to 150 bar in the H2O-CO2 and H2O-CO2-NaCl systems. A Pitzer specific-ion-interaction aqueous model was developed and confirmed the accuracy and consistency of the measurements, at least up to 250 °C. The revised Pitzer parameters for the H2O-CO2-NaCl system were formatted for the Phreeqc geochemical software. Significant changes with respect to the Pitzer.dat database currently associated with Phreeqc were observed. The new model parameters are now available for further applications. The Raman and pH probes tested here may also be applied to field monitoring of hydrothermal springs, geothermal wells, and oil and gas boreholes.

  7. Label-free DNA imaging in vivo with stimulated Raman scattering microscopy.

    PubMed

    Lu, Fa-Ke; Basu, Srinjan; Igras, Vivien; Hoang, Mai P; Ji, Minbiao; Fu, Dan; Holtom, Gary R; Neel, Victor A; Freudiger, Christian W; Fisher, David E; Xie, X Sunney

    2015-09-15

    Label-free DNA imaging is highly desirable in biology and medicine to perform live imaging without affecting cell function and to obtain instant histological tissue examination during surgical procedures. Here we show a label-free DNA imaging method with stimulated Raman scattering (SRS) microscopy for visualization of the cell nuclei in live animals and intact fresh human tissues with subcellular resolution. Relying on the distinct Raman spectral features of the carbon-hydrogen bonds in DNA, the distribution of DNA is retrieved from the strong background of proteins and lipids by linear decomposition of SRS images at three optimally selected Raman shifts. Based on changes on DNA condensation in the nucleus, we were able to capture chromosome dynamics during cell division both in vitro and in vivo. We tracked mouse skin cell proliferation, induced by drug treatment, through in vivo counting of the mitotic rate. Furthermore, we demonstrated a label-free histology method for human skin cancer diagnosis that provides comparable results to other conventional tissue staining methods such as H&E. Our approach exhibits higher sensitivity than SRS imaging of DNA in the fingerprint spectral region. Compared with spontaneous Raman imaging of DNA, our approach is three orders of magnitude faster, allowing both chromatin dynamic studies and label-free optical histology in real time.

  8. Label-free DNA imaging in vivo with stimulated Raman scattering microscopy

    PubMed Central

    Lu, Fa-Ke; Basu, Srinjan; Igras, Vivien; Hoang, Mai P.; Ji, Minbiao; Fu, Dan; Holtom, Gary R.; Neel, Victor A.; Freudiger, Christian W.; Fisher, David E.; Xie, X. Sunney

    2015-01-01

    Label-free DNA imaging is highly desirable in biology and medicine to perform live imaging without affecting cell function and to obtain instant histological tissue examination during surgical procedures. Here we show a label-free DNA imaging method with stimulated Raman scattering (SRS) microscopy for visualization of the cell nuclei in live animals and intact fresh human tissues with subcellular resolution. Relying on the distinct Raman spectral features of the carbon-hydrogen bonds in DNA, the distribution of DNA is retrieved from the strong background of proteins and lipids by linear decomposition of SRS images at three optimally selected Raman shifts. Based on changes on DNA condensation in the nucleus, we were able to capture chromosome dynamics during cell division both in vitro and in vivo. We tracked mouse skin cell proliferation, induced by drug treatment, through in vivo counting of the mitotic rate. Furthermore, we demonstrated a label-free histology method for human skin cancer diagnosis that provides comparable results to other conventional tissue staining methods such as H&E. Our approach exhibits higher sensitivity than SRS imaging of DNA in the fingerprint spectral region. Compared with spontaneous Raman imaging of DNA, our approach is three orders of magnitude faster, allowing both chromatin dynamic studies and label-free optical histology in real time. PMID:26324899

  9. Detecting mineral content in turbid medium using nonlinear Raman imaging: feasibility study

    PubMed Central

    Arora, Rajan; Petrov, Georgi I.; Noojin, Gary D.; Thomas, Patrick A.; Denton, Michael L.; Rockwell, Benjamin A.; Thomas, Robert J.; Yakovlev, Vladislav V.

    2012-01-01

    Osteoporosis is a bone disease characterized by reduced mineral content with resulting changes in bone architecture, which in turn increases the risk of bone fracture. Raman spectroscopy has an intrinsic sensitivity to the chemical content of the bone, but its application to study bones in vivo is limited due to strong optical scattering in tissue. It has been proposed that Raman excitation with photoacoustic detection can successfully address the problem of chemically specific imaging in deep tissue. In this report, the principal possibility of photoacoustic imaging for detecting mineral content is evaluated. PMID:22337734

  10. Chemical imaging with Fourier transform coherent anti-Stokes Raman scattering microscopy.

    PubMed

    Cui, Meng; Skodack, Joshua; Ogilvie, Jennifer P

    2008-11-01

    We report chemical imaging using Fourier transform coherent anti-Stokes Raman scattering (FTCARS) microscopy. Adding a passively phase-stable local field to amplify the weak FTCARS signal, we also demonstrate interferometric FTCARS microscopy, permitting reduced incident power to be used for imaging. We discuss signal-to-noise considerations and the conditions necessary to effectively suppress background noise, allowing FTCARS microscopy that is limited by the shot noise of the detector. We also discuss differences between the signal-to-noise obtainable by time and frequency domain coherent anti-Stokes Raman scattering (CARS) methods. PMID:19122721

  11. Imaging nanometre-scale structure in cells using in situ aberration correction.

    PubMed

    Fuller, C J; Straight, A F

    2012-10-01

    Accurate distance measurements of cellular structures on a length scale relevant to single macromolecules or macromolecular complexes present a major challenge for biological microscopy. In addition to the inherent challenges of overcoming the limits imposed by the diffraction of light, cells themselves are a complex and poorly understood optical environment. We present an extension of the high-resolution colocalization method to measure three dimensional distances between diffraction-limited objects using standard widefield fluorescence microscopy. We use this method to demonstrate that in three dimensions, cells intrinsically introduce a large and variable amount of chromatic aberration into optical measurements. We present a means of correcting this aberration in situ [termed 'Colocalization and In-situ Correction of Aberration for Distance Analysis' (CICADA)] by exploiting the fact that there is a linear relationship between the degree of aberration between different wavelengths. By labelling a cellular structure with redundantly multi-colour labelled antibodies, we can create an intracellular fiducial marker for correcting the individual aberrations between two different wavelengths in the same cells. Our observations demonstrate that with suitable corrections, nanometre scale three-dimensional distance measurements can be used to probe the substructure of macromolecular complexes within cells.

  12. Semi-in situ atomic force microscopy imaging of intracellular neurofilaments under physiological conditions through the 'sandwich' method.

    PubMed

    Sato, Fumiya; Asakawa, Hitoshi; Fukuma, Takeshi; Terada, Sumio

    2016-08-01

    Neurofilaments are intermediate filament proteins specific for neurons and characterized by formation of biochemically stable, obligate heteropolymers in vivo While purified or reassembled neurofilaments have been subjected to morphological analyses by electron microscopy and atomic force microscopy, there has been a need for direct imaging of cytoplasmic genuine intermediate filaments with minimal risk of artefactualization. In this study, we applied the modified 'cells on glass sandwich' method to exteriorize intracellular neurofilaments, reducing the risk of causing artefacts through sample preparation. SW13vim(-) cells were double transduced with neurofilament medium polypeptide (NF-M) and alpha-internexin (α-inx). Cultured cells were covered with a cationized coverslip after prestabilization with tannic acid to form a sandwich and then split into two. After confirming that neurofilaments could be deposited on ventral plasma membranes exposed via unroofing, we performed atomic force microscopy imaging semi-in situ in aqueous solution. The observed thin filaments, considered to retain native structures of the neurofilaments, exhibited an approximate periodicity of 50-60 nm along their length. Their structural property appeared to reflect the morphology formed by their constituents, i.e. NF-M and α-inx. The success of semi-in situ atomic force microscopy of exposed bona fide assembled neurofilaments through separating the sandwich suggests that it can be an effective and alternative method for investigating cytoplasmic intermediate filaments under physiological conditions by atomic force microscopy.

  13. Precise voltage contrast image assisted positioning for in situ electron beam nanolithography for nanodevice fabrication with suspended nanowire structures

    NASA Astrophysics Data System (ADS)

    Long, Renhai; Chen, Jiajun; Lim, Jin-Hee; Wiley, John B.; Zhou, Weilie

    2009-07-01

    In this paper, we demonstrate precise voltage contrast image positioning for in situ electron beam (e-beam) nanolithography to integrate nanowires into suspended structures for nanoswitch fabrication. The positioning of the deflection electrodes on the nanowires can be well controlled using a precise voltage contrast image positioning technique, where the error can be minimized to about 10 nm. Using such a method, dispersed nanowires can be sandwiched between two layers of resist and suspended by one e-beam nanolithography process without any etching. The in situ e-beam nanolithography eliminates the stage movement error by preventing any movements of the stage during the nanolithography process; hence, a high precision laser stage and alignment marks on the substrate are not needed, which simplifies the traditional e-beam nanolithography process. The nanoswitches fabricated using this method show ON and OFF states with the changes of applied voltages. This simplified process provides an easy, low cost and less time-consuming route to integrating suspended nanowire based structures using a converted field emission scanning electron microscope e-beam system, which can also be customized to fabricate multi-layer structures and a site-specific nanodevice fabrication.

  14. Multiphoton microscopic imaging of histological sections without hematoxylin and eosin staining differentiates carcinoma in situ lesion from normal oesophagus

    NASA Astrophysics Data System (ADS)

    Chen, Jianxin; Xu, Jian; Kang, Deyong; Xu, Meifang; Zhuo, Shuangmu; Zhu, Xiaoqin; Jiang, Xingshan

    2013-10-01

    Multiphoton microscopy (MPM) has become a powerful, important tool for tissues imaging at the molecular level. In this paper, this technique was extended to histological investigations, differentiating carcinoma in situ (CIS) lesion from normal oesophagus by imaging histological sections without hematoxylin and eosin (H&E) staining. The results show that the histology procedures of dehydration, paraffin embedding, and de-paraffinizing highlighted two photon excited fluorescence of cytoplasm and nucleolus of epithelial cell and collagen in stroma. MPM has the ability to identify the characteristics of CIS lesion including changes of squamous cells and full epithelium, identification of basement membrane, especially prominent nucleolus. The studies described here show that MPM has the potential for future retrospective studies of tumor staging by employing on histological section specimens without H&E staining.

  15. In-situ visual observation for the formation and dissociation of methane hydrates in porous media by magnetic resonance imaging.

    PubMed

    Zhao, Jiafei; Lv, Qin; Li, Yanghui; Yang, Mingjun; Liu, Weiguo; Yao, Lei; Wang, Shenglong; Zhang, Yi; Song, Yongchen

    2015-05-01

    In this work, magnetic resonance imaging (MRI) was employed to observe the in-situ formation and dissociation of methane hydrates in porous media. Methane hydrate was formed in a high-pressure cell with controlled temperature, and then the hydrate was dissociated by thermal injection. The process was photographed by the MRI, and the pressure was recorded. The images confirmed that the direct visual observation was achieved; these were then employed to provide detailed information of the nucleation, growth, and decomposition of the hydrate. Moreover, the saturation of methane hydrate during the dissociation was obtained from the MRI intensity data. Our results showed that the hydrate saturation initially decreased rapidly, and then slowed down; this finding is in line with predictions based only on pressure. The study clearly showed that MRI is a useful technique to investigate the process of methane hydrate formation and dissociation in porous media.

  16. Volumetric neuroimaging of the atlantic white-sided dolphin (Lagenorhynchus acutus) brain from in situ magnetic resonance images.

    PubMed

    Montie, Eric W; Schneider, Gerald; Ketten, Darlene R; Marino, Lori; Touhey, Katie E; Hahn, Mark E

    2008-03-01

    The structure and development of the brain are extremely difficult to study in free-ranging marine mammals. Here, we report measurements of total white matter (WM), total gray matter (GM), cerebellum (WM and GM), hippocampus, and corpus callosum made from magnetic resonance (MR) images of fresh, postmortem brains of the Atlantic white-sided dolphin (Lagenorhynchus acutus) imaged in situ (i.e., the brain intact within the skull, with the head still attached to the body). WM:GM volume ratios of the entire brain increased from fetus to adult, illustrating the increase in myelination during ontogeny. The cerebellum (WM and GM combined) of subadult and adult dolphins ranged from 13.8 to 15.0% of total brain size, much larger than that of primates. The corpus callosum mid-sagittal area to brain mass ratios (CCA/BM) ranged from 0.088 to 0.137, smaller than in most mammals. Dolphin hippocampal volumes were smaller than those of carnivores, ungulates, and humans, consistent with previous qualitative results assessed from histological studies of the bottlenose dolphin brain. These quantitative measurements of white matter, gray matter, corpus callosum, and hippocampus are the first to be determined from MR images for any cetacean species. We establish here an approach for accurately determining the size of brain structures from in situ MR images of stranded, dead dolphins. This approach can be used not only for comparative and developmental studies of marine mammal brains but also for investigation of the potential impacts of natural and anthropogenic chemicals on neurodevelopment and neuroanatomy in exposed marine mammal populations. PMID:18286607

  17. Label-Free Nanometer-Resolution Imaging of Biological Architectures through Surface Enhanced Raman Scattering

    PubMed Central

    Ayas, Sencer; Cinar, Goksu; Ozkan, Alper Devrim; Soran, Zeliha; Ekiz, Oner; Kocaay, Deniz; Tomak, Aysel; Toren, Pelin; Kaya, Yasin; Tunc, Ilknur; Zareie, Hadi; Tekinay, Turgay; Tekinay, Ayse Begum; Guler, Mustafa Ozgur; Dana, Aykutlu

    2013-01-01

    Label free imaging of the chemical environment of biological specimens would readily bridge the supramolecular and the cellular scales, if a chemical fingerprint technique such as Raman scattering can be coupled with super resolution imaging. We demonstrate the possibility of label-free super-resolution Raman imaging, by applying stochastic reconstruction to temporal fluctuations of the surface enhanced Raman scattering (SERS) signal which originate from biomolecular layers on large-area plasmonic surfaces with a high and uniform hot-spot density (>1011/cm2, 20 to 35 nm spacing). A resolution of 20 nm is demonstrated in reconstructed images of self-assembled peptide network and fibrilated lamellipodia of cardiomyocytes. Blink rate density is observed to be proportional to the excitation intensity and at high excitation densities (>10 kW/cm2) blinking is accompanied by molecular breakdown. However, at low powers, simultaneous Raman measurements show that SERS can provide sufficient blink rates required for image reconstruction without completely damaging the chemical structure. PMID:24022059

  18. Maximizing throughput in label-free microspectroscopy with hybrid Raman imaging

    NASA Astrophysics Data System (ADS)

    Pavillon, Nicolas; Smith, Nicholas I.

    2015-01-01

    Raman spectroscopy is an optical method providing sample molecular composition, which can be analyzed (by point measurements) or spatially mapped by Raman imaging. These provide different information, signal-to-noise ratios, and require different acquisition times. Here, we quantitatively assess Raman spectral features and compare the two measurement methods by multivariate analysis. We also propose a hybrid method: scanning the beam through the sample but optically binning the signal at one location on the detector. This approach generates significantly more useful spectral signals in terms of peak visibility and statistical information. Additionally, by combination with a complementary imaging mode such as quantitative phase microscopy, hybrid imaging allows high throughput and robust spectral analysis while retaining sample spatial information. We demonstrate the improved ability to discriminate between cell lines when using hybrid scanning compared to typical point mode measurements, by quantitatively evaluating spectra taken from two macrophage-like cell lines. Hybrid scanning also provides better classification capability than the full Raman imaging mode, while providing higher signal-to-noise signals with shorter acquisition times. This hybrid imaging approach is suited for various applications including cytometry, cancer versus noncancer detection, and label-free discrimination of cell types or tissues.

  19. Segmentation of confocal Raman microspectroscopic imaging data using edge-preserving denoising and clustering.

    PubMed

    Alexandrov, Theodore; Lasch, Peter

    2013-06-18

    Over the past decade, confocal Raman microspectroscopic (CRM) imaging has matured into a useful analytical tool to obtain spatially resolved chemical information on the molecular composition of biological samples and has found its way into histopathology, cytology, and microbiology. A CRM imaging data set is a hyperspectral image in which Raman intensities are represented as a function of three coordinates: a spectral coordinate λ encoding the wavelength and two spatial coordinates x and y. Understanding CRM imaging data is challenging because of its complexity, size, and moderate signal-to-noise ratio. Spatial segmentation of CRM imaging data is a way to reveal regions of interest and is traditionally performed using nonsupervised clustering which relies on spectral domain-only information with the main drawback being the high sensitivity to noise. We present a new pipeline for spatial segmentation of CRM imaging data which combines preprocessing in the spectral and spatial domains with k-means clustering. Its core is the preprocessing routine in the spatial domain, edge-preserving denoising (EPD), which exploits the spatial relationships between Raman intensities acquired at neighboring pixels. Additionally, we propose to use both spatial correlation to identify Raman spectral features colocalized with defined spatial regions and confidence maps to assess the quality of spatial segmentation. For CRM data acquired from midsagittal Syrian hamster ( Mesocricetus auratus ) brain cryosections, we show how our pipeline benefits from the complex spatial-spectral relationships inherent in the CRM imaging data. EPD significantly improves the quality of spatial segmentation that allows us to extract the underlying structural and compositional information contained in the Raman microspectra. PMID:23701523

  20. In situ imaging and proteome profiling indicate andrographolide is a highly promiscuous compound.

    PubMed

    Li, Lin; Wijaya, Hadhi; Samanta, Sanjay; Lam, Yulin; Yao, Shao Q

    2015-06-24

    Natural products represent an enormous source of pharmacologically useful compounds, and are often used as the starting point in modern drug discovery. Many biologically interesting natural products are however not being pursued as potential drug candidates, partly due to a lack of well-defined mechanism-of-action. Traditional in vitro methods for target identification of natural products based on affinity protein enrichment from crude cellular lysates cannot faithfully recapitulate protein-drug interactions in living cells. Reported herein are dual-purpose probes inspired by the natural product andrographolide, capable of both reaction-based, real-time bioimaging and in situ proteome profiling/target identification in live mammalian cells. Our results confirm that andrographolide is a highly promiscuous compound and engaged in covalent interactions with numerous previously unknown cellular targets in cell type-specific manner. We caution its potential therapeutic effects should be further investigated in detail.

  1. In situ imaging of field-induced hexagonal columns in magnetite ferrofluids.

    PubMed

    Klokkenburg, Mark; Erné, Ben H; Meeldijk, Johannes D; Wiedenmann, Albrecht; Petukhov, Andrei V; Dullens, Roel P A; Philipse, Albert P

    2006-11-01

    Field-induced structures in a ferrofluid with well-defined magnetite nanoparticles with a permanent magnetic dipole moment are analyzed on a single-particle level by in situ cryogenic transmission electron microscopy (2D). The field-induced columnar phase locally exhibits hexagonal symmetry and confirms the structures observed in simulations for ferromagnetic dipolar fluids in 2D. The columns are distorted by lens-shaped voids, due to the weak interchain attraction relative to field-directed dipole-dipole attraction. Both dipolar coupling and the dipole concentration determine the dimensions and the spatial arrangement of the columns. Their regular spacing manifests long-range end-pole repulsions that eventually dominate the fluctuation-induced attractions between dipole chains that initiate the columnar transition. PMID:17155554

  2. In situ imaging and proteome profiling indicate andrographolide is a highly promiscuous compound

    PubMed Central

    Li, Lin; Wijaya, Hadhi; Samanta, Sanjay; Lam, Yulin; Yao, Shao Q.

    2015-01-01

    Natural products represent an enormous source of pharmacologically useful compounds, and are often used as the starting point in modern drug discovery. Many biologically interesting natural products are however not being pursued as potential drug candidates, partly due to a lack of well-defined mechanism-of-action. Traditional in vitro methods for target identification of natural products based on affinity protein enrichment from crude cellular lysates cannot faithfully recapitulate protein-drug interactions in living cells. Reported herein are dual-purpose probes inspired by the natural product andrographolide, capable of both reaction-based, real-time bioimaging and in situ proteome profiling/target identification in live mammalian cells. Our results confirm that andrographolide is a highly promiscuous compound and engaged in covalent interactions with numerous previously unknown cellular targets in cell type-specific manner. We caution its potential therapeutic effects should be further investigated in detail. PMID:26105662

  3. In situ scanning tunneling microscope tip treatment device for spin polarization imaging

    SciTech Connect

    Li, An-Ping; Jianxing, Ma; Shen, Jian

    2008-04-22

    A tip treatment device for use in an ultrahigh vacuum in situ scanning tunneling microscope (STM). The device provides spin polarization functionality to new or existing variable temperature STM systems. The tip treatment device readily converts a conventional STM to a spin-polarized tip, and thereby converts a standard STM system into a spin-polarized STM system. The tip treatment device also has functions of tip cleaning and tip flashing a STM tip to high temperature (>2000.degree. C.) in an extremely localized fashion. Tip coating functions can also be carried out, providing the tip sharp end with monolayers of coating materials including magnetic films. The device is also fully compatible with ultrahigh vacuum sample transfer setups.

  4. In situ TEM imaging of CaCO₃ nucleation reveals coexistence of direct and indirect pathways.

    PubMed

    Nielsen, Michael H; Aloni, Shaul; De Yoreo, James J

    2014-09-01

    Mechanisms of nucleation from electrolyte solutions have been debated for more than a century. Recent discoveries of amorphous precursors and evidence for cluster aggregation and liquid-liquid separation contradict common assumptions of classical nucleation theory. Using in situ transmission electron microscopy (TEM) to explore calcium carbonate (CaCO3) nucleation in a cell that enables reagent mixing, we demonstrate that multiple nucleation pathways are simultaneously operative, including formation both directly from solution and indirectly through transformation of amorphous and crystalline precursors. However, an amorphous-to-calcite transformation is not observed. The behavior of amorphous calcium carbonate upon dissolution suggests that it encompasses a spectrum of structures, including liquids and solids. These observations of competing direct and indirect pathways are consistent with classical predictions, whereas the behavior of amorphous particles hints at an underlying commonality among recently proposed precursor-based mechanisms. PMID:25190792

  5. In situ imaging and proteome profiling indicate andrographolide is a highly promiscuous compound

    NASA Astrophysics Data System (ADS)

    Li, Lin; Wijaya, Hadhi; Samanta, Sanjay; Lam, Yulin; Yao, Shao Q.

    2015-06-01

    Natural products represent an enormous source of pharmacologically useful compounds, and are often used as the starting point in modern drug discovery. Many biologically interesting natural products are however not being pursued as potential drug candidates, partly due to a lack of well-defined mechanism-of-action. Traditional in vitro methods for target identification of natural products based on affinity protein enrichment from crude cellular lysates cannot faithfully recapitulate protein-drug interactions in living cells. Reported herein are dual-purpose probes inspired by the natural product andrographolide, capable of both reaction-based, real-time bioimaging and in situ proteome profiling/target identification in live mammalian cells. Our results confirm that andrographolide is a highly promiscuous compound and engaged in covalent interactions with numerous previously unknown cellular targets in cell type-specific manner. We caution its potential therapeutic effects should be further investigated in detail.

  6. Dual Raman-Brillouin microscope for chemical and mechanical characterization and imaging (Conference Presentation)

    NASA Astrophysics Data System (ADS)

    Yakovlev, Vladislav V.

    2016-03-01

    We present a unique confocal microscope capable of measuring the Raman and Brillouin spectra simultaneously from a single spatial location. Raman and Brillouin scattering offer complementary information about a material's chemical and mechanical structure, respectively, and concurrent monitoring of both of these spectra would set a new standard for material characterization. We achieve this by applying recent innovations in Brillouin spectroscopy that reduce the necessary acquisition times to durations comparable to conventional Raman spectroscopy while attaining a high level of spectral accuracy. To demonstrate the potential of the system, we apply this system for imaging melanoma, arteriosclerotic plaque, embryonic development, bones and biomaterials. The developed instrument has the potential for very diverse analytical applications in basic biomedical science and biomedical diagnostics and imaging.

  7. 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.

  8. In situ Raman spectroscopy of the graphene/water interface of a solution-gated field-effect transistor: electron-phonon coupling and spectroelectrochemistry.

    PubMed

    Binder, J; Urban, J M; Stepniewski, R; Strupinski, W; Wysmolek, A

    2016-01-29

    We present a novel measurement approach which combines the electrical characterization of solution-gated field-effect transistors based on epitaxial bilayer graphene on 4H-SiC (0001) with simultaneous Raman spectroscopy. By changing the gate voltage, we observed Raman signatures related to the resonant electron-phonon coupling. An analysis of these Raman bands enabled the extraction of the geometrical capacitance of the system and an accurate calculation of the Fermi levels for bilayer graphene. An intentional application of higher gate voltages allowed us to trigger electrochemical reactions, which we followed in situ by Raman spectroscopy. The reactions showed a partially reversible character, as indicated by an emergence/disappearance of peaks assigned to C-H and Si-H vibration modes as well as an increase/decrease of the defect-related Raman D band intensity. Our setup provides a highly interesting platform for future spectroelectrochemical research on electrically-induced sorption processes of graphene on the micrometer scale.

  9. In Situ Visible to Short Wavelength Imaging Spectroscopy with the Ultra Compact Imaging Spectrometer (UCIS): Case Studies from the Mars Exploration Rovers

    NASA Technical Reports Server (NTRS)

    Blaney, D.; Mouroulis, P.; Green, R.; Rodriguez, J.; Sellar, G.; Van Gorp, B.; Wilson, D.

    2011-01-01

    In Situ imaging spectroscopy provides a way to address complex questions of geological evolution for both aqueous and igneous processes by mapping mineral composition at the spatial scale of rocks and outcrops. Examination of locations studied by the Mars Exploration Rovers Spirit and Opportunity can provide examples of the potential utility and define the needed measurement requirements. A compact instrument is needed to be able to adequately address these science questions from a rover platform. The Ultra Compact Imaging Spectrometer (UCIS) is an instrument designed to address the science need and implementation constraints.

  10. Fast Confocal Raman Imaging Using a 2-D Multifocal Array for Parallel Hyperspectral Detection.

    PubMed

    Kong, Lingbo; Navas-Moreno, Maria; Chan, James W

    2016-01-19

    We present the development of a novel confocal hyperspectral Raman microscope capable of imaging at speeds up to 100 times faster than conventional point-scan Raman microscopy under high noise conditions. The microscope utilizes scanning galvomirrors to generate a two-dimensional (2-D) multifocal array at the sample plane, generating Raman signals simultaneously at each focus of the array pattern. The signals are combined into a single beam and delivered through a confocal pinhole before being focused through the slit of a spectrometer. To separate the signals from each row of the array, a synchronized scan mirror placed in front of the spectrometer slit positions the Raman signals onto different pixel rows of the detector. We devised an approach to deconvolve the superimposed signals and retrieve the individual spectra at each focal position within a given row. The galvomirrors were programmed to scan different focal arrays following Hadamard encoding patterns. A key feature of the Hadamard detection is the reconstruction of individual spectra with improved signal-to-noise ratio. Using polystyrene beads as test samples, we demonstrated not only that our system images faster than a conventional point-scan method but that it is especially advantageous under noisy conditions, such as when the CCD detector operates at fast read-out rates and high temperatures. This is the first demonstration of multifocal confocal Raman imaging in which parallel spectral detection is implemented along both axes of the CCD detector chip. We envision this novel 2-D multifocal spectral detection technique can be used to develop faster imaging spontaneous Raman microscopes with lower cost detectors. PMID:26654100

  11. Magnetic resonance imaging analysis on the in-situ mixing zone of CO2 miscible displacement flows in porous media

    NASA Astrophysics Data System (ADS)

    Song, Yongchen; Yang, Wenzhe; Wang, Dayong; Yang, Mingjun; Jiang, Lanlan; Liu, Yu; Zhao, Yuechao; Dou, Binlin; Wang, Zhiguo

    2014-06-01

    The in-situ mixing zone represents dynamic characteristics of CO2 miscible displacement flows, which is important for carbon dioxide enhanced oil recovery (CO2-EOR) projects. However, the migration characteristics of the in-situ mixing zone under reservoir conditions has been neither well studied nor fully understood. The in-situ mixing zone with the flowing mixture of supercritical CO2 and n-decane (nC10) was investigated by using a magnetic resonance imaging apparatus at a reservoir condition of 8.5 MPa and 37.8 °C in porous media. The experimental results showed that the CO2-frontal velocity was larger than the mixing-frontal velocity. The mixing zone length was linearly declined in the miscible displacement process. And the declining rate of the mixing zone length was increased with injection rate. It indicates that the mixing zone length is not constant in a vertically stable CO2 misible displacement and a volume contraction due to phase behavior effects may occur. Then, an error function based on the convection-dispersion equation was fitted with CO2 miscible displacement experiments. The error function was well fitted both at a series of fixed core positions and a series of fixed displacement times. Furthermore, the longitudinal dispersion coefficients (Klx and Klt) and the longitudinal Peclet numbers (Ped and PeL) were quantified from the fitting results. The evolutions of the longitudinal dispersion coefficient were reduced along the displacement time. And the declining rate was increased with injection rate. And with proceeding, the longitudinal dispersion coefficient was tending towards stability and constant. But the evolutions of the longitudinal Peclet numbers were increased along the displacement time. And the increasing rate was increased with injection rate.

  12. In-line near-infrared (NIR) and Raman spectroscopy coupled with principal component analysis (PCA) for in situ evaluation of the transesterification reaction.

    PubMed

    Fontalvo-Gómez, Miriam; Colucci, José A; Velez, Natasha; Romañach, Rodolfo J

    2013-10-01

    Biodiesel was synthesized from different commercially available oils while in-line Raman and near-infrared (NIR) spectra were obtained simultaneously, and the spectral changes that occurred during the reaction were evaluated with principal component analysis (PCA). Raman and NIR spectra were acquired every 30 s with fiber optic probes inserted into the reaction vessel. The reaction was performed at 60-70 °C using magnetic stirring. The time of reaction was 90 min, and during this time, 180 Raman and NIR spectra were collected. NIR spectra were collected using a transflectance probe and an optical path length of 1 mm at 8 cm(-1) spectral resolution and averaging 32 scans; for Raman spectra a 3 s exposure time and three accumulations were adequate for the analysis. Raman spectroscopy showed the ester conversion as evidenced by the displacement of the C=O band from 1747 to 1744 cm(-1) and the decrease in the intensity of the 1000-1050 cm(-1) band and the 1405 cm(-1) band as methanol was consumed in the reaction. NIR spectra also showed the decrease in methanol concentration with the band in the 4750-5000 cm(-1) region; this signal is present in the spectra of the transesterification reaction but not in the neat oils. The variations in the intensity of the methanol band were a main factor in the in-line monitoring of the transesterification reaction using Raman and NIR spectroscopy. The score plot of the first principal component showed the progress of the reaction. The final product was analyzed using (1)H nuclear magnetic resonance ((1)H NMR) spectroscopy and using mid-infrared spectroscopy, confirming the conversion of the oils to biodiesel. PMID:24067570

  13. The micro-distribution of carbonaceous matter in the Murchison meteorite as investigated by Raman imaging.

    PubMed

    El Amri, Chahrazade; Maurel, Marie-Christine; Sagon, Gérard; Baron, Marie-Hélène

    2005-07-01

    The carbonaceous Murchison chondrite is one of the most studied meteorites. It is considered to be an astrobiology standard for detection of extraterrestrial organic matter. Considerable work has been done to resolve the elemental composition of this meteorite. Raman spectroscopy is a very suitable technique for non-destructive rapid in situ analyses to establish the spatial distribution of carbonaceous matter. This report demonstrates that Raman cartography at a resolution of 1 microm2 can be performed. Two-dimensional distribution of graphitised carbon, amorphous carbonaceous matter and minerals were obtained on 100 microm2 maps. Maps of the surface of native stones and of a powdered sample are compared. Graphitic and amorphous carbonaceous domains are found to be highly overlapping in all tested areas at the surface of the meteorite and in its interior as well. Pyroxene, olivine and iron oxide grains are embedded into this mixed carbonaceous material. The results show that every mineral grain with a size of less than a few microm2 is encased in a thin carbonaceous matrix, which accounts for only 2.5 wt.%. This interstitial matter sticks together isolated mineral crystallites or concretions, including only very few individualized graphitised grains. Grinding separates the mineral particles but most of them retain their carbonaceous coating. This Raman study complements recent findings deduced from other spatial analyses performed by microprobe laser-desorption laser-ionisation mass spectrometry (microL2MS), transmission electron microscopy (TEM) and scanning transmission X-ray microscopy (STXM).

  14. In Situ Analysis of a High-Temperature Cure Reaction in Real Time Using Modulated Fiber-Optic FT-Raman Spectroscopy

    NASA Technical Reports Server (NTRS)

    Aust, Jeffrey F.; Cooper, John B.; Wise, Kent L.; Jensen, Brian J.

    1999-01-01

    The vibrational spectrum of a high-temperature (330 C) polymerization reaction was successfully monitored in real time with the use of a modulated fiber-optic Fourier transform (FT)-Raman spectrometer. A phenylethynyl-terminated monomer was cured, and spectral evidence for two different reaction products was acquired. The products are a conjugated polyene chain and a cyclized trimer. This is the first report describing the use of FT-Raman spectroscopy to monitor a high temperature (greater than 250 C) reaction in real time.

  15. Screening of adulterants in milk powder using a high-throughput Raman chemical imaging method

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Milk is one of the most common targets for economically motivated adulteration. Adulterants in milk can cause illness and death when consumed, thus rapid and accurate detection method is needed for authenticating milk products. Our previous studies based on a point-scan Raman imaging system have dem...

  16. Study on Raman spectral imaging method for simultaneous estimation of ingredients concentration in food powder

    Technology Transfer Automated Retrieval System (TEKTRAN)

    This study investigated the potential of point scan Raman spectral imaging method for estimation of different ingredients and chemical contaminant concentration in food powder. Food powder sample was prepared by mixing sugar, vanillin, melamine and non-dairy cream at 5 different concentrations in a ...

  17. Spatial correlation of confocal Raman scattering and secondary ion mass spectrometric molecular images of lignocellulosic materials.

    PubMed

    Li, Zhen; Chu, Li-Qiang; Sweedler, Jonathan V; Bohn, Paul W

    2010-04-01

    A detailed chemical and structural understanding of pre-enzymatic processing of lignocellulosic materials (LCMs) is a key objective in the development of renewable energy. Efficient rendering of biomass components into fermentable substrates for conversion into biofuel feedstocks would benefit greatly from the development of new technologies to provide high-quality, spatially resolved chemical information about LCMs during the various processing states. In an effort to realize this important goal, spatially correlated confocal Raman and mass spectrometric images allow the extraction of three-dimensional information from the perennial grass, Miscanthus x giganteus. An optical microscopy-based landmark registry scheme was developed that allows samples to be transferred between laboratories at different institutions, while retaining the capability to access the same physical regions of the samples. Subsequent to higher resolution imaging via confocal Raman microscopy and secondary ion mass spectrometry (SIMS), laser desorption-ionization mass spectrometry was used to place these regions within the overall sample architecture. Excellent sample registry was evident in the highly correlated Raman and SIMS images. In addition, the correlation of vibrational Raman scattering with mass spectra from specific spatial locations allowed confirmation of the assignment of intracellular globular structures to hemicellulose-rich lignin complexes, an assignment which could only be made tentatively from either image alone. PMID:20205411

  18. High-throughput Raman chemical imaging for evaluating food safety and quality

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A line-scan hyperspectral system was developed to enable Raman chemical imaging for large sample areas. A custom-designed 785 nm line-laser based on a scanning mirror serves as an excitation source. A 45° dichroic beamsplitter reflects the laser light to form a 24 cm × 1 mm excitation line normally ...

  19. A line-scan hyperspectral system for high-throughput Raman chemical imaging

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A line-scan hyperspectral system was developed to enable Raman chemical imaging for large sample areas. A custom-designed 785 nm line-laser, based on a scanning mirror, serves as an excitation source. A 45° dichroic beamsplitter reflects the laser light to form a 24 cm × 1 mm excitation line normall...

  20. Raman spectral imaging technique on detection of melamine in skim milk powder

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A point-scan Raman spectral imaging system was used for quantitative detection of melamine in milk powder. A sample depth of 2 mm and corresponding laser intensity of 200 mW were selected after evaluating the penetration of a 785 nm laser through milk powder. Horizontal and vertical spatial resoluti...

  1. Line-scan macro-scale Raman chemical imaging for authentication of powdered foods and ingredients

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Adulteration and fraud for powdered foods and ingredients are rising food safety risks that threaten consumers’ health. In this study, a newly developed line-scan macro-scale Raman imaging system using a 5 W 785 nm line laser as excitation source was used to authenticate the food powders. The system...

  2. Raman spectral imaging for quantitative contaminant evaluation in skim milk powder

    Technology Transfer Automated Retrieval System (TEKTRAN)

    This study uses a point-scan Raman spectral imaging system for quantitative detection of melamine in milk powder. A sample depth of 2 mm and corresponding laser intensity of 200 mW were selected after evaluating the penetration of a 785 nm laser through milk powder. Horizontal and vertical spatial r...

  3. Image quality method as a possible way of in situ monitoring of in-vessel mirrors in a fusion reactor

    NASA Astrophysics Data System (ADS)

    Konovalov, V. G.; Voitsenya, V. S.; Makhov, M. N.; Ryzhkov, I. V.; Shapoval, A. N.; Solodovchenko, S. I.; Stan, A. F.; Bondarenko, V. N.; Donné, A. J. H.; Litnovsky, A.

    2016-09-01

    The plasma-facing (first) mirrors in ITER will be subject to sputtering and/or contamination with rates that will depend on the precise mirror locations. The resulting influence of both these factors can reduce the mirror reflectance (R) and worsen the transmitted image quality (IQ). This implies that monitoring the mirror quality in situ is an actual desire, and the present work is an attempt towards a solution. The method we propose is able to elucidate the reason for degradation of the mirror reflectance: sputtering by charge exchange atoms or deposition of contaminated layers. In case of deposition of contaminants, the mirror can be cleaned in situ, but a rough mirror (due to sputtering) cannot be used anymore and has to be replaced. To demonstrate the feasibility of the IQ method, it was applied to mirror specimens coated with carbon film in laboratory conditions and to mirrors coated with contaminants during exposure in fusion devices (TRIAM-1M and Tore Supra), as well as to mirrors of different materials exposed to sputtering by plasma ions in the DSM-2 plasma stand (in IPP NSC KIPT).

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

    NASA Astrophysics Data System (ADS)

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

    2011-10-01

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

  5. Effects of tissue fixation on coherent anti-Stokes Raman scattering images of brain

    NASA Astrophysics Data System (ADS)

    Galli, Roberta; Uckermann, Ortrud; Koch, Edmund; Schackert, Gabriele; Kirsch, Matthias; Steiner, Gerald

    2014-07-01

    Coherent anti-Stokes Raman scattering (CARS) microscopy is an emerging multiphoton technique for the label-free histopathology of the central nervous system, by imaging the lipid content within the tissue. In order to apply the technique on standard histology sections, it is important to know the effects of tissue fixation on the CARS image. Here, we report the effects of two common fixation methods, namely with formalin and methanol-acetone, on mouse brain and human glioblastoma tissue. The variations induced by fixation on the CARS contrast and intensity were compared and interpreted using Raman microspectroscopy. The results show that, whenever unfixed cryosections cannot be used, fixation with formalin constitutes an alternative which does not deteriorate substantially the contrast generated by the different brain structures in the CARS image. Fixation with methanol-acetone strongly modifies the tissue lipid content and is therefore incompatible with the CARS imaging.

  6. Measuring Mass-Based Hygroscopicity of Atmospheric Particles through in Situ Imaging.

    PubMed

    Piens, Dominique S; Kelly, Stephen T; Harder, Tristan H; Petters, Markus D; O'Brien, Rachel E; Wang, Bingbing; Teske, Ken; Dowell, Pat; Laskin, Alexander; Gilles, Mary K

    2016-05-17

    Quantifying how atmospheric particles interact with water vapor is critical for understanding the effects of aerosols on climate. We present a novel method to measure the mass-based hygroscopicity of particles while characterizing their elemental and carbon functional group compositions. Since mass-based hygroscopicity is insensitive to particle geometry, it is advantageous for probing the hygroscopic behavior of atmospheric particles, which can have irregular morphologies. Combining scanning electron microscopy with energy dispersive X-ray analysis (SEM/EDX), scanning transmission X-ray microscopy (STXM) analysis, and in situ STXM humidification experiments, this method was validated using laboratory-generated, atmospherically relevant particles. Then, the hygroscopicity and elemental composition of 15 complex atmospheric particles were analyzed by leveraging quantification of C, N, and O from STXM, and complementary elemental quantification from SEM/EDX. We found three types of hygroscopic responses, and correlated high hygroscopicity with Na and Cl content. The mixing state of 158 other particles from the sample broadly agreed with those of the humidified particles, indicating the potential to infer atmospheric hygroscopic behavior from a selected subset of particles. These methods offer unique quantitative capabilities to characterize and correlate the hygroscopicity and chemistry of individual submicrometer atmospheric particles.

  7. CT imaging techniques for two-phase and three-phase in-situ saturation measurements

    SciTech Connect

    Sharma, B.C.; Brigham, W.E.; Castanier, L.M.

    1997-06-01

    The aim of this research is to use the SUPRI 3D steam injection laboratory model to establish a reliable method for 3-phase in-situ saturation measurements, and thereafter investigate the mechanism of steamflood at residual oil saturation. Demiral et al. designed and constructed a three dimensional laboratory model that can be used to measure temperature, pressure and heat loss data. The model is also designed so that its construction materials are not a limiting factor for CT scanning. We have used this model for our study. In this study, we saturated the model with mineral oil, and carried out waterflood until residual oil saturation. Steamflood was then carried out. A leak appeared at the bottom of the model. Despite this problem, the saturation results, obtained by using 2-phase and 3-phase saturation equations and obtained from the Cat scanner, were compared with the saturations obtained from material balance. The errors thus obtained were compared with those obtained by an error analysis carried out on the saturation equations. This report gives details of the experimental procedures, the data acquisition and data processing computer programs, and the analysis of a steamflood experiment carried out at residual oil saturation.

  8. Measuring mass-based hygroscopicity of atmospheric particles through in situ imaging

    DOE PAGES

    Piens, Dominique S.; Kelly, Stephen T.; Harder, Tristan H.; Petters, Markus D.; O’Brien, Rachel E.; Wang, Bingbing; Teske, Ken; Dowell, Pat; Laskin, Alexander; Gilles, Mary K.

    2016-04-18

    Quantifying how atmospheric particles interact with water vapor is critical for understanding the effects of aerosols on climate. We present a novel method to measure the mass-based hygroscopicity of particles while characterizing their elemental and carbon functional group compositions. Since mass-based hygroscopicity is insensitive to particle geometry, it is advantageous for probing the hygroscopic behavior of atmospheric particles, which can have irregular morphologies. Combining scanning electron microscopy with energy dispersive X-ray analysis (SEM/EDX), scanning transmission X-ray microscopy (STXM) analysis, and in situ STXM humidification experiments, this method was validated using laboratory-generated, atmospherically relevant particles. Then, the hygroscopicity and elemental compositionmore » of 15 complex atmospheric particles were analyzed by leveraging quantification of C, N, and O from STXM, and complementary elemental quantification from SEM/EDX. We found three types of hygroscopic responses, and correlated high hygroscopicity with Na and Cl content. The mixing state of 158 other particles from the sample broadly agreed with those of the humidified particles, indicating the potential to infer atmospheric hygroscopic behavior from a selected subset of particles. As a result, these methods offer unique quantitative capabilities to characterize and correlate the hygroscopicity and chemistry of individual submicrometer atmospheric particles.« less

  9. Measuring Mass-Based Hygroscopicity of Atmospheric Particles through in Situ Imaging.

    PubMed

    Piens, Dominique S; Kelly, Stephen T; Harder, Tristan H; Petters, Markus D; O'Brien, Rachel E; Wang, Bingbing; Teske, Ken; Dowell, Pat; Laskin, Alexander; Gilles, Mary K

    2016-05-17

    Quantifying how atmospheric particles interact with water vapor is critical for understanding the effects of aerosols on climate. We present a novel method to measure the mass-based hygroscopicity of particles while characterizing their elemental and carbon functional group compositions. Since mass-based hygroscopicity is insensitive to particle geometry, it is advantageous for probing the hygroscopic behavior of atmospheric particles, which can have irregular morphologies. Combining scanning electron microscopy with energy dispersive X-ray analysis (SEM/EDX), scanning transmission X-ray microscopy (STXM) analysis, and in situ STXM humidification experiments, this method was validated using laboratory-generated, atmospherically relevant particles. Then, the hygroscopicity and elemental composition of 15 complex atmospheric particles were analyzed by leveraging quantification of C, N, and O from STXM, and complementary elemental quantification from SEM/EDX. We found three types of hygroscopic responses, and correlated high hygroscopicity with Na and Cl content. The mixing state of 158 other particles from the sample broadly agreed with those of the humidified particles, indicating the potential to infer atmospheric hygroscopic behavior from a selected subset of particles. These methods offer unique quantitative capabilities to characterize and correlate the hygroscopicity and chemistry of individual submicrometer atmospheric particles. PMID:27088454

  10. Characterizing liver capsule microstructure via in situ bulge test coupled with multiphoton imaging.

    PubMed

    Jayyosi, C; Coret, M; Bruyère-Garnier, K

    2016-02-01

    The characterization of biological tissue at the microscopic scale is the starting point of many applications in tissue engineering and especially in the development of structurally based constitutive models. In the present study, focus is made on the liver capsule, the membrane encompassing hepatic parenchyma, which takes a huge part in liver mechanical properties. An in situ bulge test experiment under a multiphoton microscope has been developed to assess the microstructure changes that arise with biaxial loading. Multiphoton microscopy allows to observe the elastin and collagen fiber networks simultaneously. Thus a description of the microstructure organization of the capsule is given, characterizing the shapes, geometry and arrangement of fibers. The orientation of fibers is calculated and orientation distribution evolution with loading is given, in the case of an equibiaxial and two non equibiaxial loadings, thanks to a circular and elliptic set up of the bulge test. The local strain fields have also been computed, by the mean of a photobleaching grid, to get an idea of what the liver capsule might experience when subjected to internal pressure. Results show that strain fields present some heterogeneity due to anisotropy. Reorientation occurs in non equibiaxial loadings and involves fibers layers from the inner to the outer surface as expected. Although there is a fiber network rearrangement to accommodate with loading in the case of equibiaxial loading, there is no significant reorientation of the main fibers direction of the different layers.

  11. Proximal Analysis of Regolith Habitats and Protective Biomolecules in Situ by Laser Raman Spectroscopy: Overview of Terrestrial Antarctic Habitats and Mars Analogs

    NASA Astrophysics Data System (ADS)

    Wynn-Williams, D. D.; Edwards, H. G. M.

    2000-04-01

    Fourier-transform laser Raman spectroscopy in the near infrared (1064 nm) has been used to characterize a variety of key pigments and biomolecules produced by cyanobacteria and other stresstolerant microbes in material from extreme Antarctic cold deserts analogous to martian habitats. These compounds include photosynthetic pigments and sunscreens to protect against harmful UV radiation in the light zone (chlorophyll, scytonemin, β-carotene) and photoprotective minerals, such as silica containing iron (III) oxide. Calcium oxalate mono- and dihydrate produced as a result of the biological weathering processes and stress-protective compounds, necessary to protect organisms against desiccation, freezing temperatures, and hypersalinity, such as water-replacement molecules (trehalose), are also monitored. From the results obtained using Antarctic samples, it is shown that a laser-based system can be used to characterize biomolecules in their natural state within their mineral microhabitats. Because of the similarities between the Antarctic cold desert ecosystems, which represent some of the most extreme terrestrial environmental habitats, and putative martian analogs, the laser-Raman spectrosocopic approach is proposed for the detection of former life on Mars analogs to terrestrial cyanobacteria under stress, such as stromatolites, evaporites, and endolithic communities. To this end, the spectral database that is being accumulated from laser-Raman studies of these Antarctic communities will provide a resource of potential biomarkers for future remote laser-Raman analysis on future Mars missions.

  12. An Assessment of macro-scale in situ Raman and ultraviolet-induced fluorescence spectroscopy for rapid characterization of frozen peat and ground ice

    NASA Astrophysics Data System (ADS)

    Laing, Janelle R.; Robichaud, Hailey C.; Cloutis, Edward A.

    2016-04-01

    The search for life on other planets is an active area of research. Many of the likeliest planetary bodies, such as Europa, Enceladus, and Mars are characterized by cold surface environments and ice-rich terrains. Both Raman and ultraviolet-induced fluorescence (UIF) spectroscopies have been proposed as promising tools for the detection of various kinds of bioindicators in these environments. We examined whether macro-scale Raman and UIF spectroscopy could be applied to the analysis of unprocessed terrestrial frozen peat and clear ground ice samples for detection of bioindicators. It was found that this approach did not provide unambiguous detection of bioindicators, likely for a number of reasons, particularly due to strong broadband induced fluorescence. Other contributing factors may include degradation of organic matter in frozen peat to the point that compound-specific emitted fluorescence or Raman peaks were not resolvable. Our study does not downgrade the utility of either UIF or Raman spectroscopy for astrobiological investigations (which has been demonstrated in previous studies), but does suggest that the choice of instrumentation, operational conditions and sample preparation are important factors in ensuring the success of these techniques.

  13. Validation of break-apart and fusion MYC probes using a digital fluorescence in situ hybridization capture and imaging system

    PubMed Central

    Liew, Michael; Rowe, Leslie; Clement, Parker W.; Miles, Rodney R.; Salama, Mohamed E.

    2016-01-01

    Introduction: Detection of MYC translocations using fluorescence in situ hybridization (FISH) is important in the evaluation of lymphomas, in particular, Burkitt lymphoma and diffuse large B-cell lymphoma. Our aim was to validate a digital FISH capture and imaging system for the detection of MYC 8q24 translocations using LSI-MYC (a break-apart probe) and MYC 8;14 translocation using IGH-MYC (a fusion probe). Materials and Methods: LSI-MYC probe was evaluated using tissue sections from 35 patients. IGH-MYC probe was evaluated using tissue sections from forty patients. Sections were processed for FISH and analyzed using traditional methods. FISH slides were then analyzed using the GenASIs capture and analysis system. Results: Results for LSI-MYC had a high degree of correlation between traditional method of FISH analysis and digital FISH analysis. Results for IGH-MYC had a 100% concordance between traditional method of FISH analysis and digital FISH analysis. Conclusion: Annotated whole slide images of H and E and FISH sections can be digitally aligned, so that areas of tumor within a section can be matched and evaluated with a greater degree of accuracy. Images can be archived permanently, providing a means for examining the results retrospectively. Digital FISH imaging of the MYC translocations provides a better diagnostic tool compared to traditional methods for evaluating lymphomas. PMID:27217970

  14. Let there be bioluminescence: development of a biophotonic imaging platform for in situ analyses of oral biofilms in animal models.

    PubMed

    Merritt, Justin; Senpuku, Hidenobu; Kreth, Jens

    2016-01-01

    In the current study, we describe a novel biophotonic imaging-based reporter system that is particularly useful for the study of virulence in polymicrobial infections and interspecies interactions within animal models. A suite of luciferase enzymes was compared using three early colonizing species of the human oral flora (Streptococcus mutans, Streptococcus gordonii and Streptococcus sanguinis) to determine the utility of the different reporters for multiplexed imaging studies in vivo. Using the multiplex approach, we were able to track individual species within a dual-species oral infection model in mice with both temporal and spatial resolution. We also demonstrate how biophotonic imaging of multiplexed luciferase reporters could be adapted for real-time quantification of bacterial gene expression in situ. By creating an inducible dual-luciferase expressing reporter strain of S. mutans, we were able to exogenously control and measure expression of nlmAB (encoding the bacteriocin mutacin IV) within mice to assess its importance for the persistence ability of S. mutans in the oral cavity. The imaging system described in the current study circumvents many of the inherent limitations of current animal model systems, which should now make it feasible to test hypotheses that were previously impractical to model.

  15. Wide-band IR imaging in the NIR-MIR-FIR regions for in situ analysis of frescoes

    NASA Astrophysics Data System (ADS)

    Daffara, C.; Pezzati, L.; Ambrosini, D.; Paoletti, D.; Di Biase, R.; Mariotti, P. I.; Frosinini, C.

    2011-06-01

    Imaging methods offer several advantages in the field of conservation allowing to perform non-invasive inspection of works of art. In particular, non-invasive techniques based on imaging in different infrared (IR) regions are widely used for the investigation of paintings. Using radiation beyond the visible range, different characteristics of the inspected artwork may be revealed according to the bandwidth acquired. In this paper we present the recent results of a joint project among the two research institutes DIMEG and CNR-INO, and the restoration facility Opificio delle Pietre Dure, concerning the wide-band integration of IR imaging techniques, in the spectral ranges NIR 0.8-2.5 μm, MIR 3-5 μm, and FIR 8-12 μm, for in situ analysis of artworks. A joint, multi-mode use of reflection and thermal bands is proposed for the diagnostics of mural paintings, and it is demonstrated to be an effective tool in inspecting the layered structure. High resolution IR reflectography and, to a greater extent, IR imaging in the 3-5 μm band, are effectively used to characterize the superficial layer of the fresco and to analyze the stratigraphy of different pictorial layers. IR thermography in the 8-12 μm band is used to characterize the support deep structure. The integration of all the data provides a multi- layered and multi-spectral representation of the fresco that yields a comprehensive analysis.

  16. Real time early detection imaging system of failed wounds and heterotopic ossification using unique Raman signatures

    NASA Astrophysics Data System (ADS)

    Papour, Asael; Taylor, Zach; Stafsudd, Oscar; Grundfest, Warren

    2015-03-01

    Our team has established a method to enable imaging of heterotopic ossification and bone growth locations in tissue using Stokes Raman signals with fast acquisition times. This technique relies on the unique Raman signatures of bone to capture parallel, full-field, 1 cm2 field of view, without utilizing a spectrometer. This system was built in mind as a compact complementary tool for in vivo patient monitoring that can offer a high resolution optical characterization for early detection of failed wounds. Preliminary results of bone detection in flesh are presented here and pave the way for further development of this tool in clinical setting.

  17. Hyperspectral imaging with in-line interferometric femtosecond stimulated Raman scattering spectroscopy

    NASA Astrophysics Data System (ADS)

    Dobner, Sven; Fallnich, Carsten

    2014-02-01

    We present the hyperspectral imaging capabilities of in-line interferometric femtosecond stimulated Raman scattering. The beneficial features of this method, namely, the improved signal-to-background ratio compared to other applicable broadband stimulated Raman scattering methods and the simple experimental implementation, allow for a rather fast acquisition of three-dimensional raster-scanned hyperspectral data-sets, which is shown for PMMA beads and a lipid droplet in water as a demonstration. A subsequent application of a principle component analysis displays the chemical selectivity of the method.

  18. Hyperspectral imaging with in-line interferometric femtosecond stimulated Raman scattering spectroscopy.

    PubMed

    Dobner, Sven; Fallnich, Carsten

    2014-02-28

    We present the hyperspectral imaging capabilities of in-line interferometric femtosecond stimulated Raman scattering. The beneficial features of this method, namely, the improved signal-to-background ratio compared to other applicable broadband stimulated Raman scattering methods and the simple experimental implementation, allow for a rather fast acquisition of three-dimensional raster-scanned hyperspectral data-sets, which is shown for PMMA beads and a lipid droplet in water as a demonstration. A subsequent application of a principle component analysis displays the chemical selectivity of the method.

  19. Comparison of hair from rectum cancer patients and from healthy persons by Raman microspectroscopy and imaging

    NASA Astrophysics Data System (ADS)

    Wei, Xiaoli; Wang, Xin; Fang, Yusheng; Huang, Qing

    2013-09-01

    In this work, Raman microspectroscopy and imaging was employed to analyze cancer patients' hair tissue. The comparison between the hair from rectum cancer patients and the hair from healthy people reveals some remarkable differences, such as for the rectum cancer patients, there are more lipids but less content of α-helix proteins in the hair medulla section. Though more statistic data are required to establish universary rules for practical and accurate diagnosis, this work based on case study demonstrates the possibility of applying Raman microspectroscopy to reveal abnormality in non-cancer tissues such as hair in order to predict and diagnose cancers.

  20. Matrix assisted laser desorption/ionization-mass spectrometry imaging (MALDI-MSI) for direct visualization of plant metabolites in situ

    DOE PAGES

    Sturtevant, Drew; Lee, Young -Jin; Chapman, Kent D.

    2015-11-22

    Direct visualization of plant tissues by matrix assisted laser desorption ionization-mass spectrometry imaging (MALDI-MSI) has revealed key insights into the localization of metabolites in situ. Recent efforts have determined the spatial distribution of primary and secondary metabolites in plant tissues and cells. Strategies have been applied in many areas of metabolism including isotope flux analyses, plant interactions, and transcriptional regulation of metabolite accumulation. Technological advances have pushed achievable spatial resolution to subcellular levels and increased instrument sensitivity by several orders of magnitude. Furthermore, it is anticipated that MALDI-MSI and other MSI approaches will bring a new level of understanding tomore » metabolomics as scientists will be encouraged to consider spatial heterogeneity of metabolites in descriptions of metabolic pathway regulation.« less

  1. Identification of lesion subtypes in biopsies of ductal carcinoma in situ of the breast using biomarker ratio imaging microscopy.

    PubMed

    Clark, Andrea J; Petty, Howard R

    2016-01-01

    Although epidemiological studies propose aggressive and non-aggressive forms of ductal carcinoma in situ (DCIS), they cannot be identified with conventional histopathology. We now report a retrospective study of human biopsy samples using biomarker ratio imaging microscopy (BRIM). Using BRIM, micrographs of biomarkers whose expression correlates with breast cancer aggressiveness are divided by micrographs of biomarkers whose expression negatively correlates with aggressiveness to create computed micrographs reflecting aggressiveness. The biomarker pairs CD44/CD24, N-cadherin/E-cadherin, and CD74/CD59 stratified DCIS samples. BRIM identified subpopulations of DCIS lesions with ratiometric properties resembling either benign fibroadenoma or invasive carcinoma samples. Our work confirms the existence of distinct subpopulations of DCIS lesions, which will likely have utility in breast cancer research and clinical practice. PMID:27247112

  2. Identification of lesion subtypes in biopsies of ductal carcinoma in situ of the breast using biomarker ratio imaging microscopy

    PubMed Central

    Clark, Andrea J.; Petty, Howard R.

    2016-01-01

    Although epidemiological studies propose aggressive and non-aggressive forms of ductal carcinoma in situ (DCIS), they cannot be identified with conventional histopathology. We now report a retrospective study of human biopsy samples using biomarker ratio imaging microscopy (BRIM). Using BRIM, micrographs of biomarkers whose expression correlates with breast cancer aggressiveness are divided by micrographs of biomarkers whose expression negatively correlates with aggressiveness to create computed micrographs reflecting aggressiveness. The biomarker pairs CD44/CD24, N-cadherin/E-cadherin, and CD74/CD59 stratified DCIS samples. BRIM identified subpopulations of DCIS lesions with ratiometric properties resembling either benign fibroadenoma or invasive carcinoma samples. Our work confirms the existence of distinct subpopulations of DCIS lesions, which will likely have utility in breast cancer research and clinical practice. PMID:27247112

  3. Screening of adulterants in powdered foods and ingredients using line-scan Raman chemical imaging

    NASA Astrophysics Data System (ADS)

    Qin, Jianwei; Chao, Kuanglin; Kim, Moon S.

    2015-05-01

    A newly developed line-scan Raman imaging system using a 785 nm line laser was used to authenticate powdered foods and ingredients. The system was used to collect hyperspectral Raman images in a wavenumber range of 102-2865 cm-1 from three representative food powders mixed with selected adulterants with a concentration of 0.5%, including milk and melamine, flour and benzoyl peroxide, and starch and maleic anhydride. An acoustic mixer was used to create food adulterant mixtures. All the mixed samples were placed in sample holders with a surface area of 50 mm×50 mm. Spectral and image processing algorithms were developed based on single-band images at unique Raman peaks of the individual adulterants. Chemical images were created to show identification, spatial distribution, and morphological features of the adulterant particles mixed in the food powders. The potential of estimating mass concentrations of the adulterants using the percentages of the adulterant pixels in the chemical images was also demonstrated.

  4. A comparison of methods for in situ discrimination of imaged phase boundaries using electrical capacitance tomography

    NASA Astrophysics Data System (ADS)

    Clark, P. J.; Tsoligkas, A. N.; Simmons, M. J. H.; Robbins, P. T.; Stitt, E. H.

    2016-02-01

    The detection of hard boundaries using tomographic techniques is challenging due to the measurement resolution inherent in the hardware and smoothing effects created during image reconstruction. This paper is concerned with the development of data processing approaches which enable the use of electrical capacitance tomography (ECT) in real-time applications to visualise interfaces in liquid/liquid and solid/liquid systems based upon phase permittivity differences in media with a high di-electric continuum. The methodologies developed were applied to a series of phantoms to investigate their validity as a tool for imaging phase boundaries in two and three phase systems. In an ECT based tomogram, the interface between phases is exhibited as a transition region; by applying a threshold technique based upon known areas of each respective phase within the system, the transient region can be resolved into a sharp interface. The image error of a tomogram, defined as the deviation of all pixels from their theoretical value, has been calculated using a pixel-by-pixel approach; however this requires exact a priori knowledge and is unsuitable for in-line application; the areal method used in this paper requires global phase distribution information thereby allowing for real-time application. A range of threshold values were applied to tomograms of phantoms of varying geometry and the corresponding image error for each threshold value calculated using both the areal and pixel-by-pixel approaches given above. The threshold value yielding lowest image error from this range is further used in the binary images giving improved tomograms with approximately 40% increase in image accuracy when compared with a default threshold value. Close to the sensor wall, the image becomes distorted due to reconstruction errors arising from decreased density in the electrical field lines, resulting in a circular phantom appearing elongated by approximately 10% when positioned near the wall.

  5. Distribution of amygdalin in apricot (Prunus armeniaca) seeds studied by Raman microscopic imaging.

    PubMed

    Krafft, Christoph; Cervellati, Claudia; Paetz, Christian; Schneider, Bernd; Popp, Jürgen

    2012-06-01

    Amygdalin is a cyanogenic glycoside found in the seeds of several plants belonging to the Rosaceae family. Cyanogenic glycosides can be specifically probed by Raman spectroscopy due to an inherent nitrile group which shows a well-resolved band near 2245 cm(-1). In the current study the subcellular distribution of amygdalin in thin apricot (Prunus armeniaca) seed sections is probed by high-resolution Raman imaging with a step size of 2.5 μm. Further, Raman images and line maps were collected from four apricot seeds with step sizes between 30 and 70 μm. The data were processed by functional group mapping and the spectral unmixing algorithm vertex component analysis. Spectral contributions of amygdalin, lipids, and cellulose were identified. One seed had low amygdalin content in its center and higher content toward its epidermis. The other three specimens showed different distributions of amygdalin, with highest concentration in the center and local concentration spots throughout the seed. We conclude from these preliminary results on Raman imaging in apricot seeds that amygdalin is unevenly distributed and its location does not follow the same pattern for all seeds. The observed biological variability of the amygdalin distribution cannot yet be explained satisfactorily and requires further investigation.

  6. Raman spectroscopic imaging as complementary tool for histopathologic assessment of brain tumors

    NASA Astrophysics Data System (ADS)

    Krafft, Christoph; Bergner, Norbert; Romeike, Bernd; Reichart, Rupert; Kalff, Rolf; Geiger, Kathrin; Kirsch, Matthias; Schackert, Gabriele; Popp, Jürgen

    2012-02-01

    Raman spectroscopy enables label-free assessment of brain tissues and tumors based on their biochemical composition. Combination of the Raman spectra with the lateral information allows grading of tumors, determining the primary tumor of brain metastases and delineating tumor margins - even during surgery after coupling with fiber optic probes. This contribution presents exemplary Raman spectra and images collected from low grade and high grade regions of astrocytic gliomas and brain metastases. A region of interest in dried tissue sections encompassed slightly increased cell density. Spectral unmixing by vertex component analysis (VCA) and N-FINDR resolved cell nuclei in score plots and revealed the spectral contributions of nucleic acids, cholesterol, cholesterol ester and proteins in endmember signatures. The results correlated with the histopathological analysis after staining the specimens by hematoxylin and eosin. For a region of interest in non-dried, buffer immersed tissue sections image processing was not affected by drying artifacts such as denaturation of biomolecules and crystallization of cholesterol. Consequently, the results correspond better to in vivo situations. Raman spectroscopic imaging of a brain metastases from renal cell carcinoma showed an endmember with spectral contributions of glycogen which can be considered as a marker for this primary tumor.

  7. Holographic coherent anti-Stokes Raman scattering bio-imaging

    PubMed Central

    Shi, Kebin; Edwards, Perry S.; Hu, Jing; Xu, Qian; Wang, Yanming; Psaltis, Demetri; Liu, Zhiwen

    2012-01-01

    CARS holography captures both the amplitude and the phase of a complex anti-Stokes field, and can perform three-dimensional imaging by digitally focusing onto different depths inside a specimen. The application of CARS holography for bio-imaging is demonstrated. It is shown that holographic CARS imaging of sub-cellular components in live HeLa cells can be achieved. PMID:22808443

  8. Heliosheath ENA images by Cassini/INCA and in-situ hot plasma ion measurements by Voyagers

    NASA Astrophysics Data System (ADS)

    Krimigis, Stamatios; Roelof, Edmond; Mitchell, Donald; Decker, Robert; Dialynas, Konstantinos

    2016-07-01

    The advent of Energetic Neutral Atom (ENA) imaging, (the result of charge-exchange with energetic ions), has revealed the global nature of the heliosheath (HS) at both high ( > 5 keV, Cassini from 10 AU) and low (< 6 keV, IBEX from 1 AU) energies. Voyager 1 (V1) entered the HS in December 2004 at 94 AU and crossed the heliopause (HP) in August 2012 at 121.6 AU, while Voyager 2 (V2) has been in the HS since August 2007. Thus the properties of the HS along the V1, V2 trajectories are now well-established. Portions of the global HS have been imaged by the Cassini/ INCA (Ion and Neutral CAmera) since 2003 with a full image available since 2009, when IBEX global imaging observations also became available. The presence of the two Voyagers measuring ions locally in the HS contemporaneously with INCA global imaging through ENA in overlapping energy bands provides a powerful tool for examining the spatial, temporal, and spectral evolution of the source hot plasma ions and the global variability of the neutral component. Some of the key findings from the Voyagers and INCA measurements are as follows: (a) The HS contains a hot plasma population that carries a substantial part (30-50%) of the total pressure at E > 5 keV, the rest residing below that range, resulting in a beta (particle/magnetic pressure) always > 1, typically > 10. (b) The width of the HS in the direction of V1 is ˜~ 30 AU, but is thought to be larger (40-70 AU) in the southern ecliptic where V2 currently travels. (c) The ENA intensities at E > 5 keV exhibit a correlation with the solar cycle (SC) over the period 2003 to 2014, with minimum intensities in the anti-nose direction observed ˜~ 1.5 yrs after solar minimum followed by a recovery thereafter, and (d) The in situ ion measurements at V2 within the HS also show a similar SC dependence. The totality of the observations, together with the near-contemporaneous variability in intensities of ions in situ in the HS and ENA in the inner heliosphere suggests

  9. Cyanea capillata Bell Kinematics Analysis through Corrected In Situ Imaging and Modeling Using Strategic Discretization Techniques

    PubMed Central

    Villanueva, Alex A.; Priya, Shashank

    2014-01-01

    Obtaining accurate kinematic data of animals is essential for many biological studies and bio-inspired engineering. Many animals, however, are either too large or too delicate to transport to controlled environments where accurate kinematic data can be easily obtained. Often, in situ recordings are the only means available but are often subject to multi-axis motion and relative magnification changes with time leading to large discrepancies in the animal kinematics. Techniques to compensate for these artifacts were applied to a large jellyfish, Cyanea capillata, freely swimming in ocean waters. The bell kinematics were captured by digitizing exumbrella profiles for two full swimming cycles. Magnification was accounted for by tracking a reference point on the ocean floor and by observing the C. capillata exumbrella arclength in order to have a constant scale through the swimming cycles. A linear fit of the top bell section was used to find the body angle with respect to the camera coordinate system. Bell margin trajectories over two swimming cycles confirmed the accuracy of the correction techniques. The corrected profiles were filtered and interpolated to provide a set of time-dependent points along the bell. Discrete models of the exumbrella were used to analyze the bell kinematics. Exumbrella discretization was conducted using three different methods. Fourier series were fitted to the discretized models and subsequently used to analyze the bell kinematics of the C. capillata. The analysis showed that the bell did not deform uniformly over time with different segments lagging behind each other. Looping of the bell trajectory between contraction and relaxation was also present through most of the exumbrella. The bell margin had the largest looping with an outer path during contraction and inner path during relaxation. The subumbrella volume was approximated based on the exumbrella kinematics and was found to increase during contraction. PMID:25541980

  10. Effect of cargo properties on in situ forming implant behavior determined by noninvasive ultrasound imaging

    PubMed Central

    Solorio, Luis; Olear, Alexander M.; Zhou, Haoyan; Beiswenger, Ashlei C.; Exner, Agata A.

    2012-01-01

    Diagnostic ultrasound has been shown to be an effective method for the noninvasive characterization of in situ forming implant behavior both in vivo and in vitro through the evaluation of the echogenic signal that forms as a consequence of the polymer phase transition from liquid to solid. The kinetics of this phase transition have a direct effect on drug release and can be altered through factors that change the mass transfer events of the solvent and aqueous environment, including properties of the entrapped active agent. This study examined the effect of payload properties on implant phase inversion, swelling, drug release, and polymer degradation. Poly(DL-lactide-co-gylcolide) implants were loaded with either: sodium fluorescein, bovine serum albumin (BSA), doxorubicin (Dox), or 1′-dioctadecyl-3,3,3′,3′-tetramethylindocarbocyanine perchlorate (DiI). Fluorescein and Dox were released at near equivalent rates throughout the diffusion phase of release but due to differing drug–matrix interactions, Dox-loaded implants released a lower mass of drug during the degradation phase of release. DiI was not readily released, and due to increased depot hydrophobicity, resulted in significantly lower swelling than the other formulations. The initial echogenicity was higher in Dox-loaded implants than those loaded with fluorescein, but after the initial precipitation, phase inversion and drug release occurred at near equivalent rates for both Dox and fluorescein-loaded implants. Nonlinear mathematical fitting was used to correlate drug release and phase inversion, providing a noninvasive method for evaluating implant release (R2>0.97 for Dox, BSA, and fluorescein; DiI had a correlation coefficient of 0.56). PMID:22712054

  11. Phase-shift effect of amplitude spread function on spectrum and image formation in coherent Raman scattering microspectroscopy.

    PubMed

    Fukutake, Naoki

    2016-03-01

    Coherent Raman scattering microspectroscopy, which includes coherent anti-Stokes Raman scattering (CARS) and stimulated Raman scattering (SRS) microspectroscopy, permits label-free hyperspectral imaging. We report the theoretical study of the phase-shift effect of the impulse response function on the spectral and image-forming properties of coherent Raman scattering microspectroscopy. We show that the spectrum and image are influenced by not only the NA of objective for excitation (NA(ex)) but also that for signal collection (NA(col)), in association with the phase-shift effect. We discuss that, under the condition NA(ex)≠NA(col), both the spectrum and the image become deformed by the phase-shift effect, which can be applied to the direct measurement of the imaginary part of the nonlinear susceptibility in CARS spectroscopy. We point out that, even in SRS microscopy, the nonresonant background can contribute to the image formation and cause the artifact in the image.

  12. Surface-Enhanced Raman Imaging of Intracellular Bioreduction of Chromate in Shewanella oneidensis

    PubMed Central

    Ravindranath, Sandeep P.; Henne, Kristene L.; Thompson, Dorothea K.; Irudayaraj, Joseph

    2011-01-01

    This proposed research aims to use novel nanoparticle sensors and spectroscopic tools constituting surface-enhanced Raman spectroscopy (SERS) and Fluorescence Lifetime imaging (FLIM) to study intracellular chemical activities within single bioremediating microorganism. The grand challenge is to develop a mechanistic understanding of chromate reduction and localization by the remediating bacterium Shewanella oneidensis MR-1 by chemical and lifetime imaging. MR-1 has attracted wide interest from the research community because of its potential in reducing multiple chemical and metallic electron acceptors. While several biomolecular approaches to decode microbial reduction mechanisms exist, there is a considerable gap in the availability of sensor platforms to advance research from population-based studies to the single cell level. This study is one of the first attempts to incorporate SERS imaging to address this gap. First, we demonstrate that chromate-decorated nanoparticles can be taken up by cells using TEM and Fluorescence Lifetime imaging to confirm the internalization of gold nanoprobes. Second, we demonstrate the utility of a Raman chemical imaging platform to monitor chromate reduction and localization within single cells. Distinctive differences in Raman signatures of Cr(VI) and Cr(III) enabled their spatial identification within single cells from the Raman images. A comprehensive evaluation of toxicity and cellular interference experiments conducted revealed the inert nature of these probes and that they are non-toxic. Our results strongly suggest the existence of internal reductive machinery and that reduction occurs at specific sites within cells instead of at disperse reductive sites throughout the cell as previously reported. While chromate-decorated gold nanosensors used in this study provide an improved means for the tracking of specific chromate interactions within the cell and on the cell surface, we expect our single cell imaging tools to be

  13. Detection of malathion in food peels by surface-enhanced Raman imaging spectroscopy and multivariate curve resolution.

    PubMed

    Albuquerque, Carlos D L; Poppi, Ronei J

    2015-06-16

    An analytical methodology was developed for detection of malathion in the peels of tomatoes and Damson plums by surface-enhanced Raman imaging spectroscopy and multivariate curve resolution. To recover the pure spectra and the distribution mapping of the analyzed surfaces, non-negative matrix factorization (NMF), multivariate curve calibration methods with alternating least squares (MCR-ALS) and MCR with weighted alternating least square (MCR-WALS) were utilized. Error covariance matrices were estimated to evaluate the structure of the error over all the data. For the tomato data, NMF-ALS and MCR-ALS presented excellent spectral recovery even in the absence of initial knowledge of the pesticide spectrum. For the Damson plum data, owing to heteroscedastic noise, MCR-WALS produced better results. This methodology enabled detection below to the maximum residue limit permitted for this pesticide. This approach can be implemented for in situ monitoring because it is fast and does not require extensive manipulation of samples, making its use feasible for other fruits and pesticides as well.

  14. Video-rate molecular imaging in vivo with stimulated Raman scattering.

    PubMed

    Saar, Brian G; Freudiger, Christian W; Reichman, Jay; Stanley, C Michael; Holtom, Gary R; Xie, X Sunney

    2010-12-01

    Optical imaging in vivo with molecular specificity is important in biomedicine because of its high spatial resolution and sensitivity compared with magnetic resonance imaging. Stimulated Raman scattering (SRS) microscopy allows highly sensitive optical imaging based on vibrational spectroscopy without adding toxic or perturbative labels. However, SRS imaging in living animals and humans has not been feasible because light cannot be collected through thick tissues, and motion-blur arises from slow imaging based on backscattered light. In this work, we enable in vivo SRS imaging by substantially enhancing the collection of the backscattered signal and increasing the imaging speed by three orders of magnitude to video rate. This approach allows label-free in vivo imaging of water, lipid, and protein in skin and mapping of penetration pathways of topically applied drugs in mice and humans.

  15. Toward One Giga Frames per Second — Evolution of in Situ Storage Image Sensors

    PubMed Central

    Etoh, Takeharu G.; Dao, V. T. Son; Yamada, Tetsuo; Charbon, Edoardo

    2013-01-01

    The ISIS is an ultra-fast image sensor with in-pixel storage. The evolution of the ISIS in the past and in the near future is reviewed and forecasted. To cover the storage area with a light shield, the conventional frontside illuminated ISIS has a limited fill factor. To achieve higher sensitivity, a BSI ISIS was developed. To avoid direct intrusion of light and migration of signal electrons to the storage area on the frontside, a cross-sectional sensor structure with thick pnpn layers was developed, and named “Tetratified structure”. By folding and looping in-pixel storage CCDs, an image signal accumulation sensor, ISAS, is proposed. The ISAS has a new function, the in-pixel signal accumulation, in addition to the ultra-high-speed imaging. To achieve much higher frame rate, a multi-collection-gate (MCG) BSI image sensor architecture is proposed. The photoreceptive area forms a honeycomb-like shape. Performance of a hexagonal CCD-type MCG BSI sensor is examined by simulations. The highest frame rate is theoretically more than 1Gfps. For the near future, a stacked hybrid CCD/CMOS MCG image sensor seems most promising. The associated problems are discussed. A fine TSV process is the key technology to realize the structure. PMID:23567529

  16. Spot counting on fluorescence in situ hybridization in suspension images using Gaussian mixture model

    NASA Astrophysics Data System (ADS)

    Liu, Sijia; Sa, Ruhan; Maguire, Orla; Minderman, Hans; Chaudhary, Vipin

    2015-03-01

    Cytogenetic abnormalities are important diagnostic and prognostic criteria for acute myeloid leukemia (AML). A flow cytometry-based imaging approach for FISH in suspension (FISH-IS) was established that enables the automated analysis of several log-magnitude higher number of cells compared to the microscopy-based approaches. The rotational positioning can occur leading to discordance between spot count. As a solution of counting error from overlapping spots, in this study, a Gaussian Mixture Model based classification method is proposed. The Akaike information criterion (AIC) and Bayesian information criterion (BIC) of GMM are used as global image features of this classification method. Via Random Forest classifier, the result shows that the proposed method is able to detect closely overlapping spots which cannot be separated by existing image segmentation based spot detection methods. The experiment results show that by the proposed method we can obtain a significant improvement in spot counting accuracy.

  17. Capturing a failure of an ASIC in-situ, using infrared radiometry and image processing software

    NASA Technical Reports Server (NTRS)

    Ruiz, Ronald P.

    2003-01-01

    Failures in electronic devices can sometimes be tricky to locate-especially if they are buried inside radiation-shielded containers designed to work in outer space. Such was the case with a malfunctioning ASIC (Application Specific Integrated Circuit) that was drawing excessive power at a specific temperature during temperature cycle testing. To analyze the failure, infrared radiometry (thermography) was used in combination with image processing software to locate precisely where the power was being dissipated at the moment the failure took place. The IR imaging software was used to make the image of the target and background, appear as unity. As testing proceeded and the failure mode was reached, temperature changes revealed the precise location of the fault. The results gave the design engineers the information they needed to fix the problem. This paper describes the techniques and equipment used to accomplish this failure analysis.

  18. Neutron, fluorescence, and optical imaging: An in situ combination of complementary techniques

    SciTech Connect

    Wagner, D.; Egelhaaf, S. U.; Hermes, H. E.; Börgardts, M.; Müller, T. J. J.; Grünzweig, C.; Lehmann, E.

    2015-09-15

    An apparatus which enables the simultaneous combination of three complementary imaging techniques, optical imaging, fluorescence imaging, and neutron radiography, is presented. While each individual technique can provide information on certain aspects of the sample and their time evolution, a combination of the three techniques in one setup provides a more complete and consistent data set. The setup can be used in transmission and reflection modes and thus with optically transparent as well as opaque samples. Its capabilities are illustrated with two examples. A polymer hydrogel represents a transparent sample and the diffusion of fluorescent particles into and through this polymer matrix is followed. In reflection mode, the absorption of solvent by a nile red-functionalized mesoporous silica powder and the corresponding change in fluorescent signal are studied.

  19. Novel MEMS-based gas-cell/heating specimen holder provides advanced imaging capabilities for in situ reaction studies.

    PubMed

    Allard, Lawrence F; Overbury, Steven H; Bigelow, Wilbur C; Katz, Michael B; Nackashi, David P; Damiano, John

    2012-08-01

    In prior research, specimen holders that employ a novel MEMS-based heating technology (Aduro™) provided by Protochips Inc. (Raleigh, NC, USA) have been shown to permit sub-Ångström imaging at elevated temperatures up to 1,000°C during in situ heating experiments in modern aberration-corrected electron microscopes. The Aduro heating devices permit precise control of temperature and have the unique feature of providing both heating and cooling rates of 10⁶°C/s. In the present work, we describe the recent development of a new specimen holder that incorporates the Aduro heating device into a "closed-cell" configuration, designed to function within the narrow (2 mm) objective lens pole piece gap of an aberration-corrected JEOL 2200FS STEM/TEM, and capable of exposing specimens to gases at pressures up to 1 atm. We show the early results of tests of this specimen holder demonstrating imaging at elevated temperatures and at pressures up to a full atmosphere, while retaining the atomic resolution performance of the microscope in high-angle annular dark-field and bright-field imaging modes.

  20. A Comparison of Auroral In-Situ Rocket Electron Measurements and Ground-Based Multi-spectral EMCCD Imaging

    NASA Astrophysics Data System (ADS)

    Grubbs, G. A., II; Samara, M.; Michell, R.; Hampton, D.; Hecht, J. H.

    2015-12-01

    The Ground-to-Rocket Electrodynamics-Electrons Correlative Experiment (GREECE) mission successfully launched from Poker Flat, Alaska on 03 March 2014 at 11:09:50 UT and reached an apogee of approximately 335 km during a luminous auroral event. Multiple ground-based electron-multiplying charge-coupled device (EMCCD) imagers were positioned at Venetie, Alaska and aimed along magnetic zenith in order to observe the brightness of different auroral emission lines (427.8, 557.7, and 844.6 nm with a 47 degree field of view) at the magnetic footpoint of the payload, near apogee. Emission line brightness data are presented at the footpoint of the rocket flight and compared with electron characteristics taken by the Acute Precipitating Electron Spectrometer (APES) on-board instrument. Ratios of different auroral emission lines are combined with previously published models in order to estimate the characteristic energy of the incident electron population, which is directly compared to the APES data for validation. Our goal is to describe the auroral emissions produced from a known precipitating electron distribution, such that we can more accurately use ground-based imaging and photometry to infer the characteristics of the precipitating electrons. These techniques can then be applied over larger scales and longer times, when only multi-spectral imaging data are available with no corresponding in situ data.

  1. The potential for imaging of in situ damage in inflatable space structures.

    SciTech Connect

    Madaras, Eric I.

    2007-07-01

    NASA is investigating the use of inflatable habitat structures for orbital transfer and planetary applications. Since space structures are vulnerable to damage from micrometeoroid and orbital debris, it is important to investigate means of detecting such damage. This study is an investigation into methods for performing non-destructive evaluation (NDE) on inflatable habitat modules. Results of this work showed that various electromagnetic imaging modalities from microwaves to terahertz imaging have the greatest potential for a viable, portable, NDE tool which could possibly be deployed aboard an inflatable habitat module.

  2. The Potential for Imaging in Situ Damage in Inflatable Space Structures

    NASA Technical Reports Server (NTRS)

    Madaras, Eric I.; Anastasi, Robert F.; Seebo, Jeffrey P.; Studor, George; McMakin, Douglas L.; Nellums, Robert; Winfree, William P.

    2007-01-01

    NASA is investigating the use of inflatable habitat structures for orbital transfer and planetary applications. Since space structures are vulnerable to damage from micrometeoroid and orbital debris, it is important to investigate means of detecting such damage. This study is an investigation into methods for performing non-destructive evaluation (NDE) on inflatable habitat modules. Results of this work showed that various electromagnetic imaging modalities from microwaves to terahertz imaging have the greatest potential for a viable, portable, NDE tool which could possibly be deployed aboard an inflatable habitat module.

  3. Photoacoustic imaging and surface-enhanced Raman spectroscopy using dual modal contrast agents

    NASA Astrophysics Data System (ADS)

    Park, Sungjo; Lee, Seunghyun; Cha, Myeonggeun; Jeong, Cheolhwan; Kang, Homan; Park, So Yeon; Lee, Yoon-sik; Jeong, Daehong; Kim, Chulhong

    2016-03-01

    Recently, photoacoustic tomography (PAT) has emerged as a remarkable non-invasive imaging modality that provides a strong optical absorption contrast, high ultrasonic resolution, and great penetration depth. Thus, PAT has been widely used as an in vivo preclinical imaging tool. Surface-enhanced Raman spectroscopy (SERS) is another attractive sensing technology in biological research because it offers highly sensitive chemical analyses and multiplexed detection. By performing dual-modal imaging of SERS and PAT, high-resolution structural PAT imaging and high-sensitivity SERS sensing can be achieved. At the same time, it is equally important to develop a dual modal contrast agent for this purpose. To perform both PAT and SERS, we synthesized PEGylated silver bumpy nanoshells (AgBSs). The AgBSs generate strong PA signals owing to their strong optical absorption properties as well as sensitive SERS signals because of the surface plasmon resonance effect. Then, multiplexed Raman chemicals were synthesized to enhance the sensitivity of Raman. We have photoacoustically imaged the sentinel lymph nodes of small animals after intradermal injection of multiplexed agents. Furthermore, the chemical composition of each agent has been distinguished through SERS.

  4. Improving in situ data acquisition using training images and a Bayesian mixture model

    NASA Astrophysics Data System (ADS)

    Abdollahifard, Mohammad Javad; Mariethoz, Gregoire; Pourfard, Mohammadreza

    2016-06-01

    Estimating the spatial distribution of physical processes using a minimum number of samples is of vital importance in earth science applications where sampling is costly. In recent years, training image-based methods have received a lot of attention for interpolation and simulation. However, training images have never been employed to optimize spatial sampling process. In this paper, a sequential compressive sampling method is presented which decides the location of new samples based on a training image. First, a Bayesian mixture model is developed based on the training patterns. Then, using this model, unknown values are estimated based on a limited number of random samples. Since the model is probabilistic, it allows estimating local uncertainty conditionally to the available samples. Based on this, new samples are sequentially extracted from the locations with maximum uncertainty. Experiments show that compared to a random sampling strategy, the proposed supervised sampling method significantly reduces the number of samples needed to achieve the same level of accuracy, even when the training image is not optimally chosen. The method has the potential to reduce the number of observations necessary for the characterization of environmental processes.

  5. In situ monitoring of surgical flap viability using THz imaging (Conference Presentation)

    NASA Astrophysics Data System (ADS)

    Bajwa, Neha; Sung, Shijun; Grundfest, Warren; Taylor, Zachary

    2016-03-01

    This paper explores the utility of reflective THz imaging to assess the viability of surgical flaps. Flap surgery is a technique where tissue is harvested from a donor site and moved to a recipient while keeping the blood supply intact. This technique is common in head and neck tumor resection surgery where the reconstruction of complex and sensitive anatomic structures is routine following the resection of large and/or invasive tumors. Successful flap surgery results in tissue that is sufficiently perfused with both blood and extracellular water. If insufficient fluid levels are maintained, the flap tissue becomes necrotic and must be excised immediately to prevent infection developing and spreading to the surrounding areas. The goal of this work is to investigate the hydration of surgical flaps and correlate image features to successful graft outcomes. Advancement flaps were created on the abdomens of rat models. One rat model was labeled control and care was taken to ensure a successful flap outcome. The flap on the second rat was compromised with restricted blood flow and allowed to fail. The flaps of both rats were imaged once a day over the course of a week at which point the compromised flap had begun to show signs of necrosis. Significant differences in tissue water content were observed between rats over the experimental period. The results suggest that THz imaging may enable early assessment of flap viability.

  6. In-situ imaging of charge carriers in an electrochemical cell.

    SciTech Connect

    Gerald, R. E. II

    1998-01-30

    A toroid cavity nuclear magnetic resonance (NMR) detector capable of quantitatively recording radial concentration profiles, diffusion constants, displacements of charge carriers, and radial profiles of spin-lattice relaxation time constants was employed to investigate the charge/discharge cycle of a solid-state electrochemical cell. One-dimensional radial concentration profiles (1D-images) of ions solvated in a polyethylene oxide matrix were recorded by {sup 19}F and {sup 7}Li NMR for several cells. A sequence of {sup 19}F NMR images, recorded at different stages of cell polarization, revealed the evolution of a region of the polymer depleted of charge carriers. From these images it is possible to extract the transference number for the Li{sup +} ion. Spatially localized diffusion coefficients and spin-lattice relaxation time constants can be measured simultaneously for the ions in the polymer electrolyte by a spin-labeling method that employs the radial B{sub 1}-field gradient of the toroid cavity. A spatial resolution of 7 {micro}m near the working electrode was achieved with a gradient strength of 800 gauss/cm. With this apparatus, it is also possible to investigate novel intercalation anode materials for lithium ion storage. These materials are coated onto the working electrode in a thin film. The penetration depth of lithium cations in these films can be imaged at different times in the charge/discharge cycle of the battery.

  7. High-Speed Tandem Mass Spectrometric in Situ Imaging by Nanospray Desorption Electrospray Ionization Mass Spectrometry

    SciTech Connect

    Lanekoff, Ingela T.; Burnum-Johnson, Kristin E.; Thomas, Mathew; Short, Joshua TL; Carson, James P.; Cha, Jeeyeon; Dey, Sudhansu K.; Yang, Pengxiang; Prieto Conaway, Maria C.; Laskin, Julia

    2013-10-15

    Nanospray desorption electrospray ionization (nano-DESI) combined with tandem mass spectrometry (MS/MS), high-resolution mass analysis (m/m=17,500 at m/z 200), and rapid spectral acquisition enabled simultaneous imaging and identification of more than 300 molecules from 92 selected m/z windows (± 1 Da) with a spatial resolution of better than 150 um. Uterine sections of implantation sites on day 6 of pregnancy were analyzed in the ambient environment without any sample pre-treatment. MS/MS imaging was performed by scanning the sample under the nano-DESI probe at 10 um/s while acquiring higher-energy collision-induced dissociation (HCD) spectra for a targeted inclusion list of 92 m/z values at a rate of ~6.3 spectra/s. Molecular ions and their corresponding fragments, separated using high-resolution mass analysis, were assigned based on accurate mass measurement. Using this approach, we were able to identify and image both abundant and low-abundance isobaric species within each m/z window. MS/MS analysis enabled efficient separation and identification of isobaric sodium and potassium adducts of phospholipids. Furthermore, we identified several metabolites associated with early pregnancy and obtained the first 2D images of these molecules.

  8. QUANTITATIVE IMAGING AND STATISTICAL ANALYSIS OF FLUORESCENCE IN SITU HYBRIDIZATION (FISH) OF AUREOBASIDIUM PULLULANS. (R823845)

    EPA Science Inventory

    Abstract

    Image and multifactorial statistical analyses were used to evaluate the intensity of fluorescence signal from cells of three strains of A. pullulans and one strain of Rhodosporidium toruloides, as an outgroup, hybridized with either a universal o...

  9. Development of in-situ imaging tools to quantify vegetation stress, plant mortality, and species composition

    NASA Astrophysics Data System (ADS)

    Goulden, M.

    2014-12-01

    We have developed and deployed an imaging system at an eddy covariance site in a Southern California Pinyon-Juniper woodland; our goals are to quantify the species-level patterns of stress and mortality over time, and also to learn how to better interpret the Landsat record. Our imaging system combines a four channel spectrometer with cameras that are sensitive to Visible, Near Infrared (NIR), Shortwave Infrared (SWIR), and Thermal radiation; these cameras include filters that mimic the spectral sensitivity of several Landsat bands. The cameras and spectrometer foreoptic are positioned on a pan-tilt mount on the tower that scans a 300o x 90o area every hour and allows us to collect images of hundreds of distinct plants. The imaging system is being used to test several approaches that have been proposed to detect vegetation stress, mortality, and species composition. We are exploring the potential to detect stomatal closure and stress by: a) increased canopy temperature with decreased evaporative cooling, b) Photochemical Reflectance Index (PRI), c) Fraunhofer line fluorescence, and d) water band indices. Similarly, we are exploring the po