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Sample records for in-situ raman imaging

  1. Novel, in-situ Raman and fluorescence measurement techniques: Imaging using optical waveguides

    NASA Astrophysics Data System (ADS)

    Carter, Jerry Chance

    The following dissertation describes the development of methods for performing standoff and in- situ Raman and fluorescence spectroscopy for chemical imaging and non-imaging analytical applications. The use of Raman spectroscopy for the in- situ identification of crack cocaine and cocaine.HCl using a fiberoptic Raman probe and a portable Raman spectrograph has been demonstrated. We show that the Raman spectra of both forms of cocaine are easily distinguishable from common cutting agents and impurities such as benzocaine and lidocaine. We have also demonstrated the use of Raman spectroscopy for in-situ identification of drugs separated by thin layer chromatography. We have investigated the use of small, transportable, Raman systems for standoff Raman spectroscopy (e.g. <20 m). For this work, acousto-optical (AOTF) and liquid crystal tunable filters (LCTF) are being used both with, and in place of dispersive spectrographs and fixed filtering devices. In addition, we improved the flexibility of the system by the use of a modified holographic fiber-optic probe for light and image collection. A comparison of tunable filter technologies for standoff Raman imaging is discussed along with the merits of image transfer devices using small diameter image guides. A standoff Raman imaging system has been developed that utilizes a unique polymer collection mirror. The techniques used to produce these mirrors make it easy to design low f/# polymer mirrors. The performance of a low f/# polymer mirror system for standoff Raman chemical imaging has been demonstrated and evaluated. We have also demonstrated remote Raman hyperspectral imaging using a dimension-reduction, 2-dimensional (2-D) to 1-dimensional (1-D), fiber optic array. In these studies, a modified holographic fiber-optic probe was combined with the dimension-reduction fiber array for remote Raman imaging. The utility of this setup for standoff Raman imaging is demonstrated by monitoring the polymerization of

  2. In-situ Raman Spectroscopic Imaging of a Mussel Coating and Adhesive

    NASA Astrophysics Data System (ADS)

    Mašić, Admir; Harrington, Matthew; Waite, J. Herbert; Fratzl, Peter

    2010-08-01

    The mussel has evolved a very interesting and efficient way of attaching to hard substrata in wave-swept rocky seashores. This is enabled by a bundle of fine protein based threads called the byssus. The byssus is emerging as an effective model system for studying the requirements for underwater adhesion, wear resistance and combined hardness and extensibility (1, 2). Careful secretion of different mussel foot proteins (mfp) combined with some metal ions (Fe3+, Zn2+ etc.) allows the mussel to tune properties and optimize function of diverse parts of byssus thread (3). Here we report in-situ high-resolution Raman spectroscopic imaging of the byssal coating and plaque showing micron level spatial distribution of various proteins and their interaction with Fe3+ using specific Resonance Raman (RR) spectral features. 3,4-dihydroxyphenylalanine (dopa) is a strong chelator of Fe3+ within a specific pH window (stability constant of [Fe(dopa)3]3- complex can reach values up to Kf˜1045). The charge transfer from the catechol ring to Fe(III) characteristic of such complexes generates absorption bands in whole visible a part of near infra-red spectrum. As a consequence, a characteristic RR signal can be detected using 785 nm laser line. This method was recently utilized to localize Fe-dopa complexation of mfp-1 in the protective cuticles of mussel byssal threads (2), and the same approach was taken here to investigate metal complexation in the plaque. In figure 1A a scanning electron micrograph of a cross section of plaque is presented. Characteristic foam-like morphology of internal part of the plaque is visible. Figure 1B shows the results of Raman spectroscopic imaging (for specifications see reference (2)) on a thin (10 μm) section of the byssus plaque integrated for Fe3+-dopa complexation bands (500-650 cm-1, see Fig. 1D). The components distribution map in Fig. 1C was obtained using the basis analysis and image color combination functions (Witec Project software). In

  3. 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

  4. In situ label-free imaging of hemicellulose in plant cell walls using stimulated Raman scattering microscopy

    SciTech Connect

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

    2016-11-22

    Plant hemicellulose (largely xylan) is an excellent feedstock for renewable energy production and second only to cellulose in abundance. Beyond a source of fermentable sugars, xylan constitutes a critical polymer in the plant cell wall, where its precise role in wall assembly, maturation, and deconstruction remains primarily hypothetical. Effective detection of xylan, particularly by in situ imaging of xylan in the presence of other biopolymers, would provide critical information for tackling the challenges of understanding the assembly and enhancing the liberation of xylan from plant materials. Raman-based imaging techniques, especially the highly sensitive stimulated Raman scattering (SRS) microscopy, have proven to be valuable tools for label-free imaging. However, due to the complex nature of plant materials, especially those same chemical groups shared between xylan and cellulose, the utility of specific Raman vibrational modes that are unique to xylan have been debated. Here, we report a novel approach based on combining spectroscopic analysis and chemical/enzymatic xylan removal from corn stover cell walls, to make progress in meeting this analytical challenge. We have identified several Raman peaks associated with xylan content in cell walls for label-free in situ imaging xylan in plant cell wall. We demonstrated that xylan can be resolved from cellulose and lignin in situ using enzymatic digestion and label-free SRS microscopy in both 2D and 3D. As a result, we believe that this novel approach can be used to map xylan in plant cell walls and that this ability will enhance our understanding of the role played by xylan in cell wall biosynthesis and deconstruction.

  5. In situ label-free imaging of hemicellulose in plant cell walls using stimulated Raman scattering microscopy

    DOE PAGES

    Zeng, Yining; Yarbrough, John M.; Mittal, Ashutosh; ...

    2016-11-22

    Plant hemicellulose (largely xylan) is an excellent feedstock for renewable energy production and second only to cellulose in abundance. Beyond a source of fermentable sugars, xylan constitutes a critical polymer in the plant cell wall, where its precise role in wall assembly, maturation, and deconstruction remains primarily hypothetical. Effective detection of xylan, particularly by in situ imaging of xylan in the presence of other biopolymers, would provide critical information for tackling the challenges of understanding the assembly and enhancing the liberation of xylan from plant materials. Raman-based imaging techniques, especially the highly sensitive stimulated Raman scattering (SRS) microscopy, have provenmore » to be valuable tools for label-free imaging. However, due to the complex nature of plant materials, especially those same chemical groups shared between xylan and cellulose, the utility of specific Raman vibrational modes that are unique to xylan have been debated. Here, we report a novel approach based on combining spectroscopic analysis and chemical/enzymatic xylan removal from corn stover cell walls, to make progress in meeting this analytical challenge. We have identified several Raman peaks associated with xylan content in cell walls for label-free in situ imaging xylan in plant cell wall. We demonstrated that xylan can be resolved from cellulose and lignin in situ using enzymatic digestion and label-free SRS microscopy in both 2D and 3D. As a result, we believe that this novel approach can be used to map xylan in plant cell walls and that this ability will enhance our understanding of the role played by xylan in cell wall biosynthesis and deconstruction.« less

  6. In situ Raman mapping of art objects.

    PubMed

    Lauwers, D; Brondeel, Ph; Moens, L; Vandenabeele, P

    2016-12-13

    Raman spectroscopy has grown to be one of the techniques of interest for the investigation of art objects. The approach has several advantageous properties, and the non-destructive character of the technique allowed it to be used for in situ investigations. However, compared with laboratory approaches, it would be useful to take advantage of the small spectral footprint of the technique, and use Raman spectroscopy to study the spatial distribution of different compounds. In this work, an in situ Raman mapping system is developed to be able to relate chemical information with its spatial distribution. Challenges for the development are discussed, including the need for stable positioning and proper data treatment. To avoid focusing problems, nineteenth century porcelain cards are used to test the system. This work focuses mainly on the post-processing of the large dataset which consists of four steps: (i) importing the data into the software; (ii) visualization of the dataset; (iii) extraction of the variables; and (iv) creation of a Raman image. It is shown that despite the challenging task of the development of the full in situ Raman mapping system, the first steps are very promising.This article is part of the themed issue 'Raman spectroscopy in art and archaeology'. © 2016 The Author(s).

  7. In situ Raman mapping of art objects

    NASA Astrophysics Data System (ADS)

    Lauwers, D.; Brondeel, Ph.; Moens, L.; Vandenabeele, P.

    2016-12-01

    Raman spectroscopy has grown to be one of the techniques of interest for the investigation of art objects. The approach has several advantageous properties, and the non-destructive character of the technique allowed it to be used for in situ investigations. However, compared with laboratory approaches, it would be useful to take advantage of the small spectral footprint of the technique, and use Raman spectroscopy to study the spatial distribution of different compounds. In this work, an in situ Raman mapping system is developed to be able to relate chemical information with its spatial distribution. Challenges for the development are discussed, including the need for stable positioning and proper data treatment. To avoid focusing problems, nineteenth century porcelain cards are used to test the system. This work focuses mainly on the post-processing of the large dataset which consists of four steps: (i) importing the data into the software; (ii) visualization of the dataset; (iii) extraction of the variables; and (iv) creation of a Raman image. It is shown that despite the challenging task of the development of the full in situ Raman mapping system, the first steps are very promising. This article is part of the themed issue "Raman spectroscopy in art and archaeology".

  8. Sequential electrochemical unzipping of single-walled carbon nanotubes to graphene ribbons revealed by in situ Raman spectroscopy and imaging.

    PubMed

    John, Robin; Shinde, Dhanraj B; Liu, Lili; Ding, Feng; Xu, Zhiping; Vijayan, Cherianath; Pillai, Vijayamohanan K; Pradeep, Thalappil

    2014-01-28

    We report an in situ Raman spectroscopic and microscopic investigation of the electrochemical unzipping of single-walled carbon nanotubes (SWNTs). Observations of the radial breathing modes (RBMs) using Raman spectral mapping reveal that metallic SWNTs are opened up rapidly followed by gradual unzipping of semiconducting SWNTs. Consideration of the resonant Raman scattering theory suggests that two metallic SWNTs with chiralities (10, 4) and (12, 0) get unzipped first at a lower electrode potential (0.36 V) followed by the gradual unzipping of another two metallic tubes, (9, 3) and (10, 1), at a relatively higher potential (1.16 V). The semiconducting SWNTs with chiralities (11, 7) and (12, 5), however, get open up gradually at ±1.66 V. A rapid decrease followed by a subsequent gradual decrease in the metallicity of the SWNT ensemble as revealed from a remarkable variation of the peak width of the G band complies well with the variations of RBM. Cyclic voltammetry also gives direct evidence for unzipping in terms of improved capacitance after oxidation followed by more important removal of oxygen functionalities during the reduction step, as reflected in subtle changes of the morphology confirming the formation of graphene nanoribbons. The density functional-based tight binding calculations show additional dependence of chirality and diameter of nanotubes on the epoxide binding energies, which is in agreement with the Raman spectroscopic results and suggests a possible mechanism of unzipping determined by combined effects of the structural characteristics of SWNTs and applied field.

  9. Evaluating drug delivery with salt formation: Drug disproportionation studied in situ by ATR-FTIR imaging and Raman mapping.

    PubMed

    Ewing, Andrew V; Wray, Patrick S; Clarke, Graham S; Kazarian, Sergei G

    2015-01-01

    Two different vibrational spectroscopic approaches, ATR-FTIR spectroscopic imaging and Raman mapping, were used to investigate the components within a tablet containing an ionised drug during dissolution experiments. Delivering certain drugs in their salt form is a method that can be used to improve the bioavailability and dissolution of the poorly aqueous soluble materials. However, these ionised species have a propensity to covert back to their thermodynamically favourable free acid or base forms. Dissolution experiments of the ionised drug in different aqueous media resulted in conversion to the more poorly soluble free acid form, which is detrimental for controlled drug release. This study investigates the chemical changes occurring to formulations containing a development ionised drug (37% by weight), in different aqueous pH environments. Firstly, dissolution in a neutral medium was studied, showing that there was clear release of ionised monosodium form of the drug from the tablet as it swelled in the aqueous medium. There was no presence of any drug in the monohydrate free acid form detected in these experiments. Dissolution in an acidic (0.1M HCl) solution showed disproportionation forming the free acid form. Disproportionation occurred rapidly upon contact with the acidic solution, initially resulting in a shell of the monohydrate free acid form around the tablet edges. This slowed ingress of the solution into the tablet before full conversion of the ionised form to the free acid form was characterised in the spectroscopic data.

  10. In situ cellular level Raman spectroscopy of the thyroid

    PubMed Central

    Law, Alan Wing Lun; Ahmed, Rafay; Cheung, Tsz Wing; Mak, Chun Yu; Lau, Condon

    2017-01-01

    We report a novel Raman spectroscopy method for in situ cellular level analysis of the thyroid. Thyroids are harvested from control and lithium treated mice. Lithium is used to treat bipolar disorder, but affects thyroid function. Raman spectra are acquired with a confocal setup (514 nm laser, 20 µm spot) focused on a follicular lumen. Raman peaks are observed at 1440, 1656, and 1746 cm−1, corresponding to tyrosine, an important amino acid for protein synthesis. Peaks are also observed at 563, 1087, 1265 and 1301 cm−1. With lithium, the tyrosine peaks increase, indicating tyrosine buildup. Raman spectroscopy can study the impact of many exogenous treatments on thyroid biochemistry. PMID:28270975

  11. In situ cellular level Raman spectroscopy of the thyroid.

    PubMed

    Law, Alan Wing Lun; Ahmed, Rafay; Cheung, Tsz Wing; Mak, Chun Yu; Lau, Condon

    2017-02-01

    We report a novel Raman spectroscopy method for in situ cellular level analysis of the thyroid. Thyroids are harvested from control and lithium treated mice. Lithium is used to treat bipolar disorder, but affects thyroid function. Raman spectra are acquired with a confocal setup (514 nm laser, 20 µm spot) focused on a follicular lumen. Raman peaks are observed at 1440, 1656, and 1746 cm(-1), corresponding to tyrosine, an important amino acid for protein synthesis. Peaks are also observed at 563, 1087, 1265 and 1301 cm(-1). With lithium, the tyrosine peaks increase, indicating tyrosine buildup. Raman spectroscopy can study the impact of many exogenous treatments on thyroid biochemistry.

  12. Cell design and image analysis for in situ Raman mapping of inhomogeneous state-of-charge profiles in lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Fang, Shuyu; Yan, Min; Hamers, Robert J.

    2017-06-01

    The study of inhomogeneous battery failure processes requires proper tools with high spatial resolving power. Here we describe a simple way to adapt industry-standard coin cells to enable in situ Raman mapping of lithium-ion battery materials. We describe the important cell design parameters and validate that the design achieves a uniform potential distribution within the region probed by Raman. We further validate that the cell yields electrical performance characteristics equivalent to a standard, non-modified coin cell. Using this cell, we probe the local charging profiles of LiNi0.5Mn0.3Co0.2O2 (;NMC;) particles during cycling and demonstrate the ability to achieve spatial maps of the Raman spectra. In order to reduce the effects of local topography, we further analyze these data by numerically extracting the local frequency of the A1g vibrational mode, which is sensitive to the local extent of lithiation, and producing spatial maps of the local frequency of the A1g mode. This work demonstrates a way to collect and analyze high quality in situ spectra with an easy-to-implement cell design that can be applied to a wide range of electrode materials.

  13. 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.

  14. 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.

  15. Raman microscopy and surface-enhanced Raman scattering (SERS) for in situ analysis of biofilms.

    PubMed

    Ivleva, Natalia P; Wagner, Michael; Horn, Harald; Niessner, Reinhard; Haisch, Christoph

    2010-08-01

    Biofilms are communities of micro-organisms enclosed in a matrix of extracellular polymeric substances (EPS). They represent a ubiquitous form of microbial life on Earth. Detailed information on chemical composition and structure of the EPS matrix is relevant in medicine, industry and technological processes. Raman microscopy (RM) provides whole-organism fingerprints for biological samples with spatial resolution in the microm range and enables correlations between optical and chemical images to be made. Low water background makes RM beneficial for in situ studies of biofilms, since water is the major component of the biofilm matrix. In this paper we discuss the feasibility of RM for chemical characterization of different structures in a multispecies biofilm matrix, including microbial constituents and EPS. We show that by improving the sensitivity of RM with surface-enhanced Raman scattering (SERS) one can perform rapid biofilm analysis. In particular, by choosing appropriate SERS substrates and solving the problem of SERS measurement reproducibility one can carry out in situ study of different components in the complex biofilm matrix. (c) 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. 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. Copyright © 2015 Elsevier B.V. All rights reserved.

  17. Confocal Raman Microscopy on in-situ Structural Evolution of Polyolefin Blends

    NASA Astrophysics Data System (ADS)

    Chang, Wansoo; Jeon, Byungho; Lee, Jong-Won; Ryu, Chang Y.

    2011-03-01

    Polyolefins account for more than half of world-wide consumption of plastic materials, and are typically blended with fillers and other types of polymers in applications. In particular, understanding the miscibility and phase behaviors of polyolefin blends is important for the advancement of a wide array of new applications in medicine, packaging, and other fields. We have used Confocal Raman Microscopy to take the advantages of it capability to locally probe the transformation of physical states in polymeric materials and to characterize morphology of polyolefin blends in-situ for lateral and in-depth imaging with a micron-scale spatial resolution. Upon distinct changes of Raman spectra associated with the melting of semicrystaline polyolefins, we report the in-situ morphological changes upon heating and cooling of polyethylene-polyethylene and polypropylene-polyethylene using confocal Raman microscopy with heating stage. NSF MRI-0722563.

  18. 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.

  19. Precise determination of graphene functionalization by in situ Raman spectroscopy

    PubMed Central

    Vecera, Philipp; Chacón-Torres, Julio C.; Pichler, Thomas; Reich, Stephanie; Soni, Himadri R.; Görling, Andreas; Edelthalhammer, Konstantin; Peterlik, Herwig; Hauke, Frank; Hirsch, Andreas

    2017-01-01

    The verification of a successful covalent functionalization of graphene and related carbon allotropes can easily be carried out by Raman spectroscopy. Nevertheless, the unequivocal assignment and resolution of individual lattice modes associated with the covalent binding of addends was elusive up to now. Here we present an in situ Raman study of a controlled functionalization of potassium intercalated graphite, revealing several new bands appearing in the D-region of the spectrum. The evolution of these bands with increasing degree of functionalization from low to moderate levels provides a basis for the deconvolution of the different components towards quantifying the extent of functionalization. By complementary DFT calculations we were able to identify the vibrational changes in the close proximity of the addend bearing lattice carbon atoms and to assign them to specific Raman modes. The experimental in situ observation of the developing functionalization along with the reoxidation of the intercalated graphite represents an important step towards an improved understanding of the chemistry of graphene. PMID:28480893

  20. 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. Copyright © 2016 Elsevier B.V. All rights reserved.

  1. 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

  2. In situ Raman and X-ray spectroscopies to monitor microbial activities under high hydrostatic pressure.

    PubMed

    Oger, Phil M; Daniel, Isabelle; Picard, Aude

    2010-02-01

    Until recently, monitoring of cells and cellular activities at high hydrostatic pressure (HHP) was mainly limited to ex situ observations. Samples were analyzed prior to and following the depressurization step to evaluate the effect of the pressure treatment. Such ex situ measurements have several drawbacks: (i) it does not allow for kinetic measurements and (ii) the depressurization step often leads to artifactual measurements. Here, we describe recent advances in diamond anvil cell (DAC) technology to adapt it to the monitoring of microbial processes in situ. The modified DAC is asymmetrical, with a single anvil and a diamond window to improve imaging quality and signal collection. Using this novel DAC combined to Raman and X-ray spectroscopy, we monitored the metabolism of glucose by baker's yeast and the reduction of selenite by Agrobacterium tumefaciens in situ under HHP. In situ spectroscopy is also a promising tool to study piezophilic microorganisms.

  3. Raman spectroscopy - in situ characterization of growth and surface processes

    NASA Astrophysics Data System (ADS)

    Perkins, James Robert

    The goal of this thesis is to expand on the usefulness of Raman spectroscopy as an in situ probe to aid in the growth and implementation of electronic, optical, and biodetection materials. We accomplish this goal by developing two diverse optical characterization projects. In the first project, an autoclave similar to those used in solvothermal growth which has been outfitted with an optical window is used to collect vibrational spectra of solvents and mineralizers commonly used in the ammonothermal growth of gallium nitride. Secondly, novel silver nanowires created by ferroelectric lithography are evaluated by surface enhanced micro-Raman spectroscopy for use as surface enhanced substrates for low detection limit or single molecule bio-detectors. Raman spectroscopy is already a widely accepted method to characterize and identify a wide variety of materials. Vibrational spectra can yield much information on the presence of chemical species as well as information regarding the phase and interactive properties. Because Raman spectroscopy is a generally non-intrusive technique it is ideal for analysis of hazardous or far-from-ambient liquids, gases, or solids. This technique is used in situ to characterize crystal growth and surface enhanced photochemistry. The phenomenon of Surface Enhanced Raman Spectroscopy (SERS) has been observed in many systems but some fundamental understanding is still lacking and the technique has been slow to transition from the laboratory to the industry. Aggregated colloids and lithographically created islands have shown the best success as reproducible substrates for SERS detection. These techniques, however, lack control over shape, size, and position of the metal nanoparticles which leave them reliant on hotspots. Because of the potential for control of the position of aggregates, ferroelectric lithographically created silver nanowires are evaluated as a potential SERS substrate using pyridine, benzoic acid, and Rhodamine 6g. Surface

  4. 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

  5. (Hadamard Raman imaging)

    SciTech Connect

    Not Available

    1991-01-01

    We have used newly developed holographic notch filters for obtaining both Stokes and anti-Stokes Raman images. The filters can be used as close as {plus minus}70 cm{sup {minus}1} from the Rayleigh line. We have demonstrated that they are insensitive to polarization, have 80% transmission across their clear apertures and block laser light by 10{sup 4}. The devices now have replaced sharp-cut glass filters on our microscope. We have successfully developed multispectral control and display software for the microscope. 4 refs., 3 figs.

  6. 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

  7. 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

  8. 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

  9. 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.

  10. Raman molecular chemical imaging: 3D Raman using deconvolution

    NASA Astrophysics Data System (ADS)

    Maier, John S.; Treado, Patrick J.

    2004-12-01

    Chemical imaging is a powerful technique combining molecular spectroscopy and digital imaging for rapid, non-invasive and reagentless analysis of materials, including biological cells and tissues. Raman chemical imaging is suited to the characterization of molecular composition and structure of biomateials at submicron spatial resolution (< 250 nm). As a result, Raman imaging has potential as a routine tool for the assessment of cells and subcellular components. In this presentation, we discuss Raman chemical imaging and spectroscopy of single human cells obtained from a culture line. Rapid three dimensional Raman imaging is shown using deconvolution to improve image quality.

  11. In situ Raman cell for high pressure and temperature studies of metal and complex hydrides.

    PubMed

    Domènech-Ferrer, Roger; Ziegs, Frank; Klod, Sabrina; Lindemann, Inge; Voigtländer, Ralf; Dunsch, Lothar; Gutfleisch, Oliver

    2011-04-15

    A novel cell for in situ Raman studies at hydrogen pressures up to 200 bar and at temperatures as high as 400 °C is presented. This device permits in situ monitoring of the formation and decomposition of chemical structures under high pressure via Raman scattering. The performance of the cell under extreme conditions is stable as the design of this device compensates much of the thermal expansion during heating which avoids defocusing of the laser beam. Several complex and metal hydrides were analyzed to demonstrate the advantageous use of this in situ cell. Temperature calibration was performed by monitoring the structural phase transformation and melting point of LiBH(4). The feasibility of the cell in hydrogen atmosphere was confirmed by in situ studies of the decomposition of NaAlH(4) with added TiCl(3) at different hydrogen pressures and the decomposition and rehydrogenation of MgH(2) and LiNH(2).

  12. 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

  13. Novel in situ cell for Raman diagnostics of lithium-ion batteries.

    PubMed

    Gross, T; Giebeler, L; Hess, C

    2013-07-01

    A novel in situ cell for Raman diagnostics of working lithium-ion batteries is described. The design closely mimics that of standard battery testing cells and therefore allows to obtain Raman spectra under representative electrochemical conditions. Both cathode and anode materials can be studied. First results on the intercalation of a Li1-xCoO2 cathode material demonstrate the potential of the experimental approach for structural studies and underline the importance of studying lithium-ion batteries at work.

  14. Snapshot Raman Spectral Imager

    DTIC Science & Technology

    2010-03-31

    range is appealing in this regard as upper atmospheric absorption by oxygen and ozone eliminate almost all radiation in the Raman shifted range of a...customer wanted to replace a bulky Fourier-Transform Infrared ( FTIR ) system with a dispersive system to lower the cost and size of the instrument. AQT

  15. In situ laser-Raman imagery of precambrian microscopic fossils.

    PubMed

    Kudryavtsev, A B; Schopf, J W; Agresti, D G; Wdowiak, T J

    2001-01-30

    Laser-Raman imagery is a sensitive, noninvasive, and nondestructive technique that can be used to correlate directly chemical composition with optically discernable morphology in ancient carbonaceous fossils. By affording means to investigate the molecular makeup of specimens ranging from megascopic to microscopic, it holds promise for providing insight into aspects of organic metamorphism and biochemical evolution, and for clarifying the nature of ancient minute fossil-like objects of putative but uncertain biogenicity.

  16. In situ laser-Raman imagery of Precambrian microscopic fossils

    PubMed Central

    Kudryavtsev, Anatoliy B.; Schopf, J. William; Agresti, David G.; Wdowiak, Thomas J.

    2001-01-01

    Laser-Raman imagery is a sensitive, noninvasive, and nondestructive technique that can be used to correlate directly chemical composition with optically discernable morphology in ancient carbonaceous fossils. By affording means to investigate the molecular makeup of specimens ranging from megascopic to microscopic, it holds promise for providing insight into aspects of organic metamorphism and biochemical evolution, and for clarifying the nature of ancient minute fossil-like objects of putative but uncertain biogenicity. PMID:11158554

  17. Deformation mechanisms of carbon nanotube fibres under tensile loading by in situ Raman spectroscopy analysis.

    PubMed

    Li, Qiu; Kang, Yi-Lan; Qiu, Wei; Li, Ya-Li; Huang, Gan-Yun; Guo, Jian-Gang; Deng, Wei-Lin; Zhong, Xiao-Hua

    2011-06-03

    Deformation mechanisms of carbon nanotube (CNT) fibres under tensile loading are studied by means of in situ Raman spectroscopy to detect the CNT deformation and stress distributions in the fibres. The G' band in the Raman spectrum responds distinctly to the tensile stress in Raman shift, width and intensity. The G' band changes with the tensile deformation of the fibre at different stages, namely elastic deformation, strengthening and damage-fracture. It is deduced that the individual CNTs only deform elastically without obvious damage or bond breaking. The yield and fracture of fibres can be due to the slippage among the CNTs.

  18. Orthorhombic boron oxide under pressure: In situ study by X-ray diffraction and Raman scattering

    NASA Astrophysics Data System (ADS)

    Cherednichenko, Kirill A.; Le Godec, Yann; Kalinko, Aleksandr; Mezouar, Mohamed; Solozhenko, Vladimir L.

    2016-11-01

    High-pressure phase of boron oxide, orthorhombic β-B2O3, has been studied in situ by synchrotron X-ray diffraction to 22 GPa and Raman scattering to 46 GPa at room temperature. The bulk modulus of β-B2O3 has been found to be 169(3) GPa that is in good agreement with our ab initio calculations. Raman and IR spectra of β-B2O3 have been measured at ambient pressure; all experimentally observed bands have been attributed to the theoretically calculated ones, and the mode assignment has been performed. Based on the data on Raman shift as a function of pressure, combined with equation-of-state data, the Grüneisen parameters of all experimentally observed Raman bands have been calculated. β-B2O3 enriched by 10B isotope has been synthesized, and the effect of boron isotopic substitution on Raman spectra has been studied.

  19. Molecular microanalysis of pathological specimens in situ with a laser-Raman microprobe.

    PubMed

    Abraham, J L; Etz, E S

    1979-11-09

    A laser-Raman microprobe has been used to identify microscopic inclusions of silicone polymer in standard paraffin sections of lymph node. This example of organic chemical microanalysis in situ in pathological tissue represents an extension of microanalytical capabilities from elemental analysis, performed with electron and ion microprobes, to compound-specific molecular microanalysis.

  20. 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.

  1. 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)

  2. In Situ Correlated Molecular Imaging of Chemically Communicating Microbial Communities

    SciTech Connect

    Bohn, Paul W.; Shrout, J. D.; Sweedler, J. V.; Farrand, S.

    2016-01-25

    This document constitutes the final technical report for DE-SC0006642, In Situ Correlated Molecular Imaging of Chemically Communicating Microbial Communities, a project carried out collaboratively by investigators at Notre Dame and UIUC. The work carried out under DOE support in this project produced advances in two areas: development of new highly sophisticated correlated imaging approaches and the application of these new tools to the growth and differentiation of microbial communities under a variety of environmental conditions. A significant effort involved the creation of technical enhancements and sampling approaches to allow us to advance heterocorrelated mass spectrometry imaging (MSI) and correlated Raman microscopy (CRM) from bacterial cultures and biofilms. We then exploited these measurement advances in heterocorrelated MS/CRM imaging to determine relationship of signaling molecules and excreted signaling molecules produced by P. aeruginosa to conditions relevant to the rhizosphere. In particular, we: (1) developed a laboratory testbed mimic for the rhizosphere to enable microbial growth on slides under controlled conditions; (2) integrated specific measurements of (a) rhamnolipids, (b) quinolone/quinolones, and (c) phenazines specific to P. aeruginosa; and (3) utilized the imaging tools to probe how messenger secretion, quorum sensing and swarming behavior are correlated with behavior.

  3. In-situ Raman spectroscopy to elucidate the influence of adsorption in graphene electrochemistry

    NASA Astrophysics Data System (ADS)

    van den Beld, Wesley T. E.; Odijk, Mathieu; Vervuurt, René H. J.; Weber, Jan-Willem; Bol, Ageeth A.; van den Berg, Albert; Eijkel, Jan C. T.

    2017-03-01

    Electrochemistry on graphene is of particular interest due to graphene’s high surface area, high electrical conductivity and low interfacial capacitance. Because the graphene Fermi level can be probed by its strong Raman signal, information on the graphene doping can be obtained which in turn can provide information on adsorbed atoms or molecules. For this paper, the adsorption analysis was successfully performed using three electroactive substances with different electrode interaction mechanisms: hexaammineruthenium(III) chloride (RuHex), ferrocenemethanol (FcMeOH) and potassium ferricyanide/potassium ferrocyanide (Fe(CN)6). The adsorption state was probed by analysing the G-peak position in the measured in-situ Raman spectrum during electrochemical experiments. We conclude that electrochemical Raman spectroscopy on graphene is a valuable tool to obtain in-situ information on adsorbed species on graphene, isolated from the rest of the electrochemical behaviour.

  4. In-situ Raman spectroscopy to elucidate the influence of adsorption in graphene electrochemistry

    PubMed Central

    van den Beld, Wesley T. E.; Odijk, Mathieu; Vervuurt, René H. J.; Weber, Jan-Willem; Bol, Ageeth A.; van den Berg, Albert; Eijkel, Jan C. T.

    2017-01-01

    Electrochemistry on graphene is of particular interest due to graphene’s high surface area, high electrical conductivity and low interfacial capacitance. Because the graphene Fermi level can be probed by its strong Raman signal, information on the graphene doping can be obtained which in turn can provide information on adsorbed atoms or molecules. For this paper, the adsorption analysis was successfully performed using three electroactive substances with different electrode interaction mechanisms: hexaammineruthenium(III) chloride (RuHex), ferrocenemethanol (FcMeOH) and potassium ferricyanide/potassium ferrocyanide (Fe(CN)6). The adsorption state was probed by analysing the G-peak position in the measured in-situ Raman spectrum during electrochemical experiments. We conclude that electrochemical Raman spectroscopy on graphene is a valuable tool to obtain in-situ information on adsorbed species on graphene, isolated from the rest of the electrochemical behaviour. PMID:28338094

  5. Introduction to Raman chemical imaging technology

    USDA-ARS?s Scientific Manuscript database

    New developments in computer and imaging hardware have significantly advanced Raman spectroscopy and spectral imaging technologies, and have led to the recent emergence of new Raman detection techniques for rapid and online applications. This book chapter presents Raman chemical imaging technology a...

  6. Detection of latent prints by Raman imaging

    DOEpatents

    Lewis, Linda Anne [Andersonville, TN; Connatser, Raynella Magdalene [Knoxville, TN; 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.

  7. In-situ histochemical analysis of human coronary artery by Raman spectroscopy compared with biochemical assay

    NASA Astrophysics Data System (ADS)

    Brennan, James F., III; Roemer, Tjeerd J.; Tercyak, Anna M.; Wang, Yang; Fitzmaurice, Maryann; Lees, Robert S.; Kramer, John R., Jr.; Dasari, Ramachandra R.; Feld, Michael S.

    1995-05-01

    We have developed a method to analyze quantitatively the biochemical composition of human coronary artery in situ using near infrared Raman spectroscopy. Human coronary arteries were obtained from explanted hearts after heart transplantation. Samples of normal intima/media, adventitia, non-calcified and calcified plaque were illuminated with 830 nm light from a CW Ti:Sapphire laser. The Raman scattered light was collected and coupled into a 1/4 meter spectrometer that dispersed the light onto a liquid nitrogen cooled, deep-depletion CCD detector. Raman spectra with sufficiently high S/N for extracting biochemical information could be collected in under one second. The spectra were analyzed using a recently developed model to quantitate the relative weight fractions of cholesterol, cholesterol esters, triacylglycerol, phospholipids, protein, and calcium salts. After spectral examination, the artery samples were biochemically assayed to determine the total lipid weight and the amount of the major lipid categories as a percentage of the total lipid content. The results of the lipid biochemical assay and the Raman spectral model compare favorably, indicating that relative lipid weights can be accurately determined in situ. Protein and calcium salts assays are underway. This in situ biochemical information may be useful in diagnosing atherosclerosis and studying disease progression.

  8. Characterisation of a portable Raman spectrometer for in situ analysis of art objects.

    PubMed

    Lauwers, Debbie; Hutado, Anna Garcia; Tanevska, Vinka; Moens, Luc; Bersani, Danilo; Vandenabeele, Peter

    2014-01-24

    During the last decades, Raman spectroscopy has grown to an established analytical technique in archaeometry, art analysis and conservation science. Mobile Raman instruments were designed to be used for in situ characterisation and identification of inorganic and organic materials in art and archaeometry. This research paper aims to point out several aspects that need to be considered when selecting a mobile Raman spectrometer for in situ archaeometrical studies. We describe an approach to evaluate these parameters and apply this to a dual laser portable Raman spectrometer. Twofold characterisation of mobile Raman instrumentation for art analysis: (i) investigation of spectroscopic characteristics such as (amongst others) spectral resolution, spectral window, signal to noise ratio and limit of detection; (ii) evaluation of specific properties that are useful for mobile studies in archaeometry. These include options for easy positioning and focussing, the ability to reduce laser power on the surface of the art object and the working distance between the probehead and the artefact. Finally, the research was completed with field tests by studying the pigments of a mediaeval wall painting.

  9. Fiber optic Raman spectrograph for in situ environmental monitoring. Final report

    SciTech Connect

    Carrabba, M.M.

    1992-11-01

    This report discusses the development and testing of a small laboratory prototype, field Raman spectrometer which can be used with a fiber optic sampling probe incorporting substrates tailored for surface enhanced Raman spectroscopy (SERS) for low level detection of chemical species. The report also discusses demonstration of apparatus for both laboratory and field environmental samples typical of DOE environmental restoration sites. Preliminary results establish a new technique which can be used in,the field to identify and profile in situ a wide variety of pollutants at the action levels required for remediation.

  10. Study of inorganic fullerenes and carbon nanotubes by in situ Raman tribometry

    NASA Astrophysics Data System (ADS)

    Joly-Pottuz, L.; Martin, J. M.; Belin, M.; Dassenoy, F.; Montagnac, G.; Reynard, B.

    2007-10-01

    Nanoparticles such as inorganic fullerenes of metal dichalcogenides or carbon nanotubes have been recently used as lubricant additives and they present excellent tribological properties. Raman spectroscopy is a useful technique to follow modification of these two structures. We developed an original tribometer able to perform in situ Raman analyses during sliding steel on a sapphire flat. These analyses gave unique information on real-time structural changes of nanoparticles inside the contact area: inorganic fullerenes are tribologically active by a progressive exfoliation process and carbon nanotubes is changed to amorphous carbon. Lubrication mechanism of these particles are explained in the light of analytical results.

  11. 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

    2016-11-01

    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.

  12. 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.

  13. Combined In Situ Micro X-Ray Diffraction and Raman Study of Carbonaceous Matter in Ureilites and Terrestrial Materials

    NASA Astrophysics Data System (ADS)

    Izawa, M. R. M.; Wright, A. J.; McCausland, P. J. A.; Flemming, R. L.; Muirhead, D. K.; Parnell, J.

    2008-03-01

    In situ ?XRD and Raman microspectroscopy have been applied to carbonaceous material in two ureilite and four terrestrial samples. This reconnaissance provides context and impetus for other, more invasive analytical techniques.

  14. In Situ Raman Analyses of Natural Gas and Gas Hydrates at Hydrate Ridge, Oregon

    NASA Astrophysics Data System (ADS)

    Peltzer, E. T.; White, S. N.; Dunk, R. M.; Brewer, P. G.; Sherman, A. D.; Schmidt, K.; Hester, K. C.; Sloan, E. D.

    2004-12-01

    During a July 2004 cruise to Hydrate Ridge, Oregon, MBARI's sea-going laser Raman spectrometer was used to obtain in situ Raman spectra of natural gas hydrates and natural gas venting from the seafloor. This was the first in situ analysis of gas hydrates on the seafloor. The hydrate spectra were compared to laboratory analyses performed at the Center for Hydrate Research, Colorado School of Mines. The natural gas spectra were compared to MBARI gas chromatography (GC) analyses of gas samples collected at the same site. DORISS (Deep Ocean Raman In Situ Spectrometer) is a laboratory model laser Raman spectrometer from Kaiser Optical Systems, Inc modified at MBARI for deployment in the deep ocean. It has been successfully deployed to depths as great as 3600 m. Different sampling optics provide flexibility in adapting the instrument to a particular target of interest. An immersion optic was used to analyze natural gas venting from the seafloor at South Hydrate Ridge ( ˜780 m depth). An open-bottomed cube was placed over the vent to collect the gas. The immersion optic penetrated the side of the cube as did a small heater used to dissociate any hydrate formed during sample collection. To analyze solid hydrates at both South and North Hydrate Ridge ( ˜590 m depth), chunks of hydrate were excavated from the seafloor and collected in a glass cylinder with a mesh top. A stand-off optic was used to analyze the hydrate inside the cylinder. Due to the partial opacity of the hydrate and the small focal volume of the sampling optic, a precision underwater positioner (PUP) was used to focus the laser spot onto the hydrate. PUP is a stand-alone system with three degrees-of-freedom, capable of moving the DORISS probe head with a precision of 0.1 mm. In situ Raman analyses of the gas indicate that it is primarily methane. This is verified by GC analyses of samples collected from the same site. Other minor constituents (such as CO2 and higher hydrocarbons) are present but may be in

  15. Electrochemical Behavior and Characterization of Polypyrrole-Copper Phthalocyanine Tetrasulfonate Thin Film: Cyclic Voltammetry and in Situ Raman Spectroscopic Investigation

    DTIC Science & Technology

    1990-01-10

    and identify by block number) r!ELD GROUP SUB- GROUP Polypyrrole- Copper Phthalocyanine Tetrasulfonate, Thin Film, Cyclic Voltammetry, In Situ Raman...purity), copper phthalocyanine -3,4’,4’’,4’’’-tetrasulfonic acid tetrasodium salt (appr. 85% purity), and methyl viologen dichloride hydrate were obtained...Electrochemical Behavior and Characterization of Polypyrrole- Copper Phthalocyanine Tetrasulfonate Thin Film: Cyclic Voltammetry and in Situ Raman

  16. Raman chemical imaging technology for food and agricultural applications

    USDA-ARS?s Scientific Manuscript database

    This paper presents Raman chemical imaging technology for inspecting food and agricultural products. The paper puts emphasis on introducing and demonstrating Raman imaging techniques for practical uses in food analysis. The main topics include Raman scattering principles, Raman spectroscopy measurem...

  17. Dynamic Raman imaging system with high spatial and temporal resolution

    NASA Astrophysics Data System (ADS)

    Wang, Lei; Dai, Yinzhen; He, Hao; Lv, Ruiqi; Zong, Cheng; Ren, Bin

    2017-09-01

    There is an increasing need to study dynamic changing systems with significantly high spatial and temporal resolutions. In this work, we integrated point-scanning, line-scanning, and wide-field Raman imaging techniques into a single system. By using an Electron Multiplying CCD (EMCCD) with a high gain and high frame rate, we significantly reduced the time required for wide-field imaging, making it possible to monitor the electrochemical reactions in situ. The highest frame rate of EMCDD was ˜50 fps, and the Raman images for a specific Raman peak can be obtained by passing the signal from the sample through the Liquid Crystal Tunable Filter. The spatial resolutions of scanning imaging and wide-field imaging with a 100× objective (NA = 0.9) are 0.5 × 0.5 μm2 and 0.36 × 0.36 μm2, respectively. The system was used to study the surface plasmon resonance of Au nanorods, the surface-enhanced Raman scattering signal distribution for Au Nanoparticle aggregates, and dynamic Raman imaging of an electrochemical reacting system.

  18. Assessment of hand-held Raman instrumentation for in situ screening for potentially counterfeit artesunate antimalarial tablets by FT-Raman spectroscopy and direct ionization mass spectrometry.

    PubMed

    Ricci, Camilla; Nyadong, Leonard; Yang, Felicia; Fernandez, Facundo M; Brown, Christopher D; Newton, Paul N; Kazarian, Sergei G

    2008-08-15

    Pharmaceutical counterfeiting has become a significant public health problem worldwide and new, rapid, user-friendly, reliable and inexpensive methods for drug quality screening are needed. This work illustrates the chemical characterization of genuine and fake artesunate antimalarial tablets by portable Raman spectroscopy and validation by FT-Raman spectroscopy and ambient mass spectrometry. The applicability of a compact and robust portable Raman spectrometer (TruScan) for the in situ chemical identification of counterfeit tablets is reported.

  19. Microsystem technology based diode lasers and Raman sensors for in situ food quality control

    NASA Astrophysics Data System (ADS)

    Sumpf, B.; Schmidt, H.; Maiwald, M.; Müller, A.; Erbert, G.; Kronfeldt, H.-D.; Tränkle, G.

    2009-05-01

    A microsystem based Raman sensor system for the in situ control of meat was realized. As excitation laser source a compact external cavity diode laser (ECDL) emitting at 671.0 nm mounted on a micro optical bench with a total dimension of (13 x 4 x 1) mm3 is implemented. An output power of 200 mW, a stable emission at 671.0 nm, and a narrow spectral width of about 80 pm, i.e. 2 cm-1, were measured. The device is well suited for Raman measurements of liquid and solid samples. The devices parameters and the stability will be reviewed. The micro-system laser device is implemented into a specifically laboratory prototype, including an optical bench with a diameter of 25 mm and a length of 170 mm. The probe is coupled fiber-optically to a polychromator with CCD detector for rapid spectral analysis. The Raman probe is characterized and first Raman measurements of porcine musculus longissimus dorsi through the package will be presented. The usefulness of Raman spectroscopy will be discussed with a view of integrating the sensor in a handheld laser scanner for food control.

  20. In situ quantification of β-carotene partitioning in oil-in-water emulsions by confocal Raman microscopy.

    PubMed

    Wan Mohamad, W A Fahmi; Buckow, Roman; Augustin, MaryAnn; McNaughton, Don

    2017-10-15

    Confocal Raman microscopy (CRM) was able to quantify the β-carotene concentration in oil droplets and determine the partitioning characteristics of β-carotene within the emulsion system in situ. The results were validated by a conventional method involving solvent extraction of β-carotene separately from the total emulsion as well as the aqueous phase separated by centrifugation, and quantification by absorption spectrophotometry. CRM also enabled the localization of β-carotene in an emulsion. From the Raman image, the β-carotene partitioning between the aqueous and oil phases of palm olein-in-water emulsions stabilized by whey protein isolate (WPI) was observed. Increasing the concentration of β-carotene in an emulsion (from 0.1 to 0.3g/kg emulsion) with a fixed gross composition (10% palm olein:2% WPI) decreased the concentration of β-carotene in the oil droplet. CRM is a powerful tool for in situ analyses of components in heterogeneous systems such as emulsions. Copyright © 2017 Elsevier Ltd. All rights reserved.

  1. Development of an In Situ Raman Probe for Pore Water Geochemistry

    NASA Astrophysics Data System (ADS)

    Walz, P. M.; Zhang, X.; Hester, K.; Kirkwood, W. J.; Ussler, W.; Peltzer, E. T.; Brewer, P. G.

    2009-12-01

    Scientists and engineers at the Monterey Bay Aquarium Research Institute have developed a ROV-deployable sampling probe utilizing laser Raman spectroscopy for study of sediment pore water geochemistry. The Raman technique has already been used with deep sea ROV platforms successfully performing in situ measurement on targets of scientific interest including gas and hydrothermal vent fluids, and complex gas hydrates. However, in situ measurement of sediment pore water geochemistry by laser Raman methods has so far been an intractable problem because sediment particles strongly fluorescence and insufficient amounts of pore water can be extracted before filters become occluded by sediment particles. Our design incorporates a series of novel elements into a slender 35-cm-long probe that can be inserted into sediment using an ROV manipulator to obtain concentration profiles. Pore water is drawn through a 10-μm stainless steel filter that forms the probe tip into a low volume sample chamber (0.1 mL) using a small hydraulic pump controlled by the ROV. The pump is also used for flushing and clearing filter surfaces. The sampling process is repeated as we proceed incrementally deeper into the sediment. Light (532 nm) from a Raman laser system mounted on the ROV is conveyed by a fiber optic cable to the probe head and focused within the center of the sample chamber through a sapphire-windowed optical cell. Control of the Raman system and spectra acquisition are performed onboard the ship via a laptop computer in the ROV control room. Advantages of this rapid mode of detection include measurement of sulfate gradients in near-seafloor sediments at a vertical scale not easily obtainable using traditional coring and extraction techniques, direct measurement of the dissolved sulfide species H2S and HS-, and measurement of dissolved methane without incurring substantial degassing during core recovery. The chemical measurements are made quantitative by calculating an intensity

  2. Surface Enhanced Raman Scattering Based in Situ Hybridization Strategy for Telomere Length Assessment.

    PubMed

    Zong, Shenfei; Chen, Chen; Wang, Zhuyuan; Zhang, Yizhi; Cui, Yiping

    2016-02-23

    Assessing telomere length is of vital importance since telomere length is closely related with several fatal diseases such as atherosclerosis and cancer. Here, we present a strategy to assess/measure telomere length, that is, surface enhanced Raman scattering (SERS) based in situ hybridization (SISH). The SISH method uses two kinds of SERS nanoprobes to hybridize in situ with telomeres and centromeres, respectively. The telomere specific SERS nanoprobe is called the Telo-probe, while the centromere specific SERS nanoprobe is called the Centro-probe. They are composed of metal nanoparticles (NPs), Raman reporter molecules and specially designed DNA strands. With longer telomeres, more Telo-probes will hybridize with them, resulting in a stronger SERS signal. To exclude possible influence of the SERS intensity by external factors (such as the nanoprobe concentration, the cell number or different batches of nanoprobes), centromeres are used as the inner control, which can be recognized by Centro-probes. Telomere length is evaluated using a redefined telomere-to-centromere ratio (T/C ratio). The calculation method for T/C ratio in SISH method is more reliable than that in fluorescent in situ hybridization (FISH). In addition, unlike FISH method, the SISH method is insensitive to autofluorescence. Moreover, SISH method can be used to analyze single telomeres. These features make SISH an excellent alternative strategy for telomere length measurement.

  3. In situ surface-enhanced Raman spectroelectrochemical analysis system with a hemin modified nanostructured gold surface.

    PubMed

    Yuan, Tao; Le Thi Ngoc, Loan; van Nieuwkasteele, Jan; Odijk, Mathieu; van den Berg, Albert; Permentier, Hjalmar; Bischoff, Rainer; Carlen, Edwin T

    2015-03-03

    An integrated surface-enhanced Raman scattering (SERS) spectroelectrochemical (SEC) analysis system is presented that combines a small volume microfluidic sample chamber (<100 μL) with a compact three-electrode configuration for in situ surface-enhanced Raman spectroelectrochemistry. The SEC system includes a nanostructured Au surface that serves dual roles as the electrochemical working electrode (WE) and SERS substrate, a microfabricated Pt counter electrode (CE), and an external Ag/AgCl reference electrode (RE). The nanostructured Au WE enables highly sensitive in situ SERS spectroscopy through large and reproducible SERS enhancements, which eliminates the need for resonant wavelength matching of the laser excitation source with the electronic absorption of the target molecule. The new SEC analysis system has the merits of wide applicability to target molecules, small sample volume, and a low detection limit. We demonstrate in situ SERS spectroelectrochemistry measurements of the metalloporphyrin hemin showing shifts of the iron oxidation marker band ν4 with the nanostructured Au working electrode under precise potential control.

  4. 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.

  5. Signal enhancement of surface enhanced Raman scattering and surface enhanced resonance Raman scattering using in situ colloidal synthesis in microfluidics.

    PubMed

    Wilson, Rab; Bowden, Stephen A; Parnell, John; Cooper, Jonathan M

    2010-03-01

    We demonstrate the enhanced analytical sensitivity of both surface enhanced Raman scattering (SERS) and surface enhanced resonance Raman scattering (SERRS) responses, resulting from the in situ synthesis of silver colloid in a microfluidic flow structure, where both mixing and optical interrogation were integrated on-chip. The chip-based sensor was characterized with a model Raman active label, rhodamine-6G (R6G), and had a limit of detection (LOD) of ca. 50 fM (equivalent to single molecule detection). The device was also used for the determination of the natural pigment, scytonemin, from cyanobacteria (as an analogue for extraterrestrial life existing in extreme environments). The observed LOD of approximately 10 pM (ca. <400 molecules) demonstrated the analytical advantages of working with freshly synthesized colloid in such a flow system. In both cases, sensitivities were between 1 and 2 orders of magnitude greater in the microfluidic system than those measured using the same experimental parameters, with colloid synthesized off-chip, under quiescent conditions.

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

    PubMed Central

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

    2017-01-01

    We demonstrate ambient light coherent anti-Stokes Raman scattering (AL-CARS) microscopy that allows CARS imaging to be operated under environment light for field use. 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. Filters in both spectral domain and frequency domain effectively blocked room light contamination of the CARS image. In situ hyperspectral CARS imaging of tumor tissue under ambient light is demonstrated. PMID:27519113

  7. 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.

  8. Raman chemical imaging: Development and applications

    NASA Astrophysics Data System (ADS)

    Schaeberle, Michael D.

    Recent advances in electronically tunable filters, such as acousto-optic tunable filters (AOTF) and liquid crystal tunable filters (LCTF), combined with multispectral image processing strategies make Raman chemical imaging a powerful technique for the routine analysis of material chemical architecture. Raman chemical imaging combines Raman spectroscopy and digital imaging technology to assess material molecular composition and structure. Raman spectroscopy probes molecular composition and structure without being destructive to the sample. The spectrum for an analyte within even a complex host matrix is harnessed to generate unique contrast intrinsic to the analyte species without the use of stains, dyes, or contrast agents. This thesis provides a brief introduction to the field of Raman chemical imaging by describing the major methods employed. The research presented here focuses on wide field Raman imaging in conjunction with electronically tunable filters, and therefore a general methodology for performing Raman chemical imaging analysis of unknown samples is described. The AOTF and LCTF Raman chemical imaging microscopes developed during this research are also presented. The general operating principles of the AOTF and the LCTF are briefly discussed along with their specific implementation within the microscope based imaging systems. Raman chemical imaging represents an efficient, widely applicable approach for understanding the relationship between material molecular architecture and material function, which is central to the engineering of advanced materials. AOTF Raman chemical imaging has been employed in the visualization of the architecture of polypropylene and polyurethane blended polymers. High fidelity Raman images were and domains in the 3-5 mum ranges were differentiated. The AOTF Raman chemical imaging microscope has also been applied to the histopathological characterization of human breast tissue. A foreign polymer inclusion in the tissue was

  9. 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.

  10. Development of a combined portable x-ray fluorescence and Raman spectrometer for in situ analysis

    NASA Astrophysics Data System (ADS)

    Guerra, M.; Longelin, S.; Pessanha, S.; Manso, M.; Carvalho, M. L.

    2014-06-01

    In this work, we have built a portable X-ray fluorescence (XRF) spectrometer in a planar configuration coupled to a Raman head and a digital optical microscope, for in situ analysis. Several geometries for the XRF apparatus and digital microscope are possible in order to overcome spatial constraints and provide better measurement conditions. With this combined spectrometer, we are now able to perform XRF and Raman measurements in the same point without the need for sample collection, which can be crucial when dealing with cultural heritage objects, as well as forensic analysis. We show the capabilities of the spectrometer by measuring several standard reference materials, as well as other samples usually encountered in cultural heritage, geological, as well as biomedical studies.

  11. High pressure optical cell for synthesis and in situ Raman spectroscopy of hydrogen clathrate hydrates

    NASA Astrophysics Data System (ADS)

    Celli, Milva; Zoppi, Marco; Zaghloul, Mohamed A. S.; Ulivi, Lorenzo

    2012-11-01

    We report the design, realization, and test of a high-pressure optical cell that we have used to measure the Raman spectra of hydrogen clathrate hydrates, synthesized in situ by the application of 200-300 MPa of gas pressure on solid water. The optical apparatus is mounted on a cryogenic system so to allow measurements and sample treatment at any temperature between 300 and 20 K. A capillary pipe is connected to the inside of the cell to allow the gas flow into and out of the cell, and to regulate the internal pressure at any value from 0 to 300 MPa. In the experimental test described in this paper, the cell has been partly filled, at room temperature, with a small amount of water, then frozen at 263 K before injecting hydrogen gas, at pressure of 150 MPa, into the cell. This procedure has permitted to study hydrogen clathrate formation, by measuring Raman spectra as a function of time.

  12. Development of a combined portable x-ray fluorescence and Raman spectrometer for in situ analysis.

    PubMed

    Guerra, M; Longelin, S; Pessanha, S; Manso, M; Carvalho, M L

    2014-06-01

    In this work, we have built a portable X-ray fluorescence (XRF) spectrometer in a planar configuration coupled to a Raman head and a digital optical microscope, for in situ analysis. Several geometries for the XRF apparatus and digital microscope are possible in order to overcome spatial constraints and provide better measurement conditions. With this combined spectrometer, we are now able to perform XRF and Raman measurements in the same point without the need for sample collection, which can be crucial when dealing with cultural heritage objects, as well as forensic analysis. We show the capabilities of the spectrometer by measuring several standard reference materials, as well as other samples usually encountered in cultural heritage, geological, as well as biomedical studies.

  13. 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.

  14. In situ Raman monitoring of He2+ irradiation induced damage in a UO2 ceramic

    NASA Astrophysics Data System (ADS)

    Guimbretière, G.; Desgranges, L.; Canizarès, A.; Caraballo, R.; Duval, F.; Raimboux, N.; Omnée, R.; Ammar, M. R.; Jégou, C.; Simon, P.

    2013-07-01

    The in situ Raman probing of a UO2 ceramic in [Ar/H2, 95/5] gas atmosphere followed by exposure to He2+ ionic irradiation coming from a cyclotron accelerator was implemented. It was observed that the growth of Raman defect bands exhibits a unique kinetic nicely modelized by a simple direct impact model, and with an annealing rate constant of 5.6 × 10-4 ± 4 × 10-5 s-1 for an ionic flow of 50 nA and an ions-beam induced sample heating of 170 ± 10 °C. Also, it was observed that the Ar plasma induced by the ions-beam is a sensitive probe of the presence of the ions-beam.

  15. 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.

  16. 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.

  17. 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.

  18. High Fidelity Raman Chemical Imaging of Materials

    NASA Astrophysics Data System (ADS)

    Bobba, Venkata Nagamalli Koteswara Rao

    The development of high fidelity Raman imaging systems is important for a number of application areas including material science, bio-imaging, bioscience and healthcare, pharmaceutical analysis, and semiconductor characterization. The use of Raman imaging as a characterization tool for detecting the amorphous and crystalline regions in the biopolymer poly-L-lactic acid (PLLA) is the precis of my thesis. In the first chapter, a brief insight about the basics of Raman spectroscopy, Raman chemical imaging, Raman mapping, and Raman imaging techniques has been provided. The second chapter contains details about the successful development of tailored sample of PLLA. Biodegradable polymers are used in areas of tissue engineering, agriculture, packaging, and in medical field for drug delivery, implant devices, and surgical sutures. Detailed information about the sample preparation and characterization of these cold-drawn PLLA polymer substrates has been provided. Wide-field Raman hyperspectral imaging using an acousto-optic tunable filter (AOTF) was demonstrated in the early 1990s. The AOTF contributed challenges such as image walk, distortion, and image blur. A wide-field AOTF Raman imaging system has been developed as part of my research and methods to overcome some of the challenges in performing AOTF wide-field Raman imaging are discussed in the third chapter. This imaging system has been used for studying the crystalline and amorphous regions on the cold-drawn sample of PLLA. Of all the different modalities that are available for performing Raman imaging, Raman point-mapping is the most extensively used method. The ease of obtaining the Raman hyperspectral cube dataset with a high spectral and spatial resolution is the main motive of performing this technique. As a part of my research, I have constructed a Raman point-mapping system and used it for obtaining Raman hyperspectral image data of various minerals, pharmaceuticals, and polymers. Chapter four offers

  19. Innovative Raman spectroscopic concepts for in situ monitoring of chemicals in seawater

    NASA Astrophysics Data System (ADS)

    Sowoidnich, Kay; Fernández López, María.; Kronfeldt, Heinz-Detlef

    2013-05-01

    Optical sensors based on Raman spectroscopy are suitable for a rapid identification and quantification of pollutants such as Polycyclic Aromatic Hydrocarbons (PAHs). Additionally, Surface enhanced Raman spectroscopy (SERS) has gained increasing attention as a powerful technique for in-situ monitoring of these substances in seawater to achieve limits of detection (LODs) in the sub-nmol/l range. A low-cost method based on electroless plating solution of chloroauric acid (HAuCl4) and hydrogen peroxide (H2O2) was developed in our group to construct a gold island film as SERS substrate to achieve a well reproducible, high sensitive and seawater resistant SERS sensor. The substrates show good resistance against seawater determined by long-term stability tests carried out over 12 weeks of storage of the substrates in artificial seawater. The investigations show that the substrates still have about 50 % of their initial activity after 4 weeks of storage and about 15 % after two months. This type of substrate is reproducible with variability in the SERS intensities of about 8 %. Shifted excitation Raman difference spectroscopy (SERDS) was applied by using a microsystem diode laser emitting at 784.3 nm and 784.8 nm to remove the fluorescence interference and to improve the Raman signals. This combination of SERS and SERDS yields a limit of detection of 1 nmol/l for pyrene which was selected as representative PAH. These quantitative results show that the designed SERS substrates are suitable for the in-situ monitoring of PAHs in the marine environment.

  20. [In situ Raman spectroscopic observation of micro-processes of methane hydrate formation and dissociation].

    PubMed

    Liu, Chang-Ling; Ye, Yu-Guang; Meng, Qing-Guo; Lü, Wan-Jun; Wang, Fei-Fei

    2011-06-01

    Micro laser Raman spectroscopic technique was used for in situ observation of the micro-processes of methane hydrate formed and decomposed in a high pressure transparent capillary. The changes in clathrate structure of methane hydrate were investigated during these processes. The results show that, during hydrate formation, the Raman peak (2 917 cm(-1)) of methane gas gradually splits into two peaks (2 905 and 2 915 cm(-1)) representing large and small cages, respectively, suggesting that the dissolved methane molecules go into two different chemical environments. In the meantime, the hydrogen bonds interaction is strengthened because water is changing from liquid to solid state gradually. As a result, the O-H stretching vibrations of water shift to lower wavenumber. During the decomposition process of methane hydrates, the Raman peaks of the methane molecules both in the large and small cages gradually clear up, and finally turn into a single peak of methane gas. The experimental results show that laser Raman spectroscopy can accurately demonstrate some relevant information of hydrate crystal structure changes during the formation and dissociation processes of methane hydrate.

  1. 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.

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

    SciTech Connect

    Ghule, Anil Vithal; Ghule, Kalyani; Tzing, S.-H.; Punde, Tushar H.; Chang Hua; Ling, Y.C.

    2009-12-15

    Hyphenation of thermogravimetric analyzer (TGA) and thermo-Raman spectrophotometer for in situ monitoring of solid-state reaction in oxygen atmosphere forming NiO-Al{sub 2}O{sub 3} catalyst nanoparticles is investigated. In situ thermo-Raman spectra in the range from 200 to 1400 cm{sup -1} were recorded at every degree interval from 25 to 800 deg. C. Thermo-Raman spectroscopic studies reveal that, although the onset of formation is around 600 deg. C, the bulk NiAl{sub 2}O{sub 4} forms at temperatures above 800 deg. 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 deg. C, in the temperature range from 400 to 1000 deg. C, which could provide information on structural and morphological evolution of NiO-Al{sub 2}O{sub 3}. Slow controlled heating of the sample enabled better control over morphology and particle size distribution ({approx}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. - Graphical abstract: Hyphenation of thermogravimetric analyzer and thermo-Raman spectrophotometer for in situ monitoring of solid-state reaction at controlled heating rate and in oxygen atmosphere forming NiO-Al{sub 2}O{sub 3} catalyst nanoparticles is investigated.

  3. Quantitative multi-image analysis for biomedical Raman spectroscopic imaging.

    PubMed

    Hedegaard, Martin A B; Bergholt, Mads S; Stevens, Molly M

    2016-05-01

    Imaging by Raman spectroscopy enables unparalleled label-free insights into cell and tissue composition at the molecular level. With established approaches limited to single image analysis, there are currently no general guidelines or consensus on how to quantify biochemical components across multiple Raman images. Here, we describe a broadly applicable methodology for the combination of multiple Raman images into a single image for analysis. This is achieved by removing image specific background interference, unfolding the series of Raman images into a single dataset, and normalisation of each Raman spectrum to render comparable Raman images. Multivariate image analysis is finally applied to derive the contributing 'pure' biochemical spectra for relative quantification. We present our methodology using four independently measured Raman images of control cells and four images of cells treated with strontium ions from substituted bioactive glass. We show that the relative biochemical distribution per area of the cells can be quantified. In addition, using k-means clustering, we are able to discriminate between the two cell types over multiple Raman images. This study shows a streamlined quantitative multi-image analysis tool for improving cell/tissue characterisation and opens new avenues in biomedical Raman spectroscopic imaging. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. In-situ shifted excitation Raman difference spectroscopy: development and demonstration of a portable sensor system at 785 nm

    NASA Astrophysics Data System (ADS)

    Maiwald, M.; Müller, A.; Sumpf, B.

    2017-02-01

    In-situ shifted excitation Raman difference spectroscopy (SERDS) experiments are presented using a portable sensor system. Key elements of this system are an in-house developed handheld probe with an implemented dual-wavelength diode laser at 785 nm. An optical power of 120 mW is achieved ex probe. Raman experiments are carried out in the laboratory for qualification using polystyrene as test sample. Here, a shot-noise limited signal-to-noise ratio (SNR) of 120 is achieved. Stability tests were performed and show a stable position of the Raman line under study within 0.1 cm-1 and a stable Raman intensity better +/- 2% mainly limited by shot noise interference. SERDS experiments are carried out in an apple orchard for demonstration. Green apple leafs are used as test samples. The Raman spectra show huge background interferences by fluorescence and ambient daylight which almost obscure Raman signals from green leafs. The selected excitation power is 50 mW and the exposure time is 0.2 s to avoid detector saturation. SERDS efficiently separates the Raman signals from fluorescence and daylight contributions and generates an 11-fold improvement of the signal-to-background noise with respect to the measured Raman signals. The results demonstrate the capability of the portable SERDS system and enable rapid in-situ and undisturbed Raman investigations under daylight conditions.

  5. Real-time monitoring of high-gravity corn mash fermentation using in situ raman spectroscopy.

    PubMed

    Gray, Steven R; Peretti, Steven W; Lamb, H Henry

    2013-06-01

    In situ Raman spectroscopy was employed for real-time monitoring of simultaneous saccharification and fermentation (SSF) of corn mash by an industrial strain of Saccharomyces cerevisiae. An accurate univariate calibration model for ethanol was developed based on the very strong 883 cm(-1) C-C stretching band. Multivariate partial least squares (PLS) calibration models for total starch, dextrins, maltotriose, maltose, glucose, and ethanol were developed using data from eight batch fermentations and validated using predictions for a separate batch. The starch, ethanol, and dextrins models showed significant prediction improvement when the calibration data were divided into separate high- and low-concentration sets. Collinearity between the ethanol and starch models was avoided by excluding regions containing strong ethanol peaks from the starch model and, conversely, excluding regions containing strong saccharide peaks from the ethanol model. The two-set calibration models for starch (R(2)  = 0.998, percent error = 2.5%) and ethanol (R(2)  = 0.999, percent error = 2.1%) provide more accurate predictions than any previously published spectroscopic models. Glucose, maltose, and maltotriose are modeled to accuracy comparable to previous work on less complex fermentation processes. Our results demonstrate that Raman spectroscopy is capable of real time in situ monitoring of a complex industrial biomass fermentation. To our knowledge, this is the first PLS-based chemometric modeling of corn mash fermentation under typical industrial conditions, and the first Raman-based monitoring of a fermentation process with glucose, oligosaccharides and polysaccharides present. Copyright © 2013 Wiley Periodicals, Inc.

  6. Raman microspectroscopy for in situ examination of carbon-microbe-mineral interactions

    NASA Astrophysics Data System (ADS)

    Creamer, C.; Foster, A. L.; Lawrence, C. R.; Mcfarland, J. W.; Waldrop, M. P.

    2016-12-01

    The changing paradigm of soil organic matter formation and turnover is focused at the nexus of microbe-carbon-mineral interactions. However, visualizing biotic and abiotic stabilization of C on mineral surfaces is difficult given our current techniques. Therefore we investigated Raman microspectroscopy as a potential tool to examine microbially mediated organo-mineral associations. Raman microspectroscopy is a non-destructive technique that has been used to identify microorganisms and minerals, and to quantify microbial assimilation of 13C labeled substrates in culture. We developed a partial least squares regression (PLSR) model to accurately quantify (within 5%) adsorption of four model 12C substrates (glucose, glutamic acid, oxalic acid, p-hydroxybenzoic acid) on a range of soil minerals. We also developed a PLSR model to quantify the incorporation of 13C into E. coli cells. Using these two models, along with measures of the 13C content of respired CO2, we determined the allocation of glucose-derived C into mineral-associated microbial biomass and respired CO2 in situ and through time. We observed progressive 13C enrichment of microbial biomass with incubation time, as well as 13C enrichment of CO2 indicating preferential decomposition of glucose-derived C. We will also present results on the application of our in situ chamber to quantify the formation of organo-mineral associations under both abiotic and biotic conditions with a variety of C and mineral substrates, as well as the rate of turnover and stabilization of microbial residues. Application of Raman microspectroscopy to microbial-mineral interactions represents a novel method to quantify microbial transformation of C substrates and subsequent mineral stabilization without destructive sampling, and has the potential to provide new insights to our conceptual understanding of carbon-microbe-mineral interactions.

  7. Development of a Laser Raman Spectrometer for In Situ Measurements in the Deep Ocean

    NASA Astrophysics Data System (ADS)

    White, S. N.; Brewer, P. G.; Peltzer, E. T.; Malby, G. E.; Pasteris, J. D.

    2002-12-01

    We have developed an ROV-deployable laser Raman spectrometer (LRS) to make in situ measurements of solid, liquid and gaseous species in the ocean (up to 3600 m depth). The LRS can be used to determine chemical and structural composition by irradiating the target with a laser and measuring the inelastically scattered (Raman shifted) light. The frequency shift from the exciting wavelength is due to characteristic molecular vibrations of the molecule; thus, the Raman spectrum serves as a fingerprint of a substance based on molecular composition and crystal structure. Raman spectroscopy is rapid, and typically requires no sample preparation. However, the weak Raman effect (~1 in 108 photons), the need for precise laser positioning, and fluorescence, pose challenges. We have acquired an LRS from Kaiser Optical Systems, Inc. and adapted it for use in the ocean by dividing the components into three pressure cases, building penetrating fiber optic cables, developing an Ethernet interface to control the system from shipboard, and redesigning and rebuilding non-robust components. Future improvements will include weight/size reduction, adding through-the-lens visualization, and using liquid core optical waveguides to increase sensitivity. An increase in sensitivity of x10 would permit direct observation of natural seawater HCO3 and CO3 peaks. The LRS has been successfully deployed over 6 times on MBARI's two remotely operated vehicles in 2002. Initial measurements of standards (e.g., isopropanol, calcite, and diamond) at depths as great as 3600 m have proven the effectiveness of the instrument in the deep ocean and have allowed us to advance methods for its use. Detailed spectra of seawater in situ and in the lab have also been obtained to better understand the ever-present seawater background (which includes water and SO4 peaks, and very little fluorescence). We have used the LRS in a number of deep-sea CO2 sequestration studies to acquire spectra of gaseous CO2 and CO2/N2

  8. Portable Raman spectroscopy for an in-situ monitoring the ripening of tomato (Solanum lycopersicum) fruits

    NASA Astrophysics Data System (ADS)

    Trebolazabala, Josu; Maguregui, Maite; Morillas, Héctor; de Diego, Alberto; Madariaga, Juan Manuel

    2017-06-01

    Ripening is one of the most important transformations that fruits and vegetables suffer, from an unripe to a ripe stage. In this study, it was followed up and analyzed the variations in the composition of tomato fruits at different ripening stages (green or unripe, orange or middle ripe, red or ripe and brown or overripe). The results obtained from the Raman measurements carried out showed a change in the composition of tomato fruits in the transit from green to brown. The analysis confirmed an increase of carotenoids from an unripe to a ripe stage of these fruits, being lycopene the characteristic carotenoid of the optimum ripe stage. The presence of chlorophyll and cuticular waxes decrease from the unripe to the ripe stage. Moreover, the relative intensity of phytofluene, a transition compound in the carotenoid biosynthetic pathway, is higher in the orange or middle ripening stage. The results obtained in-situ, without cutting and handling the tomato fruits, by means of a portable Raman spectrometer offered the same information that can be achieved using a more expensive and sophisticated confocal Raman microscope.

  9. In situ Raman study of Electrochemically Intercalted Bisulfate Ions in Carbon Nanotube Bundles

    NASA Astrophysics Data System (ADS)

    Sumanasekera, G. U.; Allen, J. L.; Rao, A. M.; Fang, S. L.; Eklund, P. C.

    1998-03-01

    We have investigated the electrochemical intercalation of bisulfate ions in single-walled carbon nanotubes (SWNT) using in situ Raman spectroscopy. SWNTs pressed onto a Pt plate was used as the working electrode, a Pt wire and Ag/AgCl were used, respectively, as the counter electrode and reference electrode. Sulfuric acid (95%) was used as the electrolyte. Using Raman scattering we have observed an apparent rapid spontaneous reaction involving charge transfer between ionically bonded HSO_4^- anions and the nanotubes. This is evidenced by an instantaneous shift of the Raman-active tangential mode frequency from 1593 cm -1 to 1604 cm-1 (It was not possible to reverse this shift electrochemically to 1593 cm-1, even at the expense of large reverse bias). In forward bias, after this initial instantaneous reaction, the tangential mode frequency again upshifted from 1604 cm-1 to 1614 cm-1 linearly with external electrochemical charge Q. From the slope of ω(Q) we found in this regime, δω/δ f= 1220 cm-1 (f = holes/carbon). Upon further charging, a second regime with slope δω/δ f = 118 cm-1 was observed where the frequency upshifted from 1614 cm-1 to 1620 cm-1. The results are compared to similar studies in C_p^+HSO_4^-.xH_2SO4 graphite intercalation compounds.

  10. 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.

  11. 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

  12. 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

  13. 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.

  14. 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

    2016-08-07

    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.

  15. In situ X-ray-based imaging of nano materials

    DOE PAGES

    Weker, Johanna Nelson; Huang, Xiaojing; Toney, Michael F.

    2016-02-13

    We study functional nanomaterials that are heterogeneous and understanding their behavior during synthesis and operation requires high resolution diagnostic imaging tools that can be used in situ. Over the past decade, huge progress has been made in the development of X-ray based imaging, including full field and scanning microscopy and their analogs in coherent diffractive imaging. Currently, spatial resolution of about 10 nm and time resolution of sub-seconds are achievable. For catalysis, X-ray imaging allows tracking of particle chemistry under reaction conditions. In energy storage, in situ X-ray imaging of electrode particles is providing important insight into degradation processes. Recently,more » both spatial and temporal resolutions are improving to a few nm and milliseconds and these developments will open up unprecedented opportunities.« less

  16. In vivo and in situ monitoring of the nitric oxide stimulus response of single cancer cells by Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Su, L.; Chen, Y.; Zhang, G. N.; Wang, L. H.; Shen, A. G.; Zhou, X. D.; Wang, X. H.; Hu, J. M.

    2013-04-01

    Raman spectroscopy is capable of studying time-resolved information of selected biomolecular distributions inside individual cells without labeling. In this study, Raman spectroscopy was for the first time utilized to in vivo and in situ monitor the cellular response to nitric oxide (NO) in single oral squamous cell carcinoma (OSCC) cells over a period of 24 h. Sodium nitroprusside (SNP) was chosen as a NO donor to be incubated with the OSCC cell line (TCA8113) for certain time intervals. In vivo and in situ Raman analysis revealed that the degradation and conformational changes of nucleic acids, lipids and proteins could be directly observed by changes in the characteristic Raman bands. In comparison with conventional flow cytometric analysis, Raman spectroscopy not only detected more subtle NO-induced chemical changes of cells, where the SNP concentration could be even less than 1 mM, but also provided a full view of the whole chemical components of single cells. Raman spectroscopy therefore is an important candidate for label-free, nondestructive and in situ monitoring of cellular changes in response to chemotherapeutic agents, which could potentially be used in rapid screening of novel drugs.

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

    PubMed Central

    Liao, Chien-Sheng; Cheng, Ji-Xin

    2017-01-01

    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. PMID:27306307

  18. 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.

  19. In situ surface-enhanced Raman spectroscopy of monodisperse silver nanowire arrays

    NASA Astrophysics Data System (ADS)

    Sauer, G.; Brehm, G.; Schneider, S.; Graener, H.; Seifert, G.; Nielsch, K.; Choi, J.; Göring, P.; Gösele, U.; Miclea, P.; Wehrspohn, R. B.

    2005-01-01

    Highly ordered two-dimensional arrays of monodisperse coinage metal nanowires embedded in an alumina matrix have been prepared. When light is propagating in the direction of the long axis of the nanowire, plasmon-enhanced absorption and light guidance of the nanowire were observed by optical microspectroscopy and scanning near-field optical spectroscopy and compared to Mie scattering theory. By selectively dissolving the matrix at a constant etching rate, we detected in situ and ex situ the surface-enhanced Raman scattering (SERS) of organic dyes. In contrast to earlier publications, we find that the SERS signal is linearly proportional to the free-surface area of the nanowires that are in contact with the dye. We cannot detect any change in the enhancement factor due to the releasing of the nanowires from the host structure.

  20. In situ Raman spectroscopic study of marble capitals in the Alhambra monumental ensemble

    NASA Astrophysics Data System (ADS)

    Arjonilla, Paz; Domínguez-Vidal, Ana; de la Torre López, María José; Rubio-Domene, Ramón; Ayora-Cañada, María José

    2016-12-01

    The marble capitals of five different sites in the Alhambra complex (Granada, Spain), namely the Mexuar, the Hall of the Abencerrages, the Hall of the Kings, the Court of the Myrtles and the Court of the Main Canal, have been investigated. The decoration of the capitals exhibits mainly blue, red, black and gilding motifs with different states of conservation. The work has been carried out in situ by means of a portable Raman micro-spectrometer with an excitation laser of 785 nm. In addition to preserving the artwork with a non-invasive study, the on-site investigation gives a more representative knowledge of the art objects because the measurements are not limited to the samples that can be taken (few and small). The obtained Raman spectra were of good quality despite challenging adverse conditions out of the laboratory. Cinnabar, minium, carbon black, natural lapis lazuli and azurite were the main pigments found. Synthetic ultramarine blue was also detected in a capital as a result of a modern restoration. Degradation products as tin oxide in the gildings and weddellite in the preparation layers were also identified. All the results together with a careful visual inspection can be combined to elucidate the different execution techniques employed to apply the pigments on the marble substrate of the capitals in the Nasrid and Christian periods.

  1. 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.

  2. 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

  3. 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.

  4. In situ Raman spectroscopy of sulfur speciation in lithium-sulfur batteries.

    PubMed

    Wu, Heng-Liang; Huff, Laura A; Gewirth, Andrew A

    2015-01-28

    In situ Raman spectroscopy and cyclic voltammetry were used to investigate the mechanism of sulfur reduction in lithium-sulfur battery slurry cathodes with 1 M lithium bis(trifluoromethane sulfonyl)imide (LiTFSI) and tetraethylene glycol dimethyl ether (TEGDME)/1,3-dioxolane (DIOX) (1/1, v/v). Raman spectroscopy shows that long-chain polysulfides (S8(2-)) were formed via S8 ring opening in the first reduction process at ∼2.4 V vs Li/Li(+) and short-chain polysulfides such as S4(2-), S4(-), S3(•-), and S2O4(2-) were observed with continued discharge at ∼2.3 V vs Li/Li(+) in the second reduction process. Elemental sulfur can be reformed in the end of the charge process. Rate constants obtained for the appearance and disappearance polysulfide species shows that short-chain polysulfides are directly formed from S8 decomposition. The rate constants for S8 reappearance and polysulfide disappearance on charge were likewise similar. The formation of polysulfide mixtures at partial discharge was found to be quite stable. The CS2 additive was found to inhibit the sulfur reduction mechanism allowing the formation of long-chain polysulfides during discharge only and stabilizing the S8(2-) product.

  5. 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.

  6. 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.

  7. Combined Raman-LIBS, Moessbauer and XRD In-Situ Mineral Analysis of Evaporite Minerals at Rio Tinto (Spain)

    NASA Astrophysics Data System (ADS)

    Rull, F.; Klingelhöfer, G.; Sarrazin, P.; Medina, J.; Fleischer, I.; Blake, D.; Martin Ramos, J. D.

    2010-04-01

    In this study a combination of Raman, LIBS, Mössbauer and XRD portable instruments has been used to undertake a common in-situ analysis of sulphate minerals at Rio Tinto area within the CAREX Field Procedure Inter-comparison Exercise 2009.

  8. In situ Raman investigation of electrolyte solutions in the vicinity of graphite negative electrodes.

    PubMed

    Song, Hee-Youb; Fukutsuka, Tomokazu; Miyazaki, Kohei; Abe, Takeshi

    2016-10-05

    The structure of electrolyte solutions plays an important role in the lithium-ion intercalation reaction at graphite negative electrodes. The solvation structure of an electrolyte solution in bulk has been investigated previously. However, the structure of an electrolyte solution at the graphite negative electrode/electrolyte solution interface, where the lithium-ion intercalation reaction occurs is more important. In this study, the structure of electrolyte solutions in the vicinity of a graphite negative electrode was investigated using in situ Raman spectroscopy during the 1st reduction process in 1 mol dm(-3) LiClO4/ethylene carbonate (EC) + diethyl carbonate (DEC) (1 : 1 volume ratio), 1 mol dm(-3) LiCF3SO3/propylene carbonate (PC), and 1 mol dm(-3) LiCF3SO3/PC + tetraethylene glycol dimethyl ether (tetraglyme) (20 : 1 volume ratio). As a result, in the electrolyte solutions in which the lithium-ion intercalation reaction can occur (LiClO4/EC + DEC and LiCF3SO3/PC + tetraglyme), the Raman spectra of free solvent molecules (EC or PC) and anions showed a positive vibrational frequency shift during the co-intercalation reaction, and these shifts returned to their original positions during the lithium-ion intercalation reaction. On the other hand, there is no vibrational frequency shift in LiCF3SO3/PC, an electrolyte in which the lithium-ion intercalation reaction cannot occur. Based on our results, the relationship between the Raman shift and the solid electrolyte interphase (SEI) formation process was discussed.

  9. Study of the thermal stability of studtite by in situ Raman spectroscopy and DFT calculations

    NASA Astrophysics Data System (ADS)

    Colmenero, Francisco; Bonales, Laura J.; Cobos, Joaquín; Timón, Vicente

    2017-03-01

    The design of a safe spent nuclear fuel repository requires the knowledge of the stability of the secondary phases which precipitate when water reaches the fuel surface. Studtite is recognized as one of the secondary phases that play a key-role in the mobilization of the radionuclides contained in the spent fuel. Thereby, it has been identified as a product formed under oxidation conditions at the surface of the fuel, and recently found as a corrosion product in the Fukushima-Daiichi nuclear plant accident. Thermal stability is one of the properties that should be determined due to the high temperature of the fuel. In this work we report a detailed analysis of the structure and thermal stability of studtite. The structure has been studied both by experimental techniques (SEM, TGA, XRD and Raman spectroscopy) and theoretical DFT electronic structure and spectroscopic calculations. The comparison of the results allows us to perform for the first time the Raman bands assignment of the whole spectrum. The thermal stability of studtite has been analyzed by in situ Raman spectroscopy, with the aim of studying the effect of the heating rate and the presence of water. For this purpose, a new cell has been designed. The results show that studtite is stable under dry conditions only at temperatures below 30 °C, in contrast with the higher temperatures published up to date ( 130 °C). Opposite behaviour has been found when studtite is in contact with water; under these conditions studtite is stable up to 90 °C, what is consistent with the encounter of this phase after the Fukushima-Daiichi accident.

  10. Study of the thermal stability of studtite by in situ Raman spectroscopy and DFT calculations.

    PubMed

    Colmenero, Francisco; Bonales, Laura J; Cobos, Joaquín; Timón, Vicente

    2017-03-05

    The design of a safe spent nuclear fuel repository requires the knowledge of the stability of the secondary phases which precipitate when water reaches the fuel surface. Studtite is recognized as one of the secondary phases that play a key-role in the mobilization of the radionuclides contained in the spent fuel. Thereby, it has been identified as a product formed under oxidation conditions at the surface of the fuel, and recently found as a corrosion product in the Fukushima-Daiichi nuclear plant accident. Thermal stability is one of the properties that should be determined due to the high temperature of the fuel. In this work we report a detailed analysis of the structure and thermal stability of studtite. The structure has been studied both by experimental techniques (SEM, TGA, XRD and Raman spectroscopy) and theoretical DFT electronic structure and spectroscopic calculations. The comparison of the results allows us to perform for the first time the Raman bands assignment of the whole spectrum. The thermal stability of studtite has been analyzed by in situ Raman spectroscopy, with the aim of studying the effect of the heating rate and the presence of water. For this purpose, a new cell has been designed. The results show that studtite is stable under dry conditions only at temperatures below 30°C, in contrast with the higher temperatures published up to date (~130°C). Opposite behaviour has been found when studtite is in contact with water; under these conditions studtite is stable up to 90°C, what is consistent with the encounter of this phase after the Fukushima-Daiichi accident.

  11. 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.

  12. Raman microscopic applications in the biopharmaceutical industry: in situ identification of foreign particulates inside glass containers with aqueous formulated solutions.

    PubMed

    Cao, Xiaolin; Wen, Zai-Qing; Vance, Aylin; Torraca, Gianpiero

    2009-07-01

    Particle identification is an important analytical procedure for quality control and assurance in the biopharmaceutical industry. Rapid and reliable identification of micro-particles helps in evaluating the nature of particle contamination and its consequences on the product quality regulated by internal and external standards. Raman microscopy is one of the microspectroscopic techniques that can be used to identify micro-particles with the advantage of in situ detection. In this paper we demonstrate that a visible laser Raman microscope was particularly useful to identify micro-particles that were inside glass containers such as glass syringes, vials, and test tubes, which are commonly used as containers for aqueous formulated drugs. The examples include the identifications of a droplet-like particle inside a pre-filled glass syringe, a fibrous particle inside a glass test tube, and a white particle inside a glass vial; all of these examples usually demand challenging or time-consuming sample manipulation for other techniques. The Raman microscopic technique was shown to be able to solve these challenging micro-particle identifications due to its ability to carry out detection in situ. Particularly in the example of micro-droplet identification, the Raman microscopic technique was the only choice for a fast and successful particle detection. For all three identifications, Raman in situ detection has significantly accelerated particle analysis and avoided potential sample secondary contamination or losses owing to none or minimal sample manipulation.

  13. Mechanical Anisotropy and Pressure Induced Structural Changes in Piroxicam Crystals Probed by In Situ Indentation and Raman Spectroscopy

    NASA Astrophysics Data System (ADS)

    Manimunda, Praveena; Hintsala, Eric; Asif, Syed; Mishra, Manish Kumar

    2017-01-01

    The ability to correlate mechanical and chemical characterization techniques in real time is both lacking and powerful tool for gaining insights into material behavior. This is demonstrated through use of a novel nanoindentation device equipped with Raman spectroscopy to explore the deformation-induced structural changes in piroxicam crystals. Mechanical anisotropy was observed in two major faces ( 0bar{1}1 ) and (011), which are correlated to changes in the interlayer interaction from in situ Raman spectra recorded during indentation. The results of this study demonstrate the considerable potential of an in situ Raman nanoindentation instrument for studying a variety of topics, including stress-induced phase transformation mechanisms, mechanochemistry, and solid state reactivity under mechanical forces that occur in molecular and pharmaceutical solids.

  14. 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

  15. 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.

  16. Deep UV Raman spectroscopy for planetary exploration: The search for in situ organics

    NASA Astrophysics Data System (ADS)

    Abbey, William J.; Bhartia, Rohit; Beegle, Luther W.; DeFlores, Lauren; Paez, Veronica; Sijapati, Kripa; Sijapati, Shakher; Williford, Kenneth; Tuite, Michael; Hug, William; Reid, Ray

    2017-07-01

    Raman spectroscopy has emerged as a powerful, non-contact, non-destructive technique for detection and characterization of in situ organic compounds. Excitation using deep UV wavelengths (< 250 nm), in particular, offers the benefits of spectra obtained in a largely fluorescence-free region while taking advantage of signal enhancing resonance Raman effects for key classes of organic compounds, such as the aromatics. In order to demonstrate the utility of this technique for planetary exploration and astrobiological applications, we interrogated three sets of samples using a custom built Raman instrument equipped with a deep UV (248.6 nm) excitation source. The sample sets included: (1) the Mojave Mars Simulant, a well characterized basaltic sample used as an analog for Martian regolith, in which we detected ∼0.04 wt% of condensed carbon; (2) a suite of organic (aromatic hydrocarbons, carboxylic acids, and amino acids) and astrobiologically relevant inorganic (sulfates, carbonates, phosphates, nitrates and perchlorate) standards, many of which have not had deep UV Raman spectra in the solid phase previously reported in the literature; and (3) Mojave Mars Simulant spiked with a representative selection of these standards, at a concentration of 1 wt%, in order to investigate natural 'real world' matrix effects. We were able to resolve all of the standards tested at this concentration. Some compounds, such as the aromatic hydrocarbons, have especially strong signals due to resonance effects even when present in trace amounts. Phenanthrene, one of the aromatic hydrocarbons, was also examined at a concentration of 0.1 wt% and even at this level was found to have a strong signal-to-noise ratio. It should be noted that the instrument utilized in this study was designed to approximate the operation of a 'fieldable' spectrometer in order to test astrobiological applications both here on Earth as well as for current and future planetary missions. It is the foundation of

  17. 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.

  18. 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

  19. In situ mechanical and molecular investigations of collagen/apatite biomimetic composites combining Raman spectroscopy and stress-strain analysis.

    PubMed

    Chatzipanagis, Konstantinos; Baumann, Christoph G; Sandri, Monica; Sprio, Simone; Tampieri, Anna; Kröger, Roland

    2016-12-01

    We report the design, fabrication and application of a novel micro-electromechanical device coupled to a confocal Raman microscope that enables in situ molecular investigations of micro-fibers under uniaxial tensile load. This device allows for the mechanical study of micro-fibers with diameters in the range between 10 and 100μm and lengths of several hundred micrometers. By exerting forces in the mN range, the device enables an important force range to be accessed between that of atomic force microscopy and macroscopic stress-strain measurement devices. The load is varied using a stiffness-calibrated glass micro-needle driven by a piezo-translator during simultaneous Raman microscopy imaging. The method enables experiments probing the molecular response of micro-fibers to external stress. This set-up was applied to biomimetic non-mineralized and mineralized collagen micro-fibers revealing that above 30% mineralization the proline-related Raman band shows a pronounced response to stress, which is not observed in non-mineralized collagen. This molecular response coincides with a strong increase in the Young's modulus from 0.5 to 6GPa for 0% and 70% mineralized collagen, respectively. Our results are consistent with a progressive interlocking of the collagen triple-helices by apatite nanocrystals as the degree of mineralization increases. Collagen and apatite are the main constituents regulating the mechanical properties of bone. Hence, an improved understanding of the impact of mineralization on these properties is of large interest for the scientific community. This paper presents systematic studies of synthetic collagen microfibers with increasing apatite content and their response to tensile stress by using a novel self-made electromechanical device combined with a Raman spectrometer for molecular level studies. The impact of apatite on the mechanical and molecular response of collagen is evaluated giving important insights into the interaction between the

  20. 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

  1. 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.

  2. In situ dynamic tracking of heterogeneous nanocatalytic processes by shell-isolated nanoparticle-enhanced Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Zhang, Hua; Wang, Chen; Sun, Han-Lei; Fu, Gang; Chen, Shu; Zhang, Yue-Jiao; Chen, Bing-Hui; Anema, Jason R.; Yang, Zhi-Lin; Li, Jian-Feng; Tian, Zhong-Qun

    2017-05-01

    Surface molecular information acquired in situ from a catalytic process can greatly promote the rational design of highly efficient catalysts by revealing structure-activity relationships and reaction mechanisms. Raman spectroscopy can provide this rich structural information, but normal Raman is not sensitive enough to detect trace active species adsorbed on the surface of catalysts. Here we develop a general method for in situ monitoring of heterogeneous catalytic processes through shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS) satellite nanocomposites (Au-core silica-shell nanocatalyst-satellite structures), which are stable and have extremely high surface Raman sensitivity. By combining operando SHINERS with density functional theory calculations, we identify the working mechanisms for CO oxidation over PtFe and Pd nanocatalysts, which are typical low- and high-temperature catalysts, respectively. Active species, such as surface oxides, superoxide/peroxide species and Pd-C/Pt-C bonds are directly observed during the reactions. We demonstrate that in situ SHINERS can provide a deep understanding of the fundamental concepts of catalysis.

  3. In situ dynamic tracking of heterogeneous nanocatalytic processes by shell-isolated nanoparticle-enhanced Raman spectroscopy

    PubMed Central

    Zhang, Hua; Wang, Chen; Sun, Han-Lei; Fu, Gang; Chen, Shu; Zhang, Yue-Jiao; Chen, Bing-Hui; Anema, Jason R.; Yang, Zhi-Lin; Li, Jian-Feng; Tian, Zhong-Qun

    2017-01-01

    Surface molecular information acquired in situ from a catalytic process can greatly promote the rational design of highly efficient catalysts by revealing structure-activity relationships and reaction mechanisms. Raman spectroscopy can provide this rich structural information, but normal Raman is not sensitive enough to detect trace active species adsorbed on the surface of catalysts. Here we develop a general method for in situ monitoring of heterogeneous catalytic processes through shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS) satellite nanocomposites (Au-core silica-shell nanocatalyst-satellite structures), which are stable and have extremely high surface Raman sensitivity. By combining operando SHINERS with density functional theory calculations, we identify the working mechanisms for CO oxidation over PtFe and Pd nanocatalysts, which are typical low- and high-temperature catalysts, respectively. Active species, such as surface oxides, superoxide/peroxide species and Pd–C/Pt–C bonds are directly observed during the reactions. We demonstrate that in situ SHINERS can provide a deep understanding of the fundamental concepts of catalysis. PMID:28537269

  4. Recent Advances in Deep-Sea in situ Geochemical Measurements by ROV Deployed Laser Raman Spectroscopy.

    NASA Astrophysics Data System (ADS)

    Peltzer, E. T.; Henthorn, R.; Hester, K. C.; Kirkwood, W. J.; Rosal, J.; Salamy, K. A.; Scholfield, J.; Shane, F. F.; Sherman, A. D.; Walz, P. M.; Brewer, P. G.

    2007-12-01

    Raman spectroscopy is a valuable analytical technique for making in situ geochemical measurements. It is applicable to liquids, solids and gases; requires little or no sample preparation; and is rapid with typical analysis times of several minutes or less. These features combine to make it an ideal technique for deployment and use on remotely operated vehicles in a variety of applications. We report results from our second generation laser Raman spectrometer (DORISS2), developed in conjunction with Kaiser Optical Systems, Inc., which is both lighter and more robust than the original design. Packaged within a single titanium pressure housing rated to 4000m, DORISS2 has a floating optical bench which minimizes misalignments and preserves instrument calibration both during and between dives. The pressure compensated fiber optic cables have improved signal strength from 8% to 88% at 1024 m greatly reducing the time required to acquire a sample spectrum and allowing the detection of lower concentrations of trace components. Development of the precision underwater positioner (PUP) has enabled the spectroscopic analysis of opaque targets where a focusing precision of +/- 0.1 mm is required. This has allowed us to investigate the composition of authigenic minerals (such as hydrothermal vent precipitates) and gas hydrates in their native and undisturbed condition, such as the massive outcrops on the seafloor at Barkley Canyon, or to inspect the fine-scale inhomogeneities that occur in seafloor synthesis experiments conducted in Monterey Bay. The recent development of a single axis positioner (SAP) has allowed us to use DORISS2 when payload weight is an issue, in places where the seafloor is too steep to safely deploy PUP, or where operational conditions (such as an overhanging ledge) are too restrictive and where PUP does not fit. The SAP adds a new degree of flexibility we have not previously had and has even permitted the analysis of scale carotenoids in a live rock fish

  5. In situ Raman spectroscopic analysis of surface oxide films on Ni-base alloy/low alloy steel dissimilar metal weld interfaces in high-temperature water

    NASA Astrophysics Data System (ADS)

    Kim, Jongjin; Choi, Kyung Joon; Bahn, Chi Bum; Kim, Ji Hyun

    2014-06-01

    In situ Raman spectroscopy has been applied to analyze the surface oxide films formed on dissimilar metal weld (DMW) interfaces of nickel-base alloy/low alloy steel under hydrogenated high-temperature water condition. For the analysis of the oxide films under high temperature/pressure aqueous conditions, an in situ Raman spectroscopy system was developed by constructing a hydrothermal cell where the entire optics including the excitation laser and the Raman light collection system were located at the nearest position to the specimen by means of immersion optics. In situ Raman spectra of the DMW interfaces were collected in hydrogenated water condition at different temperatures up to 300 °C. The measured in situ Raman spectra showed peaks of Cr2O3, NiCr2O4 and Fe3O4 at the DMW interface. It is considered that differences in the oxide chemistry originated from the chemical element distribution inside of the DMW interface 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. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

    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.

  9. 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

  10. 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

  11. 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.

  12. High pressure synthesis and in situ Raman spectroscopy of H2 and HD clathrate hydrates.

    PubMed

    Zaghloul, Mohamed A S; Celli, Milva; Salem, N M; Elsheikh, S M; Ulivi, Lorenzo

    2012-10-28

    By means of a newly constructed high pressure and low temperature optical apparatus we have measured the Raman spectra of H(2) and HD simple clathrate hydrates, synthesized in situ by the application of more than 2500 bar gas pressure on solid water. High resolution spectra of the molecular vibration have been measured at low temperature (about 20 K). In the case of HD this band is simpler than in the case of H(2), where the presence of the ortho- and para-species complicated the interpretation of the spectrum. We have determined frequency positions of the bands arising from multiple occupancy of the large cages of the sII clathrate, some of which are almost superimposed. The intensity of the bands gives information on the average and distribution of cage occupation, and of the ortho-para (o-p) ratio of H(2) molecules. Hydrogen o-p conversion rate is measured, for molecules in the small cages and in the large cages, and it is observed that these are different. A model considering both intrinsic and extrinsic conversion processes is applied to the measured data. The intrinsic conversion rate so derived is compared favorably to that measured for pure hydrogen in different situations.

  13. 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

  14. In situ Raman probing of graphene over a broad doping range upon rubidium vapor exposure.

    PubMed

    Parret, Romain; Paillet, Matthieu; Huntzinger, Jean-Roch; Nakabayashi, Denise; Michel, Thierry; Tiberj, Antoine; Sauvajol, Jean-Louis; Zahab, Ahmed A

    2013-01-22

    We report in situ Raman scattering experiments on single-layer graphene (SLG) and Bernal bilayer graphene (BLG) during exposure to rubidium vapor. The G- and 2D-band evolutions with doping time are presented and analyzed. On SLG, the extended doping range scanned (up to about 10(14) electrons/cm(2)) allows the observation of three regimes in the evolution of the G-band frequency: a continuous upshift followed by a plateau and a downshift. Overall the measured evolution is interpreted as the signature of the competition between dynamic and adiabatic effects upon n-doping. Comparison of the obtained results with theoretical predictions indicates however that a substrate pinning effect occurs and inhibits charge-induced lattice expansion of SLG. At low doping, a direct link between electrostatic gating and Rb doping results is presented. For BLG, the added electrons are shown to be first confined in the top layer, but the system evolves with time toward a more symmetric repartition of the added electrons in both layers. The results obtained on BLG also confirm that the slope of the phonon dispersion close to the K point tends to be slightly reduced at low doping but suggest the occurrence of an unexpected increase of the phonon dispersion slope at higher electron concentration.

  15. High pressure synthesis and in situ Raman spectroscopy of H2 and HD clathrate hydrates

    NASA Astrophysics Data System (ADS)

    Zaghloul, Mohamed A. S.; Celli, Milva; Salem, N. M.; Elsheikh, S. M.; Ulivi, Lorenzo

    2012-10-01

    By means of a newly constructed high pressure and low temperature optical apparatus we have measured the Raman spectra of H2 and HD simple clathrate hydrates, synthesized in situ by the application of more than 2500 bar gas pressure on solid water. High resolution spectra of the molecular vibration have been measured at low temperature (about 20 K). In the case of HD this band is simpler than in the case of H2, where the presence of the ortho- and para-species complicated the interpretation of the spectrum. We have determined frequency positions of the bands arising from multiple occupancy of the large cages of the sII clathrate, some of which are almost superimposed. The intensity of the bands gives information on the average and distribution of cage occupation, and of the ortho-para (o-p) ratio of H2 molecules. Hydrogen o-p conversion rate is measured, for molecules in the small cages and in the large cages, and it is observed that these are different. A model considering both intrinsic and extrinsic conversion processes is applied to the measured data. The intrinsic conversion rate so derived is compared favorably to that measured for pure hydrogen in different situations.

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

    DOE PAGES

    Share, Keith; Carter, Rachel E.; Nikolaev, Pavel; ...

    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

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

    PubMed

    Maher, Robert C; 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.

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

    PubMed

    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

    2013-11-12

    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.

  19. In situ flavonoid analysis by FT-Raman spectroscopy: identification, distribution, and quantification of aspalathin in green rooibos (Aspalathus linearis).

    PubMed

    Baranska, Malgorzata; Schulz, Hartwig; Joubert, Elizabeth; Manley, Marena

    2006-11-15

    FT-Raman spectroscopy was used for the first time for in situ identification of aspalathin and quantification of the dihyrochalcones in dried, green rooibos (Aspalathus linearis). With the support of two-dimensional correlation spectroscopy, characteristic key bands of aspalathin, the main flavonoid and antioxidant occurring in rooibos, were localized and identified in the spectra obtained from various plant samples. Application of Raman mapping revealed the spatial distribution of this valuable dihydrochalcone within the intact dried leaves. Based on the spectral data and reference HPLC values, reliable multivariate calibration models were developed for quantification of aspalathin, nothofagin, and the combined dihydrochalcone contents of dried, green rooibos.

  20. In situ quantitative and kinetic study by Fourier transform raman spectroscopy of reaction between nitriles and hydroperoxides

    NASA Astrophysics Data System (ADS)

    Vacque, V.; Dupuy, N.; Sombret, B.; Huvenne, J. P.; Legrand, P.

    1997-06-01

    The reaction of nitrile with alkaline hydrogen peroxide has been studied kinetically by means of iodometry several times. We proposed to set up an in situ analytical method to follow the consumption of nitrile. We applied FT-Raman spectroscopy coupled with a partial least-squares quantitative method to the study the reactions of hydrogen peroxide or tert-butyl hydroperoxide on benzonitrile and acetonitrile. The results obtained led us to conclusions on the reactivity of the hydroperoxides and on the rate of consumption of nitrile. Our study made also clear that FT-Raman spectroscopy was a convenient tool for controlling industrial processes.

  1. Label-free in situ imaging of oil body dynamics and chemistry in germination

    PubMed Central

    Waschatko, Gustav; Billecke, Nils; Schwendy, Sascha; Jaurich, Henriette; Bonn, Mischa; Vilgis, Thomas A.

    2016-01-01

    Plant oleosomes are uniquely emulsified lipid reservoirs that serve as the primary energy source during seed germination. These oil bodies undergo significant changes regarding their size, composition and structure during normal seedling development; however, a detailed characterization of these oil body dynamics, which critically affect oil body extractability and nutritional value, has remained challenging because of a limited ability to monitor oil body location and composition during germination in situ. Here, we demonstrate via in situ, label-free imaging that oil bodies are highly dynamic intracellular organelles that are morphologically and biochemically remodelled extensively during germination. Label-free, coherent Raman microscopy (CRM) combined with bulk biochemical measurements revealed the temporal and spatial regulation of oil bodies in native soya bean cotyledons during the first eight days of germination. Oil bodies undergo a cycle of growth and shrinkage that is paralleled by lipid and protein compositional changes. Specifically, the total protein concentration associated with oil bodies increases in the first phase of germination and subsequently decreases. Lipids contained within the oil bodies change in saturation and chain length during germination. Our results show that CRM is a well-suited platform to monitor in situ lipid dynamics and local chemistry and that oil bodies are actively remodelled during germination. This underscores the dynamic role of lipid reservoirs in plant development. PMID:27798279

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

    PubMed

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

    2013-10-25

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

  3. High Speed Method for in Situ Multispectral Image Registration

    SciTech Connect

    Perrine, Kenneth A.; Lamarche, Brian L.; Hopkins, Derek F.; Budge, Scott E.; Opresko, Lee; Wiley, H. S.; Sowa, Marianne B.

    2007-01-29

    Multispectral confocal spinning disk microscopy provides a high resolution method for real-time live cell imaging. However, optical distortions and the physical misalignments introduced by the use of multiple acquisition cameras can obscure spatial information contained in the captured images. In this manuscript, we describe a multispectral method for real-time image registration whereby the image from one camera is warped onto the image from a second camera via a polynomial correction. This method provides a real-time pixel-for-pixel match between images obtained over physically distinct optical paths. Using an in situ calibration method, the polynomial is characterized by a set of coefficients using a least squares solver. Error analysis demonstrates optimal performance results from the use of cubic polynomials. High-speed evaluation of the warp is then performed through forward differencing with fixed-point data types. Image reconstruction errors are reduced through bilinear interpolation. The registration techniques described here allow for successful registration of multispectral images in real-time (exceeding 15 frame/sec) and have a broad applicability to imaging methods requiring pixel matching over multiple data channels.

  4. In situ Raman characterization of minerals and degradation processes in a variety of cultural and geological heritage sites.

    PubMed

    Gázquez, F; Rull, F; Sanz-Arranz, A; Medina, J; Calaforra, J M; de Las Heras, C; Lasheras, J A

    2017-02-05

    We test the capabilities of in situ Raman spectroscopy for non-destructive analysis of degradation processes in invaluable masterpieces, as well as for the characterization of minerals and prehistoric rock-art in caves. To this end, we have studied the mechanism of decay suffered by the 15th-century limestone sculptures that decorate the retro-choir of Burgos Cathedral (N Spain). In situ Raman probe detected hydrated sulfate and nitrate minerals on the sculptures, which are responsible for the decay of the original limestone. In addition, in situ Raman analyses were performed on unique speleothems in El Soplao Cave (Cantabria, N Spain) and in the Gruta de las Maravillas (Aracena, SW Spain). Unusual cave minerals were detected in El Soplao Cave, such as hydromagnesite (Mg5(CO3)4(OH)2·4H2O), as well as ferromanganese oxides in the black biogenic speleothems recently discovered in this cavern. In the Gruta de las Maravillas, gypsum (CaSO4·2H2O) was identified for the first time, as part of the oldest cave materials, so providing additional evidence of hypogenic mechanisms that occurred in this cave during earlier stages of its formation. Finally, we present preliminary analyses of several cave paintings in the renowned "Polychrome Hall" of Altamira Cave (Cantabria, N. Spain). Hematite (Fe2O3) is the most abundant mineral phase, which provides the characteristic ochre-reddish color to the Altamira bison and deer paintings. Thus, portable Raman spectroscopy is demonstrated to be an analytical technique compatible with preserving our cultural and natural heritage, since the analysis does not require physical contact between the Raman head and the analyzed items.

  5. In situ Raman characterization of minerals and degradation processes in a variety of cultural and geological heritage sites

    NASA Astrophysics Data System (ADS)

    Gázquez, F.; Rull, F.; Sanz-Arranz, A.; Medina, J.; Calaforra, J. M.; de las Heras, C.; Lasheras, J. A.

    2017-02-01

    We test the capabilities of in situ Raman spectroscopy for non-destructive analysis of degradation processes in invaluable masterpieces, as well as for the characterization of minerals and prehistoric rock-art in caves. To this end, we have studied the mechanism of decay suffered by the 15th-century limestone sculptures that decorate the retro-choir of Burgos Cathedral (N Spain). In situ Raman probe detected hydrated sulfate and nitrate minerals on the sculptures, which are responsible for the decay of the original limestone. In addition, in situ Raman analyses were performed on unique speleothems in El Soplao Cave (Cantabria, N Spain) and in the Gruta de las Maravillas (Aracena, SW Spain). Unusual cave minerals were detected in El Soplao Cave, such as hydromagnesite (Mg5(CO3)4(OH)2·4H2O), as well as ferromanganese oxides in the black biogenic speleothems recently discovered in this cavern. In the Gruta de las Maravillas, gypsum (CaSO4·2H2O) was identified for the first time, as part of the oldest cave materials, so providing additional evidence of hypogenic mechanisms that occurred in this cave during earlier stages of its formation. Finally, we present preliminary analyses of several cave paintings in the renowned "Polychrome Hall" of Altamira Cave (Cantabria, N. Spain). Hematite (Fe2O3) is the most abundant mineral phase, which provides the characteristic ochre-reddish color to the Altamira bison and deer paintings. Thus, portable Raman spectroscopy is demonstrated to be an analytical technique compatible with preserving our cultural and natural heritage, since the analysis does not require physical contact between the Raman head and the analyzed items.

  6. Confocal Raman imaging for cancer cell classification

    NASA Astrophysics Data System (ADS)

    Mathieu, Evelien; Van Dorpe, Pol; Stakenborg, Tim; Liu, Chengxun; Lagae, Liesbet

    2014-05-01

    We propose confocal Raman imaging as a label-free single cell characterization method that can be used as an alternative for conventional cell identification techniques that typically require labels, long incubation times and complex sample preparation. In this study it is investigated whether cancer and blood cells can be distinguished based on their Raman spectra. 2D Raman scans are recorded of 114 single cells, i.e. 60 breast (MCF-7), 5 cervix (HeLa) and 39 prostate (LNCaP) cancer cells and 10 monocytes (from healthy donors). For each cell an average spectrum is calculated and principal component analysis is performed on all average cell spectra. The main features of these principal components indicate that the information for cell identification based on Raman spectra mainly comes from the fatty acid composition in the cell. Based on the second and third principal component, blood cells could be distinguished from cancer cells; and prostate cancer cells could be distinguished from breast and cervix cancer cells. However, it was not possible to distinguish breast and cervix cancer cells. The results obtained in this study, demonstrate the potential of confocal Raman imaging for cell type classification and identification purposes.

  7. Quantitatively in Situ Imaging Silver Nanowire Hollowing Kinetics

    SciTech Connect

    Yu, Le; Yan, Zhongying; Cai, Zhonghou; Zhang, Dongtang; Han, Ping; Cheng, Xuemei; Sun, Yugang

    2016-09-28

    We report the in-situ investigation of the morphological evolution of silver nanowires to hollow silver oxide nanotubes using transmission x-ray microscopy (TXM). Complex silver diffusion kinetics and hollowing process via the Kirkendall effect have been captured in real time. Further quantitative x-ray absorption analysis reveals the difference between the longitudinal and radial diffusions. In conclusion, the diffusion coefficient of silver in its oxide nanoshell is, for the first time, calculated to be 1.2 × 10-13 cm2/s from the geometrical parameters extracted from the TXM images.

  8. Quantitatively in Situ Imaging Silver Nanowire Hollowing Kinetics

    DOE PAGES

    Yu, Le; Yan, Zhongying; Cai, Zhonghou; ...

    2016-09-28

    We report the in-situ investigation of the morphological evolution of silver nanowires to hollow silver oxide nanotubes using transmission x-ray microscopy (TXM). Complex silver diffusion kinetics and hollowing process via the Kirkendall effect have been captured in real time. Further quantitative x-ray absorption analysis reveals the difference between the longitudinal and radial diffusions. In conclusion, the diffusion coefficient of silver in its oxide nanoshell is, for the first time, calculated to be 1.2 × 10-13 cm2/s from the geometrical parameters extracted from the TXM images.

  9. Quantitatively In-situ Imaging Silver Nanowire Hollowing Kinetics

    SciTech Connect

    Yu, Le; Yan, Zhongying; Wang, Yuxin; Cai, Zhonghou; Han, Ping; Cheng, Xuemei; Sun, Yugang

    2016-10-01

    We report the in-situ investigation of the morphological evolution of silver nanowires to hollow silver oxide nanotubes using transmission x-ray microscopy (TXM). Complex silver diffusion kinetics and hollowing process via the Kirkendall effect have been captured in real time. Further quantitative x-ray absorption analysis reveals the difference between the longitudinal and radial diffusions. The diffusion coefficient of silver in its oxide nanoshell is, for the first time, calculated to be 1.2 × 10-13 cm2/s from the geometrical parameters extracted from the TXM images.

  10. Raman imaging using fixed bandpass filter

    NASA Astrophysics Data System (ADS)

    Landström, L.; Kullander, F.; Lundén, H.; Wästerby, P.

    2017-05-01

    By using fixed narrow band pass optical filtering and scanning the laser excitation wavelength, hyperspectral Raman imaging could be achieved. Experimental, proof-of-principle results from the Chemical Warfare Agent (CWA) tabun (GA) as well as the common CWA simulant tributyl phosphate (TBP) on different surfaces/substrates are presented and discussed.

  11. Raman spectroscopic identification of arsenate minerals in situ at outcrops with handheld (532 nm, 785 nm) instruments

    NASA Astrophysics Data System (ADS)

    Culka, Adam; Kindlová, Helena; Drahota, Petr; Jehlička, Jan

    2016-02-01

    Minerals are traditionally identified under field conditions by experienced mineralogists observing the basic physical properties of the samples. Under laboratory conditions, a plethora of techniques are commonly used for identification of the geological phases based on their structural and spectroscopic parameters. In this area, Raman spectrometry has become a useful tool to complement the more widely applied XRD. Today, however, there is an acute need for a technique for unambiguous in situ identification of minerals, within the geological as well as planetary/exobiology realms. With the potential for miniaturization, Raman spectroscopy can be viewed as a practical technique to achieve these goals. Here, for the first time, the successful application of handheld Raman spectrometers is demonstrated to detect and discriminate arsenic phases in the form of earthy aggregates. The Raman spectroscopic analyses of arsenate minerals were performed in situ using two handheld instruments, using 532 and 785 nm excitation. Bukovskýite, kaňkite, parascorodite, and scorodite were identified from Kaňk near Kutná Hora, CZE; kaňkite, scorodite, and zýkaite were identified at the Lehnschafter gallery in an old silver mine at Mikulov near Teplice, Bohemian Massif, CZE.

  12. Raman spectroscopic identification of arsenate minerals in situ at outcrops with handheld (532 nm, 785 nm) instruments.

    PubMed

    Culka, Adam; Kindlová, Helena; Drahota, Petr; Jehlička, Jan

    2016-02-05

    Minerals are traditionally identified under field conditions by experienced mineralogists observing the basic physical properties of the samples. Under laboratory conditions, a plethora of techniques are commonly used for identification of the geological phases based on their structural and spectroscopic parameters. In this area, Raman spectrometry has become a useful tool to complement the more widely applied XRD. Today, however, there is an acute need for a technique for unambiguous in situ identification of minerals, within the geological as well as planetary/exobiology realms. With the potential for miniaturization, Raman spectroscopy can be viewed as a practical technique to achieve these goals. Here, for the first time, the successful application of handheld Raman spectrometers is demonstrated to detect and discriminate arsenic phases in the form of earthy aggregates. The Raman spectroscopic analyses of arsenate minerals were performed in situ using two handheld instruments, using 532 and 785 nm excitation. Bukovskýite, kaňkite, parascorodite, and scorodite were identified from Kaňk near Kutná Hora, CZE; kaňkite, scorodite, and zýkaite were identified at the Lehnschafter gallery in an old silver mine at Mikulov near Teplice, Bohemian Massif, CZE. Copyright © 2015 Elsevier B.V. All rights reserved.

  13. Monitor Polyimide Production from Diamine and Dianhydride Reactions Using a Combination of In Situ Infrared and Raman Spectroscopy.

    PubMed

    Chen, Xiaoyun; Wang, Qing Min; Bu, Luke

    2017-09-01

    A two-step synthesis of polyimide reaction from dianhydride and diamine was followed by both infrared (IR) and Raman spectroscopy in situ in this case study. In the first step, the two reactants form poly(amide acid), which resulted in substantial spectral changes easily detected by both spectroscopic techniques. The reaction was found to occur rapidly and reached completion within tens of minutes at room temperature. In the second step, trimethylamine (catalyst) and acetic anhydride (dehydration agent) were added to form the five-member imide ring. Interestingly, different spectral changes were observed using IR and Raman spectroscopic methods due to their different responses toward the various functional groups involved. Conclusive evidence was also obtained based on the Raman results to demonstrate a long-lived intermediate species, which was harder to observe in the IR results. This work provides a good case study of the combined use of different vibrational spectroscopy techniques to extract maximum information from a reaction system.

  14. 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.

  15. 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.

  16. Raman chemical imaging system for food safety and quality inspection

    USDA-ARS?s Scientific Manuscript database

    Raman chemical imaging technique combines Raman spectroscopy and digital imaging to visualize composition and structure of a target, and it offers great potential for food safety and quality research. In this study, a laboratory-based Raman chemical imaging platform was designed and developed. The i...

  17. 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

  18. 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.

  19. 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

  20. Development and deployment of a precision underwater positioning system for in situ laser Raman spectroscopy in the deep ocean

    NASA Astrophysics Data System (ADS)

    White, Sheri N.; Kirkwood, William; Sherman, Alana; Brown, Mark; Henthorn, Richard; Salamy, Karen; Walz, Peter; Peltzer, Edward T.; Brewer, Peter G.

    2005-12-01

    The field of ocean geochemistry has recently been expanded to include in situ laser Raman spectroscopic measurements in the deep ocean. While this technique has proved to be successful for transparent targets, such as fluids and gases, difficulty exists in using deep submergence vehicle manipulators to position and control the very small laser spot with respect to opaque samples of interest, such as many rocks, minerals, bacterial mats, and seafloor gas hydrates. We have developed, tested, and successfully deployed by remotely operated vehicle (ROV) a precision underwater positioner (PUP) which provides the stability and precision movement required to perform spectroscopic measurements using the Deep Ocean Raman In situ Spectrometer (DORISS) instrument on opaque targets in the deep ocean for geochemical research. The positioner is also adaptable to other sensors, such as electrodes, which require precise control and positioning on the seafloor. PUP is capable of translating the DORISS optical head with a precision of 0.1 mm in three dimensions over a range of at least 15 cm, at depths up to 4000 m, and under the normal range of oceanic conditions (T, P, current velocity). The positioner is controlled, and spectra are obtained, in real time via Ethernet by scientists aboard the surface vessel. This capability has allowed us to acquire high quality Raman spectra of targets such as rocks, shells, and gas hydrates on the seafloor, including the ability to scan the laser spot across a rock surface in sub-millimeter increments to identify the constituent mineral grains. These developments have greatly enhanced the ability to obtain in situ Raman spectra on the seafloor from an enormous range of specimens.

  1. 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.

  2. 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.

  3. Tissue section AFM: In situ ultrastructural imaging of native biomolecules

    PubMed Central

    Graham, Helen K.; Hodson, Nigel W.; Hoyland, Judith A.; Millward-Sadler, Sarah J.; Garrod, David; Scothern, Anthea; Griffiths, Christopher E.M.; Watson, Rachel E.B.; Cox, Thomas R.; Erler, Janine T.; Trafford, Andrew W.; Sherratt, Michael J.

    2010-01-01

    Conventional approaches for ultrastructural high-resolution imaging of biological specimens induce profound changes in bio-molecular structures. By combining tissue cryo-sectioning with non-destructive atomic force microscopy (AFM) imaging we have developed a methodology that may be applied by the non-specialist to both preserve and visualize bio-molecular structures (in particular extracellular matrix assemblies) in situ. This tissue section AFM technique is capable of: i) resolving nm–µm scale features of intra- and extracellular structures in tissue cryo-sections; ii) imaging the same tissue region before and after experimental interventions; iii) combining ultrastructural imaging with complimentary microscopical and micromechanical methods. Here, we employ this technique to: i) visualize the macro-molecular structures of unstained and unfixed fibrillar collagens (in skin, cartilage and intervertebral disc), elastic fibres (in aorta and lung), desmosomes (in nasal epithelium) and mitochondria (in heart); ii) quantify the ultrastructural effects of sequential collagenase digestion on a single elastic fibre; iii) correlate optical (auto fluorescent) with ultrastructural (AFM) images of aortic elastic lamellae. PMID:20144712

  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. Raman chemical imaging technology for food safety and quality evaluation

    USDA-ARS?s Scientific Manuscript database

    Raman chemical imaging combines Raman spectroscopy and digital imaging to visualize composition and morphology of a target. This technique offers great potential for food safety and quality research. Most commercial Raman instruments perform measurement at microscopic level, and the spatial range ca...

  6. 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.

  7. Biomedical applications of a new portable Raman imaging probe

    NASA Astrophysics Data System (ADS)

    Sato, Hidetoshi; Tanaka, Takeyuki; Ikeda, Teruki; Wada, Satoshi; Tashiro, Hideo; Ozaki, Yukihiro

    2001-10-01

    This article reports the outline of a new portable Raman imaging probe and its applications. This probe may be the smallest and lightest Raman imaging probe in the world. It is equipped with an interchangeable long-working distance microscope objective lens. The irradiation area is about 45 and 90 μm and the spatial resolution is 1 μm. In the present study, the Raman imaging probe was used to obtain a Raman image of diamond particles and a Raman mapping of carotenoid in Euglena.

  8. In situ imaging of biofilm within opaque porous media (Invited)

    NASA Astrophysics Data System (ADS)

    Iltis, G.; Davit, Y.; Wood, B. D.; Wildenschild, D.

    2010-12-01

    Microbial biofilms are observed in both natural and engineered subsurface environments and can dramatically alter the physical properties of porous media. Current understanding of biofilm formation and the associated impacts to structural and hydrodynamic properties of porous media are limited by our ability to observe changes to pore morphology in situ. Imaging biofilm within opaque porous media has historically presented a significant challenge. Synchrotron-based x-ray computed microtomography has been a long standing tool for the non-destructive imaging of porous media; however, traditional contrast agents used in tomography research diffuse readily into both the aqueous phase as well as the porous media associated biofilm, thereby preventing easy delineation of the two phases. Two new methods for imaging biofilm within porous media using x-ray microtomography will be presented. The first method utilizes silver-coated glass microspheres as a surface attached contrast agent for delineating the biofilm-aqueous phase interface within porous media. The second method introduces a barium sulfate suspension to the aqueous phase which is excluded from the biofilm matrix. The use of these contrast agents allow for direct segmentation of the solid, biofilm and aqueous phases. Imaging results using both of these methods will be presented along with the respective advantages and limitations. Quantitative analysis of biofilm formation and changes to macropore morphology will be presented, along with potential applications for these methods.

  9. Facile synthesis of AgCl/polydopamine/Ag nanoparticles with in-situ laser improving Raman scattering effect

    NASA Astrophysics Data System (ADS)

    Zhang, Yan; Zhang, Wenqi; Wang, Lin; Wang, Feng; Yang, Haifeng

    2017-01-01

    We reported a simple and fast method to prepare a composite material of polydopamine (PDA) adlayer covered cubic AgCl core, which was inlaid with Ag nanoparticles (NPs), shortly named as AgCl/PDA/AgNPs. The resultant AgCl/PDA/AgNPs could be employed as surface-enhanced Raman scattering (SERS) substrate for in-situ detection and the SERS activity could be further greatly improved due to the production of more AgNPs upon laser irradiation. With 4-mercaptopyridine (4-Mpy) as the probe molecule, the enhancement factor could reach 107. Additionally, such SERS substrate shows good reproducibility with relative standard deviation of 7.32% and long term stability (after storage for 100 days under ambient condition, SERS intensity decay is less than 25%). In-situ elevating SERS activity of AgCl/PDA/AgNPs induced by laser may be beneficial to sensitive analysis in practical fields.

  10. Tip-enhanced Raman spectroscopy (TERS) for in situ identification of indigo and iron gall ink on paper.

    PubMed

    Kurouski, Dmitry; Zaleski, Stephanie; Casadio, Francesca; Van Duyne, Richard P; Shah, Nilam C

    2014-06-18

    Confirmatory, nondestructive, and noninvasive identification of colorants in situ is of critical importance for the understanding of historical context and for the long-term preservation of cultural heritage objects. Although there are several established techniques for analyzing cultural heritage materials, there are very few analytical methods that can be used for molecular characterization when very little sample is available, and a minimally invasive approach is required. Tip-enhanced Raman spectroscopy (TERS) is a powerful analytical technique whose key features include high mass sensitivity, high spatial resolution, and precise positioning of the tip. In the current proof-of-concept study we utilized TERS to identify indigo dye and iron gall ink in situ on Kinwashi paper. In addition, TERS was used to identify iron gall ink on a historical document with handwritten text dated to the 19th century. We demonstrate that TERS can identify both of these colorants directly on paper. Moreover, vibrational modes from individual components of a complex chemical mixture, iron gall ink, can be identified. To the best of our knowledge, this is the first demonstration of in situ TERS for colorants of artistic relevance directly on historical materials. Overall, this work demonstrates the great potential of TERS as an additional spectroscopic tool for minimally invasive compositional characterization of artworks in situ and opens exciting new possibilities for cultural heritage research.

  11. In situ micro-Raman analysis and X-ray diffraction of nickel silicide thin films on silicon.

    PubMed

    Bhaskaran, M; Sriram, S; Perova, T S; Ermakov, V; Thorogood, G J; Short, K T; Holland, A S

    2009-01-01

    This article reports on the in situ analysis of nickel silicide (NiSi) thin films formed by thermal processing of nickel thin films deposited on silicon substrates. The in situ techniques employed for this study include micro-Raman spectroscopy (microRS) and X-ray diffraction (XRD); in both cases the variations for temperatures up to 350 degrees C has been studied. Nickel silicide thin films formed by vacuum annealing of nickel on silicon were used as a reference for these measurements. In situ analysis was carried out on nickel thin films on silicon, while the samples were heated from room temperature to 350 degrees C. Data was gathered at regular temperature intervals and other specific points of interest (such as 250 degrees C, where the reaction between nickel and silicon to form Ni(2)Si is expected). The transformations from the metallic state, through the intermediate reaction states, until the desired metal-silicon reaction product is attained, are discussed. The evolution of nickel silicide from the nickel film can be observed from both the microRS and XRD in situ studies. Variations in the evolution of silicide from metal for different silicon substrates are discussed, and these include (100) n-type, (100) p-type, and (110) p-type silicon substrates.

  12. In situ Raman monitoring of He{sup 2+} irradiation induced damage in a UO{sub 2} ceramic

    SciTech Connect

    Guimbretière, G.; Canizarès, A.; Duval, F.; Raimboux, N.; Omnée, R.; Ammar, M. R.; Simon, P.

    2013-07-22

    The in situ Raman probing of a UO{sub 2} ceramic in [Ar/H{sub 2}, 95/5] gas atmosphere followed by exposure to He{sup 2+} ionic irradiation coming from a cyclotron accelerator was implemented. It was observed that the growth of Raman defect bands exhibits a unique kinetic nicely modelized by a simple direct impact model, and with an annealing rate constant of 5.6 × 10{sup −4} ± 4 × 10{sup −5} s{sup −1} for an ionic flow of 50 nA and an ions-beam induced sample heating of 170 ± 10 °C. Also, it was observed that the Ar plasma induced by the ions-beam is a sensitive probe of the presence of the ions-beam.

  13. 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; ...

    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.

  14. 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.

  15. 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.

  16. 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.

  17. In situ visualization of intracellular morphology of epidermal cells using stimulated Raman scattering microscopy

    NASA Astrophysics Data System (ADS)

    Egawa, Mariko; Tokunaga, Kyoya; Hosoi, Junichi; Iwanaga, Shinya; Ozeki, Yasuyuki

    2016-08-01

    Visualization of epidermal cells is important because the differentiation patterns of keratinocytes (KCs) are considered to be related to the functions and condition of skin. Optical microscopy has been widely used to investigate epidermal cells, but its applicability is still limited because of the need for sample fixation and staining. Here, we report our staining-free observation of epidermal cells in both tissue and culture by stimulated Raman scattering (SRS) microscopy that provides molecular vibrational contrast. SRS allowed us to observe a variety of cellular morphologies in skin tissue, including ladder-like structures in the spinous layer, enucleation of KCs in the granular layer, and three-dimensional cell column structures in the stratum corneum. We noticed that some cells in the spinous layer had a brighter signal in the cytoplasm than KCs. To examine the relevance of the observation of epidermal layers, we also observed cultured epidermal cells, including KCs at various differentiation stages, melanocytes, and Langerhans cell-like cells. Their SRS images also demonstrated various morphologies, suggesting that the morphological differences observed in tissue corresponded to the cell lineage. These results indicate the possible application of SRS microscopy to dermatological investigation of cell lineages and types in the epidermis by cellular-level analysis.

  18. In situ visualization of intracellular morphology of epidermal cells using stimulated Raman scattering microscopy

    PubMed Central

    Egawa, Mariko; Tokunaga, Kyoya; Hosoi, Junichi; Iwanaga, Shinya; Ozeki, Yasuyuki

    2016-01-01

    Abstract. Visualization of epidermal cells is important because the differentiation patterns of keratinocytes (KCs) are considered to be related to the functions and condition of skin. Optical microscopy has been widely used to investigate epidermal cells, but its applicability is still limited because of the need for sample fixation and staining. Here, we report our staining-free observation of epidermal cells in both tissue and culture by stimulated Raman scattering (SRS) microscopy that provides molecular vibrational contrast. SRS allowed us to observe a variety of cellular morphologies in skin tissue, including ladder-like structures in the spinous layer, enucleation of KCs in the granular layer, and three-dimensional cell column structures in the stratum corneum. We noticed that some cells in the spinous layer had a brighter signal in the cytoplasm than KCs. To examine the relevance of the observation of epidermal layers, we also observed cultured epidermal cells, including KCs at various differentiation stages, melanocytes, and Langerhans cell-like cells. Their SRS images also demonstrated various morphologies, suggesting that the morphological differences observed in tissue corresponded to the cell lineage. These results indicate the possible application of SRS microscopy to dermatological investigation of cell lineages and types in the epidermis by cellular-level analysis. PMID:27580366

  19. 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.

  20. 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.

  1. A comparative Raman and CARS imaging study of colon tissue.

    PubMed

    Krafft, Christoph; Ramoji, Anuradha A; Bielecki, Christiane; Vogler, Nadine; Meyer, Tobias; Akimov, Denis; Rösch, Petra; Schmitt, Michael; Dietzek, Benjamin; Petersen, Iver; Stallmach, Andreas; Popp, Jürgen

    2009-05-01

    An experimental evaluation of the information content of two complimentary techniques, linear Raman and coherent anti-Stokes Raman scattering (CARS) microscopy, is presented. CARS is a nonlinear variant of Raman spectroscopy that enables rapid acquisition of images within seconds in combination with laser scanning microscopes. CARS images were recorded from thin colon tissue sections at 2850, 1660, 1450 and 1000 cm(-1) and compared with Raman images. Raman images were obtained from univariate and multivariate (k-means clustering) methods, whereas all CARS images represent univariate results. Variances within tissue sections could be visualized in chemical maps of CARS and Raman images. However, identification of tissue types and characterization of variances between different tissue sections were only possible by analysis of cluster mean spectra, obtained from k-means cluster analysis. This first comparison establishes the foundation for further development of the CARS technology to assess tissue.

  2. 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

  3. Raman tags: Novel optical probes for intracellular sensing and imaging.

    PubMed

    Li, Yuee; Wang, Zhong; Mu, Xijiao; Ma, Aning; Guo, Shu

    Optical labels are needed for probing specific target molecules in complex biological systems. As a newly emerging category of tags for molecular imaging in live cells, the Raman label attracts much attention because of the rich information obtained from targeted and untargeted molecules by detecting molecular vibrations. Here, we list three types of Raman probes based on different mechanisms: Surface Enhanced Raman Scattering (SERS) probes, bioorthogonal Raman probes, and Resonance Raman (RR) probes. We review how these Raman probes work for detecting and imaging proteins, nucleic acids, lipids, and other biomolecules in vitro, within cells, or in vivo. We also summarize recent noteworthy studies, expound on the construction of every type of Raman probe and operating principle, sum up in tables typically targeting molecules for specific binding, and provide merits, drawbacks, and future prospects for the three Raman probes. Copyright © 2016 Elsevier Inc. All rights reserved.

  4. [Research on the Quantitative Analysis for In-Situ Detection of Acid Radical Ions Using Laser Raman Spectroscopy].

    PubMed

    Chen, Jing; Li, Ying; Du, Zeng-feng; Gu, Yan-hong; Guo, Jin-jia

    2015-09-01

    Laser Raman spectroscopy as an in situ analytical technology can enable detailed investigation of the ocean environment. It is necessary to set up a quantitative analysis method based on laser Raman spectroscopy to understand the marine status in situ. In the laboratory investigations, varied concentration of HCO3(-), SO4(2-) and coastal waters of Qingdao are taken as the samples, operating 532 nm of laser, using fiber optic probes to simulate detection mode in situ. Raman spectra are analyzed using the method of internal standard normalization, multiple linear regression (MLR), general Partial Least Squares (PLS) and PLS based on dominant factor respectively in data processing. It was found that correlation coefficients of calibration curves are not high in internal standard normalization method and predicted relative errors on the prepared samples are much high, so internal standard normalization method cannot be effectively used in the quantitative analysis of HCO3(-), SO4(2-) in the water. And with the multiple linear regression, the analysis accuracy was improved effectively. The calibration curve of PLS based on dominant factor showed that the SO4(2-) and HCO3(-) of pre-made solution with correlation coefficient R2 of 0.990 and 0.916 respectively. The 30 mmol · L(-1) of SO4(2-) and 20 mmol · L(-1) of HCO3(-) in two target samples were determined with the relative errors lower than 3.262% and 5.267% respectively. SO4(2-) in the coastal waters as the research object was analyzed by above-mentioned methods, comparing with 28.01 mmol · L(-1) by ion chromatography. It was demonstrated that PLS based on dominant factor method is superior to the rest of the three analysis methods, which can be used in situ calibration, with the mean relative error about 1.128%. All the results show that analysis accuracy would be improved by the PLS based on dominant factor method to predict concentration of acid radical ions.

  5. Optical antenna arrays on a fiber facet for in situ surface-enhanced Raman scattering detection.

    PubMed

    Smythe, Elizabeth J; Dickey, Michael D; Bao, Jiming; Whitesides, George M; Capasso, Federico

    2009-03-01

    This paper reports a bidirectional fiber optic probe for the detection of surface-enhanced Raman scattering (SERS). One facet of the probe features an array of gold optical antennas designed to enhance Raman signals, while the other facet of the fiber is used for the input and collection of light. Simultaneous detection of benzenethiol and 2-[(E)-2-pyridin-4-ylethenyl]pyridine is demonstrated through a 35 cm long fiber. The array of nanoscale optical antennas was first defined by electron-beam lithography on a silicon wafer. The array was subsequently stripped from the wafer and then transferred to the facet of a fiber. Lithographic definition of the antennas provides a method for producing two-dimensional arrays with well-defined geometry, which allows (i) the optical response of the probe to be tuned and (ii) the density of "hot spots" generating the enhanced Raman signal to be controlled. It is difficult to determine the Raman signal enhancement factor (EF) of most fiber optic Raman sensors featuring hot spots because the geometry of the Raman enhancing nanostructures is poorly defined. The ability to control the size and spacing of the antennas enables the EF of the transferred array to be estimated. EF values estimated after focusing a laser directly onto the transferred array ranged from 2.6 x 10(5) to 5.1 x 10(5).

  6. Confocal Raman Imaging of Polymeric Materials

    NASA Astrophysics Data System (ADS)

    Schmidt, Ute; Müller, Jörg; Koenen, Joachim

    Polymers play an essential role in modern materials science. Due to the wide variety of mechanical and chemical properties of polymers, they are used in almost every field of application and are still a dynamic area in the development of new materials with demanding requirements. Raman spectroscopy is one of the standard characterization techniques used to uniquely determine the chemical composition of a polymer. Modern materials, however, are generally heterogeneous, in which various chemical components or polymorphs of the same chemical species can be present in a very small sample volume. For the analysis of such heterogeneous materials, the combination of Raman spectroscopy with confocal microscopy delivers information about the spatial distribution of the various chemical species with a resolution down to 200 nm. The aim of this contribution is to demonstrate the power of confocal Raman imaging for the characterization of heterogeneous polymeric materials. The first section will deal with polymorphs of polypropylene in polymer films, followed by the nondestructive analysis of polymer blends. A later section will deal with multi-layer polymer coatings and paints and finally various additives to polymer matrices will be discussed.

  7. 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.

  8. 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.

  9. Real-Time and in Situ Monitoring of Pesticide Penetration in Edible Leaves by Surface-Enhanced Raman Scattering Mapping.

    PubMed

    Yang, Tianxi; Zhang, Zhiyun; Zhao, Bin; Hou, Ruyan; Kinchla, Amanda; Clark, John M; He, Lili

    2016-05-17

    Understanding of the penetration behaviors of pesticides in fresh produce is of great significance for effectively applying pesticides and minimizing pesticide residues in food. There is lack, however, of an effective method that can measure pesticide penetration. Herein, we developed a novel method for real-time and in situ monitoring of pesticide penetration behaviors in spinach leaves based on surface-enhanced Raman scattering (SERS) mapping. Taking advantage of penetrative gold nanoparticles (AuNPs) as probes to enhance the internalized pesticide signals in situ, we have successfully obtained the internal signals from thiabendazole, a systemic pesticide, following its penetration into spinach leaves after removing surface pesticide residues. Comparatively, ferbam, a nonsystemic pesticide, did not show internal signals after removing surface pesticide residues, demonstrating its nonsystemic behavior. In both cases, if the surface pesticides were not removed, copenetration of both AuNPs and pesticides was observed. These results demonstrate a successful application of SERS as an effective method for measuring pesticides penetration in fresh produce in situ. The information obtained could provide useful guidance for effective and safe applications of pesticides on plants.

  10. Structural changes of polyacetylenes in American ginseng root can be observed in situ by using Raman spectroscopy.

    PubMed

    Baranska, Malgorzata; Schulz, Hartwig; Christensen, Lars P

    2006-05-17

    The presented results show the special advantage of Raman spectroscopy in the investigation of polyacetylenes in American ginseng (Panax quinquefolium L.) roots. The compounds are measured directly in the plant tissue without any preliminary sample preparation. The polyacetylene signal is strong and well-separated from other bands so the spectral impact of the surrounding biological matrix can be clearly distinguished. The Raman spectrum taken in situ from the fresh ginseng root revealed a characteristic polyacetylene key band at 2237 cm(-1) whereas in the spectrum obtained from dried root this band was shifted to about 2258 cm(-1). The latter is in good agreement with signals obtained from isolated standards, falcarinol (2258 cm(-1)) and panaxydol (2260 cm(-1)), occurring as predominant polyacetylenes in this species. The shift of the polyacetylene band observed in root extracts or at a certain stage of root drying indicates the molecular modification of polyacetylenes resulting from the loss of water. Furthermore, it was found that the process upon root hydration is reversible as the shift of polyacetylene band from 2258 to 2237 cm(-1) is observed. An explanation of this phenomenon can be an interaction of polyacetylene molecules with plant components in the presence of water molecules forming a stable entity in situ that is broken after dehydration (loss of water) of the fresh ginseng root. Application of the Raman mapping technique to ginseng roots of different size showed that the content of both main polyacetylenes decreases with increasing root size in accordance with quantitative high-performance liquid chromatography data.

  11. Raman imaging of molecular dynamics during cellular events

    NASA Astrophysics Data System (ADS)

    Fujita, Katsumasa

    2017-07-01

    To overcome the speed limitation in Raman imaging, we have developed a microscope system that detects Raman spectra from hundreds of points in a sample simultaneously. The sample was illuminated by a line-shaped focus, and Raman scattering from the illuminated positions was measured simultaneously by an imaging spectrophotometer. We applied the line-illumination technique to observe the dynamics of intracellular molecules during cellular events. We found that intracellular cytochrome c can be clearly imaged by resonant Raman scattering. We demonstrated label-free imaging of redistribution of cytochrome c during apoptosis and osteoblastic mineralization. We also proposed alkyne-tagged Raman imaging to observe small molecules in living cells. Due to its small size and the unique Raman band, alkyne can tag molecules without strong perturbation to molecular functions and with the capability to be detected separately from endogenous molecules.

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

    PubMed

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

    2015-09-11

    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.

  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. 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.

  15. 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.

  16. In situ surface-enhanced Raman spectroscopy effect in zeolite due to Ag2Se quantum dots

    NASA Astrophysics Data System (ADS)

    Martinez-Nuñez, C. E.; Cortez-Valadez, M.; Delgado-Beleño, Y.; Flores-López, N. S.; Román-Zamorano, J. F.; Flores-Valenzuela, J.; Flores-Acosta, M.

    2017-02-01

    This study shows the presence of surface-enhanced Raman spectroscopy (SERS) effect caused by Ag2Se quantum dots embedded in the zeolite matrix. The quantum dots that were synthesised and stabilised in the matrix of F9-NaX zeolite show a size of 5 nm and a quasi-spherical morphology. The calculated interplanar distances confirm the presence of quantum dots in cubic phase Im-m. We suppose that the in situ SERS effect in the material is caused by chemical-enhancement mechanism (CEM). The density functional theory (DFT) is undertaken to corroborate our hypothesis. The structure H8Si8Al8O12 represents the zeolite cavity unit, and small clusters of (Ag2Se) n represent the quantum dots. Both structures interact in the cavity to obtain the local minimum of the potential energy surface, leading to new molecular orbitals. After the analysis of the predicted Raman spectrum, the Raman bands increase significantly, agreeing with the experimental results at low wavenumbers in F9-NaX zeolite.

  17. 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.

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

    PubMed Central

    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. PMID:21280898

  19. 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.

  20. In situ Raman spectroscopy of lithium electrode surface in ambient temperature lithium secondary battery. Final report

    SciTech Connect

    Tachikawa, Hiroyasu

    1992-09-01

    Raman spectroscopy was used to characterize surface layers on lithium electrodes in different solvents such as propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), and polyethylene glycol 400 dimethyl ether (PEG400DME). Both DMC and DEC were used singly, and also mixed with either methyl acetate (MA) or methyl formate (MF). The Raman spectra showed that passive films formed on the Li surface in different solvents may have different chemical structures, which changed during the charging and discharging processes. Raman spectroscopy was also applied to characterize zinc electrode surfaces in alkaline solutions. The results suggested that ZnO and Zn(OH){sub 2} formed on the Zn electrode when a passive potential was applied. A solid film of fullerene C{sub 60}, which could be used as a cathode in Li rechargeable batteries, was examined in the PEG400DME solution by both electrochemical and Raman spectroscopy. Cyclic voltammograms (CVs) showed five redox peaks which suggested the formation of C{sub 60}{sup {minus}}, C{sub 60}{sup 2{minus}}, C{sub 60}{sup 3{minus}}, C{sub 60}{sup 4{minus}}, and C{sub 60}{sup 5{minus}}. Raman spectra obtained from a thin C{sub 60} film indicated that the thin fulleride film dissolved in the PEG400DME/LiClO{sub 4} solution at negative potentials.

  1. 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.

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

    SciTech Connect

    Mohseni, Hooman; Agahi, Massoud H.; Razeghi, Manijeh; Polisetti, Sneha; Baig, Nameera; Bible, Amber; Morrell-Falvey, Jennifer; Doktycz, Mitchel; Bohn, Paul W.

    2015-08-21

    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.

  3. Spectroscopic characterization of sixteenth century panel painting references using Raman, surface-enhanced Raman spectroscopy and helium-Raman system for in situ analysis of Ibero-American Colonial paintings.

    PubMed

    García-Bucio, María Angélica; Casanova-González, Edgar; Ruvalcaba-Sil, José Luis; Arroyo-Lemus, Elsa; Mitrani-Viggiano, Alejandro

    2016-12-13

    Colonial panel paintings constitute an essential part of Latin-American cultural heritage. Their study is vital for understanding the manufacturing process, including its evolution in history, as well as its authorship, dating and other information significant to art history and conservation purposes. Raman spectroscopy supplies a non-destructive characterization tool, which can be implemented for in situ analysis, via portable equipment. Specific methodologies must be developed, comprising the elaboration of reference panel paintings using techniques and materials similar to those of the analysed period, as well as the determination of the best analysis conditions for different pigments and ground preparations. In order to do so, Raman spectroscopy at 532, 785 and 1064 nm, surface-enhanced Raman spectroscopy (SERS) and a helium-Raman system were applied to a panel painting reference, in combination with X-ray fluorescence analysis. We were able to establish the analysis conditions for a number of sixteenth century pigments and dyes, and other relevant components of panel paintings from this period, 1064 nm Raman and SERS being the most successful. The acquired spectra contain valuable specific information for their identification and they conform a very useful database that can be applied to the analysis of Ibero-American Colonial paintings.This article is part of the themed issue 'Raman spectroscopy in art and archaeology'. © 2016 The Author(s).

  4. Spectroscopic characterization of sixteenth century panel painting references using Raman, surface-enhanced Raman spectroscopy and helium-Raman system for in situ analysis of Ibero-American Colonial paintings

    NASA Astrophysics Data System (ADS)

    García-Bucio, María Angélica; Casanova-González, Edgar; Ruvalcaba-Sil, José Luis; Arroyo-Lemus, Elsa; Mitrani-Viggiano, Alejandro

    2016-12-01

    Colonial panel paintings constitute an essential part of Latin-American cultural heritage. Their study is vital for understanding the manufacturing process, including its evolution in history, as well as its authorship, dating and other information significant to art history and conservation purposes. Raman spectroscopy supplies a non-destructive characterization tool, which can be implemented for in situ analysis, via portable equipment. Specific methodologies must be developed, comprising the elaboration of reference panel paintings using techniques and materials similar to those of the analysed period, as well as the determination of the best analysis conditions for different pigments and ground preparations. In order to do so, Raman spectroscopy at 532, 785 and 1064 nm, surface-enhanced Raman spectroscopy (SERS) and a helium-Raman system were applied to a panel painting reference, in combination with X-ray fluorescence analysis. We were able to establish the analysis conditions for a number of sixteenth century pigments and dyes, and other relevant components of panel paintings from this period, 1064 nm Raman and SERS being the most successful. The acquired spectra contain valuable specific information for their identification and they conform a very useful database that can be applied to the analysis of Ibero-American Colonial paintings. This article is part of the themed issue "Raman spectroscopy in art and archaeology".

  5. 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.

  6. Feasibility investigation on deep ocean compact autonomous Raman spectrometer developed for in-situ detection of acid radical ions

    NASA Astrophysics Data System (ADS)

    Du, Zengfeng; Li, Ying; Chen, Jing; Guo, Jinjia; Zheng, Rong'er

    2015-03-01

    A newly developed Deep Ocean Compact Autonomous Raman Spectrometer (DOCARS) system is introduced and used for in-situ detection of acid radical ions in this paper. To evaluate the feasibility and capability of DOCARS for quantitative analysis of the acid radical ions in the deep ocean, extensive investigations have been carried out both in laboratory and sea trials during the development phase. In the laboratory investigations, Raman spectra of the prepared samples (acid radical ions solutions) were obtained, and analyzed using the method of internal standard normalization in data processing. The Raman signal of acid radical ions was normalized by that of water molecules. The calibration curve showed that the normalized Raman signal intensity of SO{4/2-}, NO{3/-}, and HCO{2/-} increases linearly as the concentration rises with correlation coefficient R 2 of 0.99, 0.99, and 0.98 respectively. The linear function obtained from the calibration curve was then used for the analysis of the spectra data acquired in the sea trial under a simulating chemical field in the deep-sea environment. It was found that the detected concentration of NO{3/-} according to the linear function can reflect the concentration changes of NO{3/-} after the sample was released, and the detection accuracy of the DOCARS system for SO{4/2-} is 8%. All the results showed that the DOCARS system has great potential in quantitative detection of acid radical ions under the deep-sea environment, while the sensitivity of the DOCARS system is expected to be improved.

  7. Planar Laser Imaging of Scattering and Fluorescence of Zooplankton Feeding in Layers of Phytoplankton in situ

    DTIC Science & Technology

    2007-09-30

    Planar Laser Imaging of Scattering and Fluorescence of Zooplankton Feeding in Layers of Phytoplankton in situ Peter J.S. Franks Scripps...herbivorous copepod feeding in the laboratory, and 2) to apply these methods in the field to observe the dynamics of copepod feeding in situ. In...particular we intend to test the “ feeding sorties” hypothesis vs. the “in situ feeding ” hypothesis regarding the location and timing of copepod feeding

  8. Wide-Field Raman Imaging of Dental Lesions

    PubMed Central

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

    2014-01-01

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

  9. In-situ fabrication of gold nanoparticle functionalized probes for tip-enhanced Raman spectroscopy by dielectrophoresis

    NASA Astrophysics Data System (ADS)

    Sweetenham, Claire S.; Woolley, Richard A. J.; Notingher, Ioan

    2016-07-01

    We report the use of dielectrophoresis to fabricate in-situ probes for tip-enhanced Raman spectroscopy (TERS) based on Au nanoparticles. A typical conductive atomic force microscope (AFM) was used to functionalize iridium-coated conductive silicon probes with Au nanoparticles of 10-nm diameter. Suitable TERS probes can be rapidly produced (30 to 120 s) by applying a voltage of 10 Vpp at a frequency of 1 MHz. The technique has the advantage that the Au-based probes are ready for immediate use for TERS measurements, minimizing the risks of tip contamination and damage during handling. Scanning electron microscopy and energy dispersive x-ray spectroscopy were used to confirm the quality of the probes, and used samples of p-ATP monolayers on silver substrates were used to demonstrate experimentally TERS measurements.

  10. 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).

  11. 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

  12. A microfluidic bioreactor with in situ SERS imaging for the study of controlled flow patterns of biofilm precursor materials.

    PubMed

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

    2013-10-29

    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 × 10(4), 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.

  13. 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

  14. In Situ Raman Spectroscopic Study of the Diffusion Coefficients and Solubility:Indicates to Carbon Dioxide Injection into Hexadecane

    NASA Astrophysics Data System (ADS)

    Wu, Dan; Lu, Wanjun

    2015-04-01

    Injecting CO2 into lean-oil reservoirs is not only a way to geological storage but also enhanced oil recovery. In the secondary displacements of oil reservoir by CO2-injection, diffusion coefficients and solubility of CO2 are key parameters to calculate the volume of CO2 injected and the time to achieve the desired viscosity in the numerical simulation. Unfortunately, the experimental data on the CO2 diffusion coefficient and solubility in liquid hydrocarbons under high pressure conditions are scarce. Hexadecane has properties similar to the average properties of Brazilian heavy oil. Experimental data on the diffusion coefficients and solubility of CO2 in hexadecane were reviewed by Nieuwoudt and Rand (2002), Rincon and Trejo (2001) and Breman et al (1994), indicating that the data in the literature were limited at relatively low temperatures and/or low pressures. In this paper, the diffusion coefficients of carbon dioxide in hexadecane at different temperature and pressure were determined with in situ Raman spectroscopy. A model was established to describe relationship among diffusion coefficients, temperature, and pressure. The solubility of CO2 in hexadecane was obtained from 298.15 to 473.15 K and 10 to 45 MPa. The experimental results show that:(1) Solubility of CO2 decreases with increasing temperature.(2) Increasing pressure increases the CO2 solubility. in terms of the degree of influence,100K is similar with 10MPa.(3) Diffusion coefficients of CO2 increases with increasing temperature. (4) Increasing pressure decreases the CO2 diffusion coefficients, whereas the pressure effect on CO2 diffusion coefficients is very weak. Compared with traditional sampling and analytical methods, the advantages of our method include: (1) the use of in situ Raman signals for solubility 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.

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

    PubMed

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

    2014-06-05

    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.

  16. In situ monitoring of Joule heating effects in germanium nanowires by μ-Raman spectroscopy.

    PubMed

    Lugstein, Alois; Mijić, Mario; Burchhart, Thomas; Zeiner, Clemens; Langegger, Rupert; Schneider, Michael; Schmid, Ulrich; Bertagnolli, Emmerich

    2013-02-15

    We explored a noninvasive optical method to determine the Joule heating of individual germanium nanowires. Using confocal μ-Raman spectroscopy, variations in the optical phonon frequency, in detail the downshifting of the first-order Stokes Raman band, are correlated to the temperature increase of vapor-liquid-solid grown germanium nanowires under an applied electrical bias. The germanium nanowires were found to handle high threshold current densities of more than 10(6) A cm(-2) before sustaining immediate deterioration. Failure of single crystalline germanium nanowires was directly observed when the applied electric field reached the breakdown point of 1.25 × 10(5) V cm(-1).

  17. Pressure Induced Phase Transitions In SmVO{sub 4}: An In-Situ Raman Study

    SciTech Connect

    Patel, Nishant N.; Garg, Alka B.; Meenakshi, S.; Pandey, K. K.; Sharma, S. M.; Wani, B. N.

    2010-12-01

    High pressure room temperature Raman investigation on SmVO{sub 4} was carried out up to 19 GPa. The ambient zircon phase was observed to remain stable up to 5.8 GPa. At higher pressure two structural phase transitions were observed at 6.8 GPa and 15.9 GPa respectively. The second phase transition was found to be reversible whereas the intermediate phase was retained on complete pressure release.

  18. Development of an in situ fiber optic Raman system to monitor hydrothermal vents.

    PubMed

    Battaglia, Tina M; Dunn, Eileen E; Lilley, Marvin D; Holloway, John; Dable, Brian K; Marquardt, Brian J; Booksh, Karl S

    2004-07-01

    The development of a field portable fiber optic Raman system modified from commercially available components that can operate remotely on battery power and withstand the corrosive environment of the hydrothermal vents is discussed. The Raman system is designed for continuous monitoring in the deep-sea environment. A 785 nm diode laser was used in conjunction with a sapphire ball fiber optic Raman probe, single board computer, and a CCD detector. Using the system at ambient conditions the detection limits of SO(4)(2-), CO(3)(2-) and NO(3)(-) were determined to be approximately 0.11, 0.36 and 0.12 g l(-1) respectively. Mimicking the cold conditions of the sea floor by placing the equipment in a refrigerator yielded slightly worse detection limits of approximately 0.16 g l(-1) for SO(4)(-2) and 0.20 g l(-1) for NO(3)(-). Addition of minerals commonly found in vent fluid plumes also decreased the detection limits to approximately 0.33 and 0.34 g l(-1) respectively for SO(4)(-2) and NO(3)(-).

  19. 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.

  20. In Situ Raman Study of Redox State Changes of Mitochondrial Cytochromes in a Perfused Rat Heart

    PubMed Central

    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 under hypoxia conditions. PMID:24009655

  1. 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.

  2. Raman imaging with a fiber-coupled multichannel spectrograph.

    PubMed

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

    2014-11-20

    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.

  3. 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

  4. 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

  5. Surface-enhanced Raman spectroscopy for in situ measurements of signaling molecules (autoinducers) relevant to bacteria quorum sensing.

    PubMed

    Pearman, William F; Lawrence-Snyder, Marion; Angel, S Michael; Decho, Alan W

    2007-12-01

    Autoinducer (AI) molecules are used by quorum sensing (QS) bacteria to communicate information about their environment and are critical to their ability to coordinate certain physiological activities. Studying how these organisms react to environmental stresses could provide insight into methods to control these activities. To this end, we are investigating spectroscopic methods of analysis that allow in situ measurements of these AI molecules under different environmental conditions. We found that for one class of AIs, N-acyl-homoserine lactones (AHLs), surface-enhanced Raman spectroscopy (SERS) is a method capable of performing such measurements in situ. SERS spectra of seven different AHLs with acyl chain lengths from 4 to 12 carbons were collected for the first time using Ag colloidal nanoparticles synthesized via both citrate and borohydride reduction methods. Strong SERS spectra were obtained in as little as 10 seconds for 80 microM solutions of AI that exhibited the strongest SERS response, whereas 20 seconds was typical for most AI SERS spectra collected during this study. Although all spectra were similar, significant differences were detected in the SERS spectra of C4-AHL and 3-oxo-C6-AHL and more subtle differences were noted between all AHLs. Initial results indicate a detection limit of approximately 10(-6)M for C6-AHL, which is within the limits of biologically relevant concentrations of AI molecules (nM-microM). Based on these results, the SERS method shows promise for monitoring AI molecule concentrations in situ, within biofilms containing QS bacteria. This new capability offers the possibility to "listen in" on chemical communications between bacteria in their natural environment as that environment is stressed.

  6. In situ Raman-based measurements of high dissolved methane concentrations in hydrate-rich ocean sediments

    NASA Astrophysics Data System (ADS)

    Zhang, Xin; Hester, Keith C.; Ussler, William; Walz, Peter M.; Peltzer, Edward T.; Brewer, Peter G.

    2011-04-01

    Ocean sediment dissolved CH4 concentrations are of interest for possible climate-driven venting from sea floor hydrate decomposition, for supporting the large-scale microbial anaerobic oxidation of CH4 that holds the oceanic CH4 budget in balance, and for environmental issues of the oil and gas industry. Analyses of CH4 from recovered cores near vent locations typically show a maximum of ˜1 mM, close to the 1 atmosphere equilibrium value. We show from novel in situ measurement with a Raman-based probe that geochemically coherent profiles of dissolved CH4 occur rising to 30 mM (pCH4 = 3 MPa) or an excess pressure ˜3× greater than CO2 in a bottle of champagne. Normalization of the CH4 Raman ν1 peak to the ubiquitous water ν2 bending peak provides a fundamental internal calibration. Very large losses of CH4 and fractions of other gases (CO2, H2S) must typically occur from recovered cores at gas rich sites. The new data are consistent with observations of microbial biomass and observed CH4 oxidation rates at hydrate rich sites and support estimates of a greatly expanded near surface oceanic pore water CH4 reservoir.

  7. 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.

  8. High-temperature "spectrochronopotentiometry": correlating electrochemical performance with in situ Raman spectroscopy in solid oxide fuel cells.

    PubMed

    Kirtley, John D; Halat, David M; McIntyre, Melissa D; Eigenbrodt, Bryan C; Walker, Robert A

    2012-11-20

    Carbon formation or "coking" on solid oxide fuel cell (SOFC) anodes adversely affects performance by blocking catalytic sites and reducing electrochemical activity. Quantifying these effects, however, often requires correlating changes in SOFC electrochemical efficiency measured during operation with results from ex situ measurements performed after the SOFC has been cooled and disassembled. Experiments presented in this work couple vibrational Raman spectroscopy with chronopotentiometry to observe directly the relationship between graphite deposited on nickel cermet anodes and the electrochemical performance of SOFCs operating at 725 °C. Raman spectra from Ni cermet anodes at open circuit voltage exposed to methane show a strong vibrational band at 1556 cm(-1) assigned to the "G" mode of highly ordered graphite. When polarized in the absence of a gas-phase fuel, these carbon-loaded anodes operate stably, oxidizing graphite to form CO and CO(2). Disappearance of graphite intensity measured in the Raman spectra is accompanied by a steep ∼0.8 V rise in the cell potential needed to keep the SOFC operating under constant current conditions. Continued operation leads to spectroscopically observable Ni oxidation and another steep rise in cell potential. Time-dependent spectroscopic and electrochemical measurements pass through correlated equivalence points providing unequivocal, in situ evidence that identifies how SOFC performance depends on the chemical condition of its anode. Chronopotentiometric data are used to quantify the oxide flux necessary to eliminate the carbon initially present on the SOFC anode, and data show that the oxidation mechanisms responsible for graphite removal correlate directly with the electrochemical condition of the anode as evidenced by voltammetry and impedance measurements. Electrochemically oxidizing the Ni anode damages the SOFC significantly and irreversibly. Anodes that have been reconstituted following electrochemical oxidation of

  9. Composition-thermal expandability relations and oxidation processes in tourmaline studied by in situ Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Watenphul, Anke; Malcherek, Thomas; Wilke, Franziska D. H.; Schlüter, Jochen; Mihailova, Boriana

    2017-05-01

    The crystal chemistry of tourmaline, XY3Z6(T6O18)(BO3)3V3W, has a strong influence on the structure and physical properties. Since tourmalines occur in a wide range of geological settings and have large temperature and pressure stability fields, the understanding of the relation between the tourmaline chemistry and thermal expansion allows for better thermodynamic modeling of geological processes. Here, we report dynamic and static thermal expansions as well as mode Grüneisen parameters studied by Raman spectroscopy and single-crystal X-ray diffraction data on several tourmaline species. In addition, oxidation processes in fluor-schorl and Fe2+-bearing elbaite were followed by Raman spectroscopy. Our results emphasize the role of Y-/Z-site occupancy disorder to reduce the local strains and demonstrate that small-size octahedrally coordinated cations perturb the topology of the SiO4 rings, which in turn seems to enhance the anisotropic thermal-expansion response. In addition, it is shown that the temperature-dependent behavior of the VOH modes primarily depends on the occupancy of the Y site, whereas that of the WOH modes depends on the occupancy of the X site. High-temperature Raman experiments in air allowed to follow the oxidation of Fe2+ to Fe3+ in fluor-schorl by analyzing both the framework and OH-stretching phonon modes. It is further demonstrated that under the same conditions, no oxidation of iron is observed for Fe2+-bearing elbaite, which implies that at high oxygen fugacity, iron is only oxidized in tourmaline species with prevalent divalent cations at the Y site.

  10. Characterization of Oxidation Product Films on Lead in Aqueous Media by In Situ Raman Spectroscopy

    DTIC Science & Technology

    1979-02-01

    scan rate 40 V/m/in ........... Figurc 42 Raman sp-ctra of a) lead in 0. 1 M sulfuric acid after 20 hours at +0.30 V, b, lead in 0. 1 M sulturic acid ...after 18 hours at -0.2b V, c) lead sulfate powder.............126 Fiqur, 43 Current behavior of lead oxidized in 0.1 M sulturic acid at +1.24 V for 2...Current vs. time behavior of lead exposed to 0.1 8 sulfuric acid dt +0.48 V .......... 128 Figure 45 haman spectra of a) lead sulfate surface film on

  11. In situ characterisation of a microorganism surface by Raman microspectroscopy: the shell of Ascaris eggs.

    PubMed

    Quilès, Fabienne; Balandier, Jean-Yves; Capizzi-Banas, Sandrine

    2006-09-01

    Intestinal nematodes are very common human parasites and a single species, Ascaris lumbricoïdes, is estimated to infect a quarter of the world's population. A sticky external layer covers their eggs. This work shows that Raman vibrational confocal spectroscopy is able to give information on the biochemical composition of the shell of Ascaris eggs. The biochemical localised characterisation of Ascaris eggs was performed directly on the eggs in their aqueous environment. The studied parasites came from two origins: dissections of adult females and extractions from biosolid sludges. The presence of mucopolysaccharides, proteins and chitin in the shell was demonstrated. The presence of ascaroside compounds was shown particularly via the narrow and intense bands from the organised long CH2 chains. To the best of our knowledge, this is the first time that the latter have been observed in Raman vibrational spectra of microorganisms. Hydration of the shell was different depending on the intensity of the colour of the sludge eggs. Knowledge of the biochemical structural properties of egg surfaces would be useful to understand the egg adhesion phenomena on vegetables contaminated by reused wastewater.

  12. [Real-time UV imaging of chloramphenicol intrinsic dissolution characteristics from ophthalmic in situ gel].

    PubMed

    Chen, Jian-Xiu; Guo, Zhen; Li, Hai-Yan; Wu, Li; He, Zhong-Gui; Hu, Rong-Feng; Zhang, Ji-Wen

    2013-07-01

    In this paper, chloramphenicol was selected as a model drug to prepare in situ gels. The intrinsic dissolution rate of chloramphenicol from in situ gel was evaluated using the surface dissolution imaging system. The results indicated that intrinsic dissolution rate of chloramphenicol thermosensitive in situ gel decreased significantly when the poloxamer concentration increased. The addition of the thickener reduced the intrinsic dissolution rate of chloramphenicol thermosensitive gel, wherein carbomer had the most impact. Different dilution ratios of simulated tear fluid greatly affected gel temperature, and had little influence on the intrinsic dissolution rate of chloramphenicol from the thermosensitive in situ gel. The pH of simulated tear fluid had little influence on the intrinsic dissolution rate of chloramphenicol thermosensitive in situ gel. For the pH sensitive in situ gel, the dissolution rates of chloramphenicol in weak acidic and neutral simulated tear fluids were slower than that in weak alkaline simulated tear fluid. In conclusion, the intrinsic dissolution of chloramphenicol from in situ gel was dependent on formulation and physiological factors. With advantages of small volume sample required and rapid detection, the UV imaging method can be an efficient tool for the evaluation of drug release characteristics of ophthalmic in situ gel.

  13. 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.

  14. Hand-held Raman sensor head for in-situ characterization of meat quality applying a microsystem 671 nm diode laser

    NASA Astrophysics Data System (ADS)

    Schmidt, Heinar; Sowoidnich, Kay; Maiwald, Martin; Sumpf, Bernd; Kronfeldt, Heinz-Detlef

    2009-05-01

    A hand-held Raman sensor head was developed for the in-situ characterization of meat quality. As light source, a microsystem based external cavity diode laser module (ECDL) emitting at 671 nm was integrated in the sensor head and attached to a miniaturized optical bench which contains lens optics for excitation and signal collection as well as a Raman filter stage for Rayleigh rejection. The signal is transported with an optical fiber to the detection unit which was in the initial phase a laboratory spectrometer with CCD detector. All elements of the ECDL are aligned on a micro optical bench with 13 x 4 mm2 footprint. The wavelength stability is provided by a reflection Bragg grating and the laser has an optical power of up to 200 mW. However, for the Raman measurements of meat only 35 mW are needed to obtain Raman spectra within 1 - 5 seconds. Short measuring times are essential for the hand-held device. The laser and the sensor head are characterized in terms of stability and performance for in-situ Raman investigations. The function is demonstrated in a series of measurements with raw and packaged pork meat as samples. The suitability of the Raman sensor head for the quality control of meat and other products will be discussed.

  15. Hyperspectral imaging with stimulated Raman scattering by chirped femtosecond lasers.

    PubMed

    Fu, Dan; Holtom, Gary; Freudiger, Christian; Zhang, Xu; Xie, Xiaoliang Sunney

    2013-04-25

    Raman microscopy is a quantitative, label-free, and noninvasive optical imaging technique for studying inhomogeneous systems. However, the feebleness of Raman scattering significantly limits the use of Raman microscopy to low time resolutions and primarily static samples. Recent developments in narrowband stimulated Raman scattering (SRS) microscopy have significantly increased the acquisition speed of Raman based label-free imaging by a few orders of magnitude, at the expense of reduced spectroscopic information. On the basis of a spectral focusing approach, we present a fast SRS hyperspectral imaging system using chirped femtosecond lasers to achieve rapid Raman spectra acquisition while retaining the full speed and image quality of narrowband SRS imaging. We demonstrate that quantitative concentration determination of cholesterol in the presence of interfering chemical species can be achieved with sensitivity down to 4 mM. For imaging purposes, hyperspectral imaging data in the C-H stretching region is obtained within a minute. We show that mammalian cell SRS hyperspectral imaging reveals the spatially inhomogeneous distribution of saturated lipids, unsaturated lipids, cholesterol, and protein. The combination of fast spectroscopy and label-free chemical imaging will enable new applications in studying biological systems and material systems.

  16. Raman Imaging in Cell Membranes, Lipid-Rich Organelles, and Lipid Bilayers.

    PubMed

    Syed, Aleem; Smith, Emily A

    2017-06-12

    Raman-based optical imaging is a promising analytical tool for noninvasive, label-free chemical imaging of lipid bilayers and cellular membranes. Imaging using spontaneous Raman scattering suffers from a low intensity that hinders its use in some cellular applications. However, developments in coherent Raman imaging, surface-enhanced Raman imaging, and tip-enhanced Raman imaging have enabled video-rate imaging, excellent detection limits, and nanometer spatial resolution, respectively. After a brief introduction to these commonly used Raman imaging techniques for cell membrane studies, this review discusses selected applications of these modalities for chemical imaging of membrane proteins and lipids. Finally, recent developments in chemical tags for Raman imaging and their applications in the analysis of selected cell membrane components are summarized. Ongoing developments toward improving the temporal and spatial resolution of Raman imaging and small-molecule tags with strong Raman scattering cross sections continue to expand the utility of Raman imaging for diverse cell membrane studies.

  17. In-situ monitoring by Raman spectroscopy of the thermal doping of graphene and MoS2 in O2-controlled atmosphere

    PubMed Central

    Piazza, Aurora; Giannazzo, Filippo; Buscarino, Gianpiero; Fisichella, Gabriele; Magna, Antonino La; Roccaforte, Fabrizio; Cannas, Marco; Gelardi, Franco Mario

    2017-01-01

    The effects of temperature and atmosphere (air and O2) on the doping of monolayers of graphene (Gr) on SiO2 and Si substrates, and on the doping of MoS2 multilayer flakes transferred on the same substrates have been investigated. The investigations were carried out by in situ micro-Raman spectroscopy during thermal treatments up to 430 °C, and by atomic force microscopy (AFM). The spectral positions of the G and 2D Raman bands of Gr undergo only minor changes during treatment, while their amplitude and full width at half maximum (FWHM) vary as a function of the temperature and the used atmosphere. The thermal treatments in oxygen atmosphere show, in addition to a thermal effect, an effect attributable to a p-type doping through oxygen. The thermal broadening of the line shape, found during thermal treatments by in situ Raman measurements, can be related to thermal phonon effects. The absence of a band shift results from the balance between a red shift due to thermal effects and a blue shift induced by doping. This shows the potential of in situ measurements to follow the doping kinetics. The treatment of MoS2 in O2 has evidenced a progressive erosion of the flakes without relevant spectral changes in their central zone during in situ measurements. The formation of MoO3 on the edges of the flakes is observed indicative of the oxygen-activated transformation. PMID:28326231

  18. In-situ monitoring by Raman spectroscopy of the thermal doping of graphene and MoS2 in O2-controlled atmosphere.

    PubMed

    Piazza, Aurora; Giannazzo, Filippo; Buscarino, Gianpiero; Fisichella, Gabriele; Magna, Antonino La; Roccaforte, Fabrizio; Cannas, Marco; Gelardi, Franco Mario; Agnello, Simonpietro

    2017-01-01

    The effects of temperature and atmosphere (air and O2) on the doping of monolayers of graphene (Gr) on SiO2 and Si substrates, and on the doping of MoS2 multilayer flakes transferred on the same substrates have been investigated. The investigations were carried out by in situ micro-Raman spectroscopy during thermal treatments up to 430 °C, and by atomic force microscopy (AFM). The spectral positions of the G and 2D Raman bands of Gr undergo only minor changes during treatment, while their amplitude and full width at half maximum (FWHM) vary as a function of the temperature and the used atmosphere. The thermal treatments in oxygen atmosphere show, in addition to a thermal effect, an effect attributable to a p-type doping through oxygen. The thermal broadening of the line shape, found during thermal treatments by in situ Raman measurements, can be related to thermal phonon effects. The absence of a band shift results from the balance between a red shift due to thermal effects and a blue shift induced by doping. This shows the potential of in situ measurements to follow the doping kinetics. The treatment of MoS2 in O2 has evidenced a progressive erosion of the flakes without relevant spectral changes in their central zone during in situ measurements. The formation of MoO3 on the edges of the flakes is observed indicative of the oxygen-activated transformation.

  19. In situ surface-enhanced Raman spectroscopic study of formic acid electrooxidation on spontaneously deposited platinum on gold.

    PubMed

    Muralidharan, Ranjani; McIntosh, Michael; Li, Xiao

    2013-06-28

    Present formic acid fuel cell efficiency is limited by low kinetics at the anode, indicating the need for effective catalysts to improve the formic acid oxidation. As a prerequisite, the nature of adsorbed species and specifically the reaction intermediates formed in this process needs to be examined. This work focuses on the electrooxidation of formic acid and the nature of the intermediates at a platinum-modified gold surface prepared through spontaneous deposition using a combination of electrochemistry and in situ surface enhanced Raman spectroscopy (SERS). This Pt-modified gold electrode surface assists in oxidizing formic acid at potentials as low as 0.0 V vs. Ag/AgCl which is 0.15 V more negative than a bare Pt surface. The oxidation current obtained on the Pt-modified gold electrode is 72 times higher than on a bare Au surface and 5 times higher than on a bare Pt surface at the same potential. In situ SERS has revealed the involvement of formate at a low frequency as the primary intermediate in this electrooxidation process. While previous studies mainly focused on the formate mode at ca. 1322 cm(-1), it is the first time that a formate peak at ca. 300 cm(-1) was observed on a Pt or Pt-associated surface. A unique relationship has been observed between the formic acid oxidation currents and the SERS intensity of this formate adsorbate. Furthermore, the characteristic Stark effect of the formate proves the strong interaction between the adsorbate and the catalyst. Both electrochemical and spectroscopic results suggest that the formic acid electrooxidation takes place by the dehydrogenation pathway involving a low frequency formate intermediate on the Pt-modified gold electrode catalyst.

  20. 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.

  1. 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.

  2. In situ Raman study on single- and double-walled carbon nanotubes as a function of lithium insertion.

    PubMed

    Kim, Yoong Ahm; Kojima, Masahito; Muramatsu, Hiroyuki; Umemoto, Souichiro; Watanabe, Takaaki; Yoshida, Kazuto; Sato, Keigo; Ikeda, Takuya; Hayashi, Takuya; Endo, Morinobu; Terrones, Mauricio; Dresselhaus, Mildred S

    2006-05-01

    We investigated the electrochemical lithium ion (Li(+)) insertion/desertion behavior on highly pure and bundled single- and double-walled carbon nanotubes (SWNTs and DWNTs) using an in situ Raman technique. In general, two storage sites could host Li(+) in SWNT and DWNT bundles when varying an external potential: a) the outer surface sites, and b) the interstitial spaces within the bundles. The most sensitive changes in the tangential mode (TM) of the Raman spectra upon doping with Li(+) can be divided into two regions. The first region was found from 2.8 to 1.0 V (the coverage of Li(+) on the outer surface of a bundled nanotube) and was characterized by the loss of resonant conditions via partial charge transfer, where the G(+) line of the SWNT and the TM of the outer tube of DWNTs experienced a highly depressed intensity, but remained almost constant in frequency. The appearance of a Breit-Wigner-Fano (BWF) profile provided strong evidence of metallic inner tubes within DWNTs. The second region was observed when the applied potentials ranged from 0.9 to 0 V and was characterized by Li(+) diffusion into the interstitial sites of the bundled nanotube material. This phenomenon invoked a large downshift of the G(-) band in SWNTs, and a small downshift of the TM of the inner tube of DWNTs caused by expansion of the C--C bonds due to the charge transferred to the nanotubes, and the disappearance of the BWF profile through the screening effect of the interstitial Li(+) layers.

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

    PubMed

    Kurouski, Dmitry; Van Duyne, Richard P

    2015-03-03

    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.

  4. 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.

  5. 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.

  6. 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

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

    SciTech Connect

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

    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 growth 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.

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

    PubMed

    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(BH(4))(2) and nano-LiBH(4)-LiNH(2)-MgH(2) hydrogen storage systems at elevated temperatures and pressures are reported.

  9. In situ fabrication of 3D Ag@ZnO nanostructures for microfluidic surface-enhanced Raman scattering systems.

    PubMed

    Xie, Yuliang; Yang, Shikuan; Mao, Zhangming; Li, Peng; Zhao, Chenglong; Cohick, Zane; Huang, Po-Hsun; Huang, Tony Jun

    2014-12-23

    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 ∼2×10(6) 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.

  10. 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.

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

    SciTech Connect

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

    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 growth 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.

  12. 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.

  13. 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

  14. In situ monitoring of the acetylene decomposition and gas temperature at reaction conditions for the deposition of carbon nanotubes using linear Raman scattering.

    PubMed

    Reinhold-López, Karla; Braeuer, Andreas; Popovska, Nadejda; Leipertz, Alfred

    2010-08-16

    To understand the reaction mechanisms taking place by growing carbon nanotubes via the catalytic chemical vapor deposition process, a strategy to monitor in situ the gas phase at reaction conditions was developed applying linear Raman spectroscopy. The simultaneous determination of the gas temperature and composition was possible by a new strategy of the evaluation of the Raman spectra. In agreement to the well-known exothermic decomposition of acetylene, a gas temperature increase was quantified when acetylene was added to the incident flow. Information about exhaust gas recirculation and location of the maximal acetylene conversion was derived from the composition measurements.

  15. [Ductal carcinoma in situ of the breast: role of imaging].

    PubMed

    Netter, E; Troufléau, P; Stinès, J

    1998-07-01

    The incidence of ductal carcinoma in situ (DCIS) has increased with the widespread use of screening mammography. DCIS is often suspected when clustered microcalcifications are evidenced on routinely performed mammography. High quality mammographies are required and should be completed with magnification views. Mammographic--pathologic correlations are described according to the new classifications as well as unusual forms of presentation on mammography. Early contrast enhancement in DCIS on dynamic MRI is reported and seems to be related with angiogenesis. A wire localization procedure of non-palpable lesions has to be performed and per-operative specimen radiography is mandatory. Stereotaxic large core needle biopsy is a valuable alternative to surgical biopsy but a multidisciplinary team approach is necessary and follow-up is recommended if no excisional biopsy is done. Quality in the management of DCIS depends on the coherence of the "multidisciplinary team".

  16. Molecular Resolution in situ Imaging of Spontaneous Graphene Exfoliation.

    PubMed

    Elbourne, Aaron; McLean, Ben; Voïtchovsky, Kislon; Warr, Gregory G; Atkin, Rob

    2016-08-18

    All reported methods of graphene exfoliation require external energy input, most commonly from sonication,1 shaking,2 or stirring.3 The reverse process-aggregation of single or few layer graphene sheets-occurs spontaneously in most solvents. This makes producing, and especially storing, graphene in economic quantities challenging,4,5 which is a significant barrier to widespread commercialization. This study reveals ionic liquids (ILs) can spontaneously exfoliate graphene from graphite at room temperature. The process is thermally activated and follows an Arrhenius-type behavior, resulting in thermodynamically stable IL/graphene suspensions. Using atomic force microscopy, the kinetics of the exfoliation could be followed in situ and with subnanometer resolution, showing that both the size and the charge of the constituent IL ions play a key role. Our results provide a general molecular mechanism underpinning spontaneous graphene exfoliation at room temperature in electrically conducting ILs, paving the way for their adoption in graphene-based technology.

  17. Determination of Methane Hydrate Solubility in the Absence of Vapor Phase by in-situ Raman Spectroscopy

    NASA Astrophysics Data System (ADS)

    Lu, W.; Chou, I.; Burruss, R.

    2006-12-01

    Prediction of the occurrence, distribution, and evolution of methane hydrate in porous marine sediments requires information on solubilities of methane hydrate in water. Solubilities of methane hydrate in the presence of a vapor phase are well established, but those in the absence of a vapor phase are not well defined with differences up to 30%. We have measured methane concentrations in pure water in equilibrium with sI methane hydrate, in the absence of vapor phase, by in-situ Raman spectroscopy at temperatures (T) from 2 to 20 (± 0.3) °C and pressures (P) at 10, 20, 30, and 40 (± 0.4%) MPa. Methane hydrate was synthesized in a high-pressure capillary optical cell (Chou et al., 2005; Advances in High-Pressure Technology for Geophysical Applications. Ed. J. Chen et al., Chapter 24, p. 475, Elsevier). A small quantity of methane was first loaded in an evacuated cell and then pressurized by water. Hydrate crystals were formed near the liquid-vapor interface near the enclosed end of the optical tube at room T, and were then placed at the center of a USGS-type heating-cooling stage. By adjusting sample P and T, the crystals went through dissolution-formation cycles three to four times in three days until the vapor phase was completely consumed and several crystals (typically 40 x 40 x 10 μm) were formed. These crystals were located at about 200 μm from the enclosed end and were about 20 to 40 μm from each other. Raman spectra were collected for the liquid phase adjacent to hydrate crystals near the enclosed end of the tube. A volumetric decrease in crystal size was observed away from the sampling spot; however, no such volumetric decrease was observed in or near the sampling spot. Therefore, equilibrium was likely established locally within the sampling area. The results are represented by the following linear isobaric equations: 10 MPa: ln [X(CH4)] = 0.06175 T - 6.79507; r2 = 0.9991 (n = 6) 20 MPa: ln [X(CH4)] = 0.06170 T - 6.82816; r2 = 0.9985 (n = 6) 30 MPa

  18. 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.

  19. Broadband Coherent Raman Scattering for Rapid Spectroscopic Imaging

    NASA Astrophysics Data System (ADS)

    Cicerone, Marcus

    2015-03-01

    Over the past ten years, coherent Raman imaging (CRI) has evolved from a curiosity to a practical tool for investigating some classes of biological and material questions. An, important key to this evolution has been the ability to rapidly obtain information from many spectral peaks. Most, vibrational spectroscopic information is found in the fingerprint region where spontaneous Raman can be used to achieve >3:1 signal to noise ratio for weak fingerprint peaks in biological systems, but typically requires acquisition times of several seconds; too slow for imaging. Coherent Raman methods have previously been unable to acquire high quality fingerprint spectra. We have overcome this limitation by developing a highly efficient signal excitation paradigm and appropriately harnessing the nonresonant background (NRB) signal that accompanies the resonant signal of interest. With these and other innovations, we have developed a CRI approach based on broadband coherent anti-Stokes Raman scattering (BCARS) that provides an unprecedented combination of speed, sensitivity, and chemical selectivity. Using this system we are able to obtain high quality Raman spectra in the fingerprint and CH stretch regions from biological specimens at 3.5 ms, enabling rapid, label-free chemical imaging of even delicate samples. I will briefly put our approach in context with the broader CRI field, describe key technical features of the present imaging system and provide application examples in materials and biology. I will also briefly discuss focus areas for future advances, and speculate on ultimate performance limits for coherent Raman imaging.

  20. Length-Scale-Dependent Phase Transformation of LiFePO4 : An In situ and Operando Study Using Micro-Raman Spectroscopy and XRD.

    PubMed

    Siddique, N A; Salehi, Amir; Wei, Zi; Liu, Dong; Sajjad, Syed D; Liu, Fuqiang

    2015-08-03

    The charge and discharge of lithium ion batteries are often accompanied by electrochemically driven phase-transformation processes. In this work, two in situ and operando methods, that is, micro-Raman spectroscopy and X-ray diffraction (XRD), have been combined to study the phase-transformation process in LiFePO4 at two distinct length scales, namely, particle-level scale (∼1 μm) and macroscopic scale (∼several cm). In situ Raman studies revealed a discrete mode of phase transformation at the particle level. Besides, the preferred electrochemical transport network, particularly the carbon content, was found to govern the sequence of phase transformation among particles. In contrast, at the macroscopic level, studies conducted at four different discharge rates showed a continuous but delayed phase transformation. These findings uncovered the intricate phase transformation in LiFePO4 and potentially offer valuable insights into optimizing the length-scale-dependent properties of battery materials.

  1. In Situ Raman Spectral Characteristics of Carbon Dioxide in a Deep-Sea Simulator of Extreme Environments Reaching 300 ℃ and 30 MPa.

    PubMed

    Li, Lianfu; Du, Zengfeng; Zhang, Xin; Xi, Shichuan; Wang, Bing; Luan, Zhendong; Lian, Chao; Yan, Jun

    2017-01-01

    Deep-sea carbon dioxide (CO2) plays a significant role in the global carbon cycle and directly affects the living environment of marine organisms. In situ Raman detection technology is an effective approach to study the behavior of deep-sea CO2. However, the Raman spectral characteristics of CO2 can be affected by the environment, thus restricting the phase identification and quantitative analysis of CO2. In order to study the Raman spectral characteristics of CO2 in extreme environments (up to 300 ℃ and 30 MPa), which cover most regions of hydrothermal vents and cold seeps around the world, a deep-sea extreme environment simulator was developed. The Raman spectra of CO2 in different phases were obtained with Raman insertion probe (RiP) system, which was also used in in situ Raman detection in the deep sea carried by remotely operated vehicle (ROV) "Faxian". The Raman frequency shifts and bandwidths of gaseous, liquid, solid, and supercritical CO2 and the CO2-H2O system were determined with the simulator. In our experiments (0-300 ℃ and 0-30 MPa), the peak positions of the symmetric stretching modes of gaseous CO2, liquid CO2, and supercritical CO2 shift approximately 0.6 cm(-1) (1387.8-1388.4 cm(-1)), 0.7 cm(-1) (1385.5-1386.2 cm(-1)), and 2.5 cm(-1) (1385.7-1388.2 cm(-1)), and those of the bending modes shift about 1.0 cm(-1) (1284.7-1285.7 cm(-1)), 1.9 cm(-1) (1280.1-1282.0 cm(-1)), and 4.4 cm(-1) (1281.0-1285.4 cm(-1)), respectively. The Raman spectral characteristics of the CO2-H2O system were also studied under the same conditions. The peak positions of dissolved CO2 varied approximately 4.5 cm(-1) (1282.5-1287.0 cm(-1)) and 2.4 cm(-1) (1274.4-1276.8 cm(-1)) for each peak. In comparison with our experiment results, the phases of CO2 in extreme conditions (0-3000 m and 0-300 ℃) can be identified with the Raman spectra collected in situ. This qualitative research on CO2 can also support the further quantitative

  2. Capturing the transient species at the electrode-electrolyte interface by in situ dynamic molecular imaging.

    PubMed

    Yu, Jiachao; Zhou, Yufan; Hua, Xin; Liu, Songqin; Zhu, Zihua; Yu, Xiao-Ying

    2016-09-21

    In situ time-resolved identification of interfacial transient reaction species were captured using imaging mass spectrometry, leading to the discovery of more complex elementary electrode reactions and providing an unprecedented understanding of the reaction mechanism on the electrode surface and solid-electrolyte interface using dynamic molecular imaging.

  3. Mass spectrometry imaging for in situ kinetic histochemistry

    PubMed Central

    Louie, Katherine B.; Bowen, Benjamin P.; McAlhany, Stephanie; Huang, Yurong; Price, John C.; Mao, Jian-hua; Hellerstein, Marc; Northen, Trent R.

    2013-01-01

    Tissues are composed of diverse cell subpopulations each with distinct metabolic characteristics that influence overall behavior. Unfortunately, traditional histopathology imaging techniques are ‘blind’ to the spatially ordered metabolic dynamics within tissue. While mass spectrometry imaging enables spatial mapping of molecular composition, resulting images are only a static snapshot in time of molecules involved in highly dynamic processes; kinetic information of flux through metabolic pathways is lacking. To address this limitation, we developed kinetic mass spectrometry imaging (kMSI), a novel technique integrating soft desorption/ionization mass spectrometry with clinically accepted in vivo metabolic labeling of tissue with deuterium to generate images of kinetic information of biological processes. Applied to a tumor, kMSI revealed heterogeneous spatial distributions of newly synthesized versus pre-existing lipids, with altered lipid synthesis patterns distinguishing region-specific intratumor subpopulations. Images also enabled identification and correlation of metabolic activity of specific lipids found in tumor regions of varying grade. PMID:23584513

  4. Hyperspectral Raman imaging of bone growth and regrowth chemistry

    NASA Astrophysics Data System (ADS)

    Pezzuti, Jerilyn A.; Morris, Michael D.; Bonadio, Jeffrey F.; Goldstein, Steven A.

    1998-06-01

    Hyperspectral Raman microscopic imaging of carbonated hydroxyapatite (HAP) is used to follow the chemistry of bone growth and regrowth. Deep red excitation is employed to minimize protein fluorescence interference. A passive line generator based on Powell lens optics and a motorized translation stage provide the imaging capabilities. Raman image contrast is generated from several lines of the HAP Raman spectrum, primarily the PO4-3. Factor analysis is used to minimize the integration time needed for acceptable contrast and to explore the chemical species within the bone. Bone age is visualized as variations in image intensity. High definition, high resolution images of newly formed bone and mature bone are compared qualitatively. The technique is currently under evaluation for study of experimental therapies for fracture repair.

  5. 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.

  6. Investigation of ferroelectric phase transition for modified barium titanate in multilayer ceramic capacitors by in situ Raman scattering and dielectric measurement

    NASA Astrophysics Data System (ADS)

    Yang, Gang; Yue, Zhenxing; Sun, Tieyu; Zhao, Jianqiang; Yang, Zhengwen; Li, Longtu

    2008-04-01

    The ferroelectric phase behaviors of modified BaTiO3 in X7R multilayer ceramic capacitors (MLCCs) were investigated by dielectric measurements and in situ Raman scattering. The in situ thermo-Raman scattering shows that because of a residual stress existing in the MLCCs, the tetragonal to cubic phase transition for modified BaTiO3 in MLCCs takes place over a wide temperature range of 373 K to 473 K, suggesting a diffuse-like characteristic which can be well explained by a modified phenomenological thermodynamic model, while the dielectric measurement indicates that the tetragonal to cubic transition occurs at 393 K. A disagreement exists between the two experimental results. Furthermore, a dc field-induced paraelectric to ferroelectric transition was identified by the two measurement techniques, but their phase-transition mechanisms are different. The dielectric measurement reveals the polar-micro-region to macro-domain transformation in the shell part of the core-shell structure while the in situ Raman scattering shows the cubic to tetragonal transition under a dc bias field.

  7. In Situ Focused Beam Reflectance Measurement (FBRM), Attenuated Total Reflectance Fourier Transform Infrared (ATR-FTIR) and Raman Characterization of the Polymorphic Transformation of Carbamazepine.

    PubMed

    Zhao, Yingying; Bao, Ying; Wang, Jingkang; Rohani, Sohrab

    2012-02-09

    The objective of this work was to study the polymorphic transformation of carbamazepine from Form II to Form III in 1-propanol during seeded isothermal batch crystallization. First, the pure Form II and Form III were obtained and characterized. Then their solubilities and metastable zone limits were measured by in-situ attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy and focused beam reflectance measurement (FBRM). A transition temperature at about 34.2 °C was deduced suggesting the enantiotropic nature of this compound over the studied temperature range. To quantify the polymorph ratio during the transformation process, a new in-situ quantitative method was developed to measure the fraction of Form II by Raman spectroscopy. Successful tracking of the nucleation of the stable form and the transformation from Form II to Form III during isothermal crystallization was achieved by Raman spectroscopy and FBRM. The results from these three in-situ techniques, FBRM, FTIR and Raman were consistent with each other. The results showed a strong dependency on the amount of seeds added during isothermal crystallization.

  8. Raman hyperspectral image analysis of benzoyl peroxide additive

    NASA Astrophysics Data System (ADS)

    Wang, Xiaobin; Huang, Wenqian; Wang, Qingyan; Liu, Chen; Wang, Chaopeng; Yang, Guiyan; Zhao, Chunjiang

    2017-06-01

    This study adopted a Raman hyperspectral imaging system to collect the Raman spectra and hyperspectral images of benzoyl peroxide (BPO) additive for subsequent analysis. The raw Raman spectra of BPO were preprocessed by wavelet denoising. Optimal parameters of wavelet denoising were selected by the orthogonal experimental design. The signal-noise (S/N) ratio of the optimal parameter combination was 32.848. The smoothed Raman spectra were divided into three regions (1900-1300, 1300-700, and 700-100 cm-1) for assignment and the band vibrational modes of BPO molecule were obtained. Wherein, the Raman bands at 1771, 1597, 1230, 999, 889 and 845 cm-1 are higher than others, and can be used as the Raman characteristic bands. Analysis of the grayscale images corresponding to different characteristic bands, it is found that the order of change of the image gray level was consistent with characteristic bands intensity. Findings of this study provide the research basics for the detection and analysis of BPO additive.

  9. New look inside human breast ducts with Raman imaging. Raman candidates as diagnostic markers for breast cancer prognosis: Mammaglobin, palmitic acid and sphingomyelin.

    PubMed

    Abramczyk, Halina; Brozek-Pluska, Beata

    2016-02-25

    Looking inside the human body fascinated mankind for thousands of years. Current diagnostic and therapy methods are often limited by inadequate sensitivity, specificity and spatial resolution. Raman imaging may bring revolution in monitoring of disease and treatment. The main advantage of Raman imaging is that it gives spatial information about various chemical constituents in defined cellular organelles in contrast to conventional methods (liquid chromatography/mass spectrometry, NMR, HPLC) that rely on bulk or fractionated analyses of extracted components. We demonstrated how Raman imaging can drive the progress on breast cancer just unimaginable a few years ago. We looked inside human breast ducts answering fundamental questions about location and distribution of various biochemical components inside the lumen, epithelial cells of the duct and the stroma around the duct during cancer development. We have identified Raman candidates as diagnostic markers for breast cancer prognosis: carotenoids, mammaglobin, palmitic acid and sphingomyelin as key molecular targets in ductal breast cancer in situ, and propose the molecular mechanisms linking oncogenes with lipid programming.

  10. 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

  11. 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.

  12. 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.

  13. 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

  14. 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

  15. Tip Enhanced Raman Spectroscopy and Imaging: an Apical Illumination Geometry

    PubMed Central

    Schultz, Zachary D.; Stranick, Stephan J.; Levin, Ira W.

    2009-01-01

    Results are presented illustrating the use of tip enhanced Raman spectroscopy and imaging in a top-illumination geometry. A radially polarized beam is used to generate an electric field component in the direction of beam propagation, normal to the surface, resulting in a 5× increased enhancement compared to a linearly polarized beam. This multiplicative enhancement facilitates a discrimination of the near field signal from the far field Raman background. The top illumination configuration facilitates the application of TERS for investigating molecules on a variety of surfaces, such as Au, glass, and Si. The near field Raman spectrum is presented of Si(100), rhodamine B, brilliant cresyl blue, and single wall carbon nanotubes. Sufficient enhancement is obtained to permit a sub-diffraction limited resolution Raman imaging of the surface distribution of large bundles of carbon nanotubes of various diameters. PMID:19007457

  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. 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.

  18. Using in situ Raman spectroscopy to study the drug precipitation inhibition and supersaturation mechanism of Vitamin E TPGS from self-emulsifying drug delivery systems (SEDDS).

    PubMed

    Raut, Shilpa; Karzuon, Basel; Atef, Eman

    2015-05-10

    We are reporting a new methodology of using Raman spectroscopy for studying the drug surfactant interactions in self-emulsifying drug delivery systems (SEDDS). The physicochemical properties of surfactants could affect the performance of drugs from lipid delivery systems. Thus the purpose of our research was to study the drug surfactant interactions on a molecular level to understand the mechanism of supersaturation and precipitation inhibition. Two surfactants, Labrasol® and Vitamin E TPGS, were used to formulate several SEDDS. The optimized SEDDS were further evaluated by a kinetic solubility study and in situ Raman spectroscopy for two model drugs. It was found that both drugs precipitated from Labrasol® SEDDS whereas TPGS was able to inhibit precipitation and achieve high drug supersaturation levels. In situ Raman spectroscopy indicated that hydrogen bonding with TPGS was the main factor responsible for inhibiting precipitation. This study was able to correlate the structure and physicochemical properties of the drugs and surfactants to their ability to prevent drug precipitation. Our study brings up a possible new systematic approach by using Raman spectroscopy in the development and optimization of lipid based delivery systems. Copyright © 2015 Elsevier B.V. All rights reserved.

  19. A transportable magnetic resonance imaging system for in situ measurements of living trees: the Tree Hugger.

    PubMed

    Jones, M; Aptaker, P S; Cox, J; Gardiner, B A; McDonald, P J

    2012-05-01

    This paper presents the design of the 'Tree Hugger', an open access, transportable, 1.1 MHz (1)H nuclear magnetic resonance imaging system for the in situ analysis of living trees in the forest. A unique construction employing NdFeB blocks embedded in a reinforced carbon fibre frame is used to achieve access up to 210 mm and to allow the magnet to be transported. The magnet weighs 55 kg. The feasibility of imaging living trees in situ using the 'Tree Hugger' is demonstrated. Correlations are drawn between NMR/MRI measurements and other indicators such as relative humidity, soil moisture and net solar radiation.

  20. Localization and in situ absolute quantification of chlordecone in the mouse liver by MALDI imaging.

    PubMed

    Lagarrigue, Mélanie; Lavigne, Régis; Tabet, Elise; Genet, Valentine; Thomé, Jean-Pierre; Rondel, Karine; Guével, Blandine; Multigner, Luc; Samson, Michel; Pineau, Charles

    2014-06-17

    Chlordecone is an organochlorine pesticide that was extensively used in the French West Indies to fight weevils in banana plantations from 1973 to 1993. This has led to a persistent pollution of the environment and to the contamination of the local population for several decades with effects demonstrated on human health. Chlordecone accumulates mainly in the liver where it is known to potentiate the action of hepatotoxic agents. However, there is currently no information on its in situ localization in the liver. We have thus evaluated a matrix-assisted laser desorption ionization (MALDI) imaging quantification method based on labeled normalization for the in situ localization and quantification of chlordecone. After validating the linearity and the reproducibility of this method, quantitative MALDI imaging was used to study the accumulation of chlordecone in the mouse liver. Our results revealed that normalized intensities measured by MALDI imaging could be first converted in quantitative units. These quantities appeared to be different from absolute quantities of chlordecone determined by gas chromatography (GC), but they were perfectly correlated (R(2) = 0.995). The equation of the corresponding correlation curve was thus efficiently used to convert quantities measured by MALDI imaging into absolute quantities. Our method combining labeled normalization and calibration with an orthogonal technique allowed the in situ absolute quantification of chlordecone by MALDI imaging. Finally, our results obtained on the pathological mouse liver illustrate the advantages of quantitative MALDI imaging which preserves information on in situ localization without radioactive labeling and with a simple sample preparation.

  1. NMR imaging shows water distribution and transport in plant root systems in situ

    PubMed Central

    Bottomley, Paul A.; Rogers, Hugo H.; Foster, Thomas H.

    1986-01-01

    Images of Vicia faba L. root systems at 0.6-mm resolution, undisturbed and within the soil medium in which they were grown, have been obtained by using a 1.5-Tesla proton (1H) NMR medical imaging research system. Images of root systems in seven soil media (Cahaba soil, vermiculite, sand, perlite, fritted clay, potting soil, and peatlite) exhibited variable but useful quality owing to a diversity of magnetic properties of the soils. Root structure and pathology in the form of partial decay of hypogeal cotyledons were easily discernible. Water transport in roots with light-stressed foliage was demonstrated by using water doped with a paramagnetic NMR contrast agent, and the process of plant-wilt and recovery was monitored in situ. Images of germinated seeds within soil media indicated that dynamic observations of germination and growth are possible. The results suggest that NMR imaging can be an effective noninvasive tool for studying plants in situ. Images PMID:16593642

  2. 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.

  3. 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.

  4. High-Capacitance Mechanism for Ti3C2Tx MXene by in Situ Electrochemical Raman Spectroscopy Investigation.

    PubMed

    Hu, Minmin; Li, Zhaojin; Hu, Tao; Zhu, Shihao; Zhang, Chao; Wang, Xiaohui

    2016-12-27

    MXenes represent an emerging family of conductive two-dimensional materials. Their representative, Ti3C2Tx, has been recognized as an outstanding member in the field of electrochemical energy storage. However, an in-depth understanding of fundamental processes responsible for the superior capacitance of Ti3C2Tx MXene in acidic electrolytes is lacking. Here, to understand the mechanism of capacitance in Ti3C2Tx MXene, we studied electrochemically the charge/discharge processes of Ti3C2Tx electrodes in sulfate ion-containing aqueous electrolytes with three different cations, coupled with in situ Raman spectroscopy. It is demonstrated that hydronium in the H2SO4 electrolyte bonds with the terminal O in the negative electrode upon discharging while debonding occurs upon charging. Correspondingly, the reversible bonding/debonding changes the valence state of Ti element in the MXene, giving rise to the pseudocapacitance in the acidic electrolyte. In stark contrast, only electric double layer capacitance is recognized in the other electrolytes of (NH4)2SO4 or MgSO4. The charge storage ways also differ: ion exchange dominates in H2SO4, while counterion adsorption in the rest. Hydronium that is characterized by smaller hydration radius and less charge is the most mobile among the three cations, facilitating it more kinetically accommodated on the deep adsorption sites between the MXene layers. The two key factors, i.e., surface functional group-involved bonding/debonding-induced pseudocapacitance, and ion exchange-featured charge storage, simultaneously contribute to the superior capacitance of Ti3C2Tx MXene in acidic electrolytes.

  5. In situ X-ray Raman spectroscopy study of the hydrogen sorption properties of lithium borohydride nanocomposites.

    PubMed

    Miedema, Piter S; Ngene, Peter; van der Eerden, Ad M J; Sokaras, Dimosthenis; Weng, Tsu-Chien; Nordlund, Dennis; Au, Yuen S; de Groot, Frank M F

    2014-11-07

    Nanoconfined alkali metal borohydrides are promising materials for reversible hydrogen storage applications, but the characterization of hydrogen sorption in these materials is difficult. Here we show that with in situ X-ray Raman spectroscopy (XRS) we can track the relative amounts of intermediates and final products formed during de- and re-hydrogenation of nanoconfined lithium borohydride (LiBH4) and therefore we can possibly identify the de- and re-hydrogenation pathways. In the XRS of nanoconfined LiBH4 at different points in the de- and re-hydrogenation, we identified phases that lead to the conclusion that de- and re-hydrogenation pathways in nanoconfined LiBH4 are different from bulk LiBH4: intercalated lithium (LiCx), boron and lithium hydride were formed during de-hydrogenation, but as well Li2B12H12 was observed indicating that there is possibly some bulk LiBH4 present in the nanoconfined sample LiBH4-C as prepared. Surprisingly, XRS revealed that the de-hydrogenated products of the LiBH4-C nanocomposites can be partially rehydrogenated to about 90% of Li2B12H12 and 2-5% of LiBH4 at a mild condition of 1 bar H2 and 350 °C. This suggests that re-hydrogenation occurs via the formation of Li2B12H12. Our results show that XRS is an elegant technique that can be used for in and ex situ study of the hydrogen sorption properties of nanoconfined and bulk light-weight metal hydrides in energy storage applications.

  6. Use of in situ and confocal Raman spectroscopy to study the nature and distribution of carotenoids in brown patinas from a deteriorated wall painting in Marcus Lucretius House (Pompeii).

    PubMed

    Maguregui, M; Knuutinen, U; Trebolazabala, J; Morillas, H; Castro, K; Martinez-Arkarazo, I; Madariaga, J M

    2012-02-01

    Colonisation of wall paintings by microorganisms and other organisms is a well-known problematic phenomenon. Besides taxonomic identification of the biodeteriogen, it is essential to evaluate the consequences of the colonisation, e.g., unsightly coloured patinas. This work proposes new methodology for characterisation of the nature of the main carotenoids and their distribution in brown stains or patinas of a deteriorated wall painting on the north wall of the atrium of Marcus Lucretius House (Pompeii, Italy). Characterisation of the brown patinas and surrounding areas (plaster and polychromy) from the wall painting started with in situ screening using, mainly, a portable Raman instrument with a handheld FTIR (DRIFTS sampling interface) in order to select the sampling areas suitable for further analysis in the laboratory. Two wall painting fragments were then analysed in the laboratory in two steps. First, microscopic observations (SEM and phase-contrast microscopy) were used to determine whether biodeteriogens were present in the samples. In a second step, confocal Raman microscopy (785 and 514 nm excitation lasers) was used to characterise the main biogenic compounds of the brown stains. Because of the resonance Raman effect (514 nm excitation laser), it was possible to obtain reliable Raman features to assign not only the nature of the main biogenic pigments (carotenoids) present in the stains, but also their spatial conformation. Moreover, Raman confocal applications, for example, Raman imaging and depth profiling were also used in a first attempt to determine the distribution of biosynthesised carotenoids in the stains, and to determine the thickness of the brown patinas.

  7. 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.; ...

    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

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

    SciTech Connect

    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 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. 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.

  9. 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

    2016-04-07

    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.

  10. In Situ Bioorthogonal Metabolic Labeling for Fluorescence Imaging of Virus Infection In Vivo.

    PubMed

    Pan, Hong; Li, Wen-Jun; Yao, Xiang-Jie; Wu, Ya-Yun; Liu, Lan-Lan; He, Hua-Mei; Zhang, Ren-Li; Ma, Yi-Fan; Cai, Lin-Tao

    2017-02-20

    Optical fluorescence imaging is an important strategy to explore the mechanism of virus-host interaction. However, current fluorescent tag labeling strategies often dampen viral infectivity. The present study explores an in situ fluorescent labeling strategy in order to preserve viral infectivity and precisely monitor viral infection in vivo. In contrast to pre-labeling strategy, mice are first intranasally infected with azide-modified H5N1 pseudotype virus (N3 -H5N1p), followed by injection of dibenzocyclooctyl (DBCO)-functionalized fluorescence 6 h later. The results show that DBCO dye directly conjugated to N3 -H5N1p in lung tissues through in vivo bioorthogonal chemistry with high specificity and efficacy. More remarkably, in situ labeling rather than conventional prelabeling strategy effectively preserves viral infectivity and immunogenicity both in vitro and in vivo. Hence, in situ bioorthogonal viral labeling is a promising and reliable strategy for imaging and tracking viral infection in vivo.

  11. In situ X-ray-based imaging of nano materials

    SciTech Connect

    Weker, Johanna Nelson; Huang, Xiaojing; Toney, Michael F.

    2016-02-13

    We study functional nanomaterials that are heterogeneous and understanding their behavior during synthesis and operation requires high resolution diagnostic imaging tools that can be used in situ. Over the past decade, huge progress has been made in the development of X-ray based imaging, including full field and scanning microscopy and their analogs in coherent diffractive imaging. Currently, spatial resolution of about 10 nm and time resolution of sub-seconds are achievable. For catalysis, X-ray imaging allows tracking of particle chemistry under reaction conditions. In energy storage, in situ X-ray imaging of electrode particles is providing important insight into degradation processes. Recently, both spatial and temporal resolutions are improving to a few nm and milliseconds and these developments will open up unprecedented opportunities.

  12. UV Raman imaging--a promising tool for astrobiology: comparative Raman studies with different excitation wavelengths on SNC Martian meteorites.

    PubMed

    Frosch, Torsten; Tarcea, Nicolae; Schmitt, Michael; Thiele, Hans; Langenhorst, Falko; Popp, Jürgen

    2007-02-01

    The great capabilities of UV Raman imaging have been demonstrated on the three Martian meteorites: Sayh al Uhaymir, Dar al Gani, and Zagami. Raman spectra without disturbing fluorescence and with high signal-to-noise-ratios and full of spectral features were derived. This result is of utmost importance for the development of powerful instruments for space missions. By point scanning the surfaces of the meteorite samples, it was possible for the first time to construct UV-Raman images out of the array of Raman spectra. Deep-UV Raman images are to the best of our knowledge presented for the first time. The images were used for a discussion of the chemical-mineralogical composition and texture of the meteorite surfaces. Comparative Raman studies applying visible and NIR Raman excitation wavelengths demonstrate a much better performance for UV Raman excitation. This comparative study of different Raman excitation wavelengths at the same sample spots was done by constructing a versatile, robust sample holder with a fixed micro-raster. The overall advantages of UV resonance Raman spectroscopy in terms of sensitivity and selectivity are demonstrated and discussed. Finally the application of this new technique for a UV Raman instrument for envisaged astrobiological focused space missions is suggested.

  13. Understanding the phase formation kinetics of nano-crystalline kesterite deposited on mesoscopic scaffolds via in situ multi-wavelength Raman-monitored annealing.

    PubMed

    Wang, Zhuoran; Elouatik, Samir; Demopoulos, George P

    2016-10-26

    Kesterite, a highly promising photo-absorbing crystalline form of Cu2ZnSnS4 (CZTS), has been prepared via various routes. However, the lack of in-depth understanding of the dynamic phase formation process of kesterite leads to difficulties in optimizing its annealing conditions, hence its light harvesting performance. In this paper, in situ Raman monitored-annealing is applied to study the phase formation kinetics of nano-crystalline kesterite from a precursor deposited on a TiO2 mesoscopic scaffold. By performing in situ Raman annealing under different experimental conditions and wavelengths, several facts have been discovered: kesterite crystallization starts at as low as 170 °C, but after short time annealing at 300 °C followed by cooling, the initially formed kesterite is found to decompose. Annealing at 400 °C or higher is proven to be sufficient for stabilizing the kesterite phase. Annealing at the higher temperature of 500 °C is necessary though to promote a complete reaction and thus eliminate the parasitic copper tin sulfide (CTS) impurity intermediates identified at lower annealing temperatures. More importantly, the real-time temperature dependence of Raman peak intensity enhancement, shift and broadening for CZTS is established experimentally at 500 °C for 1 h, providing a valuable reference in future CZTS research. This work demonstrates the significance of using in situ Raman spectroscopy in elucidating the kesterite phase formation kinetics, a critical step towards full crystal phase control - a prerequisite for developing fully functional CZTS-based optoelectronic devices.

  14. In situ Ca2+ imaging of the enteric nervous system.

    PubMed

    Fried, David E; Gulbransen, Brian D

    2015-01-29

    Reflex behaviors of the intestine are controlled by the enteric nervous system (ENS). The ENS is an integrative network of neurons and glia in two ganglionated plexuses housed in the gut wall. Enteric neurons and enteric glia are the only cell types within the enteric ganglia. The activity of enteric neurons and glia is responsible for coordinating intestinal functions. This protocol describes methods for observing the activity of neurons and glia within the intact ENS by imaging intracellular calcium (Ca(2+)) transients with fluorescent indicator dyes. Our technical discussion focuses on methods for Ca(2+) imaging in whole-mount preparations of the myenteric plexus from the rodent bowel. Bulk loading of ENS whole-mounts with a high-affinity Ca(2+) indicator such as Fluo-4 permits measurements of Ca(2+) responses in individual neurons or glial cells. These responses can be evoked repeatedly and reliably, which permits quantitative studies using pharmacological tools. Ca(2+) responses in cells of the ENS are recorded using a fluorescence microscope equipped with a cooled charge-coupled device (CCD) camera. Fluorescence measurements obtained using Ca(2+) imaging in whole-mount preparations offer a straightforward means of characterizing the mechanisms and potential functional consequences of Ca(2+) responses in enteric neurons and glial cells.

  15. Raman hyperspectral imaging of iron transport across membranes in cells

    NASA Astrophysics Data System (ADS)

    Das, Anupam; Costa, Xavier Felipe; Khmaladze, Alexander; Barroso, Margarida; Sharikova, Anna

    2016-09-01

    Raman scattering microscopy is a powerful imaging technique used to identify chemical composition, structural and conformational state of molecules of complex samples in biology, biophysics, medicine and materials science. In this work, we have shown that Raman techniques allow the measurement of the iron content in protein mixtures and cells. Since the mechanisms of iron acquisition, storage, and excretion by cells are not completely understood, improved knowledge of iron metabolism can offer insight into many diseases in which iron plays a role in the pathogenic process, such as diabetes, neurodegenerative diseases, cancer, and metabolic syndrome. Understanding of the processes involved in cellular iron metabolism will improve our knowledge of cell functioning. It will also have a big impact on treatment of diseases caused by iron deficiency (anemias) and iron overload (hereditary hemochromatosis). Previously, Raman studies have shown substantial differences in spectra of transferrin with and without bound iron, thus proving that it is an appropriate technique to determine the levels of bound iron in the protein mixture. We have extended these studies to obtain hyperspectral images of transferrin in cells. By employing a Raman scanning microscope together with spectral detection by a highly sensitive back-illuminated cooled CCD camera, we were able to rapidly acquire and process images of fixed cells with chemical selectivity. We discuss and compare various methods of hyperspectral Raman image analysis and demonstrate the use of these methods to characterize cellular iron content without the need for dye labeling.

  16. 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.

  17. Real time Raman imaging to understand dissolution performance of amorphous solid dispersions.

    PubMed

    Tres, Francesco; Treacher, Kevin; Booth, Jonathan; Hughes, Les P; Wren, Stephen A C; Aylott, Jonathan W; Burley, Jonathan C

    2014-08-28

    We have employed for the first time Raman spectroscopic imaging along with multi-variate curve resolution (MCR) analysis to investigate in real time and in-situ the dissolution mechanisms that underpin amorphous solid dispersions, with data being collected directly from the dosage form itself. We have also employed a novel rotating disk dissolution rate (RDDR) methodology to track, through the use of high-performance liquid chromatography (HPLC), the dissolution trends of both drug and polymer simultaneously in multi-component systems. Two formulations of poorly water-soluble felodipine in a polymeric matrix of copovidone VA64 which have different drug loadings of 5% and 50% w/w were used as models with the aim of studying the effects of increasing the amount of active ingredient on the dissolution performance. It was found that felodipine and copovidone in the 5% dispersion dissolve with the same dissolution rate and that no Raman spectral changes accompanied the dissolution, indicating that the two components dissolve as single entity, whose behaviour is dominated by water-soluble copovidone. For the 50% drug-loaded dispersion, partial RDDR values of both felodipine and copovidone were found to be extremely low. MCR Raman maps along with classical Raman/X-ray powder diffraction (XRPD) characterisation revealed that after an initial loss of copovidone from the extrudate the drug re-crystallises, pointing to a release dynamics dependent on the low water solubility and high hydrophobicity of felodipine. Raman imaging revealed different rates of transition from amorphous to crystalline felodipine at different locations within the dosage form.

  18. Label-Free Raman Imaging to Monitor Breast Tumor Signatures.

    PubMed

    Manciu, Felicia S; Ciubuc, John D; Parra, Karla; Manciu, Marian; Bennet, Kevin E; Valenzuela, Paloma; Sundin, Emma M; Durrer, William G; Reza, Luis; Francia, Giulio

    2017-08-01

    Although not yet ready for clinical application, methods based on Raman spectroscopy have shown significant potential in identifying, characterizing, and discriminating between noncancerous and cancerous specimens. Real-time and accurate medical diagnosis achievable through this vibrational optical method largely benefits from improvements in current technological and software capabilities. Not only is the acquisition of spectral information now possible in milliseconds and analysis of hundreds of thousands of data points achieved in minutes, but Raman spectroscopy also allows simultaneous detection and monitoring of several biological components. Besides demonstrating a significant Raman signature distinction between nontumorigenic (MCF-10A) and tumorigenic (MCF-7) breast epithelial cells, our study demonstrates that Raman can be used as a label-free method to evaluate epidermal growth factor activity in tumor cells. Comparative Raman profiles and images of specimens in the presence or absence of epidermal growth factor show important differences in regions attributed to lipid, protein, and nucleic acid vibrations. The occurrence, which is dependent on the presence of epidermal growth factor, of new Raman features associated with the appearance of phosphothreonine and phosphoserine residues reflects a signal transduction from the membrane to the nucleus, with concomitant modification of DNA/RNA structural characteristics. Parallel Western blotting analysis reveals an epidermal growth factor induction of phosphorylated Akt protein, corroborating the Raman results. The analysis presented in this work is an important step toward Raman-based evaluation of biological activity of epidermal growth factor receptors on the surfaces of breast cancer cells. With the ultimate future goal of clinically implementing Raman-guided techniques for the diagnosis of breast tumors (e.g., with regard to specific receptor activity), the current results just lay the foundation for

  19. 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.

  20. Ultrasensitive in situ tracing of the alkaloid dioncophylline A in the tropical liana Triphyophyllum peltatum by applying deep-UV resonance Raman microscopy.

    PubMed

    Frosch, Torsten; Schmitt, Michael; Noll, Torsten; Bringmann, Gerhard; Schenzel, Karla; Popp, Jürgen

    2007-02-01

    UV resonance Raman microspectroscopy was applied for a localization of the antiplasmodial naphthylisoquinoline alkaloid dioncophylline A in very low concentrations in different parts of the samples (e.g., in the roots) of the tropical liana Triphyophyllum peltatum. The application of resonance Raman microspectroscopy was characterized by a very high sensitivity and selectivity. It was possible to assign the resonance Raman spectra of dioncophylline A, dioncophylline C, and dioncopeltine A by means of a combination of NIR Raman spectroscopy and DFT calculations. The UV resonance Raman spectra of T. peltatum are very well resembled by the spectra of dioncophylline A, while they can be clearly distinguished from the spectra of dioncophylline C and dioncopeltine A. This distinction between the various naphthylisoquinolines was possible by the two modes at 1356 and 1613 cm-1. These two modes were assigned to C=C stretching and CH bending vibrations. The presented results of a highly sensitive and selective in situ localization of the active agent dioncophylline A in different parts of the plant material of T. peltatum are of high importance for the acquisition of new antimalarials and for plant science in general.

  1. 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.

  2. 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.

  3. 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.

  4. Platforms for hyperspectral imaging, in-situ optical and acoustical imaging in urbanized regions

    NASA Astrophysics Data System (ADS)

    Bostater, Charles R.; Oney, Taylor

    2016-10-01

    Hyperspectral measurements of the water surface of urban coastal waters are presented. Oblique bidirectional reflectance factor imagery was acquired made in a turbid coastal sub estuary of the Indian River Lagoon, Florida and along coastal surf zone waters of the nearby Atlantic Ocean. Imagery was also collected using a pushbroom hyperspectral imager mounted on a fixed platform with a calibrated circular mechatronic rotation stage. Oblique imagery of the shoreline and subsurface features clearly shows subsurface bottom features and rip current features within the surf zone water column. In-situ hyperspectral optical signatures were acquired from a vessel as a function of depth to determine the attenuation spectrum in Palm Bay. A unique stationary platform methodology to acquire subsurface acoustic images showing the presence of moving bottom boundary nephelometric layers passing through the acoustic fan beam. The acoustic fan beam imagery indicated the presence of oscillatory subsurface waves in the urbanized coastal estuary. Hyperspectral imaging using the fixed platform techniques are being used to collect hyperspectral bidirectional reflectance factor (BRF) measurements from locations at buildings and bridges in order to provide new opportunities to advance our scientific understanding of aquatic environments in urbanized regions.

  5. Biological imaging with coherent Raman scattering microscopy: a tutorial

    PubMed Central

    Alfonso-García, Alba; Mittal, Richa; Lee, Eun Seong; Potma, Eric O.

    2014-01-01

    Abstract. Coherent Raman scattering (CRS) microscopy is gaining acceptance as a valuable addition to the imaging toolset of biological researchers. Optimal use of this label-free imaging technique benefits from a basic understanding of the physical principles and technical merits of the CRS microscope. This tutorial offers qualitative explanations of the principles behind CRS microscopy and provides information about the applicability of this nonlinear optical imaging approach for biological research. PMID:24615671

  6. Biological imaging with coherent Raman scattering microscopy: a tutorial

    NASA Astrophysics Data System (ADS)

    Alfonso-García, Alba; Mittal, Richa; Lee, Eun Seong; Potma, Eric O.

    2014-07-01

    Coherent Raman scattering (CRS) microscopy is gaining acceptance as a valuable addition to the imaging toolset of biological researchers. Optimal use of this label-free imaging technique benefits from a basic understanding of the physical principles and technical merits of the CRS microscope. This tutorial offers qualitative explanations of the principles behind CRS microscopy and provides information about the applicability of this nonlinear optical imaging approach for biological research.

  7. Following lithiation fronts in paramagnetic electrodes with in situ magnetic resonance spectroscopic imaging

    NASA Astrophysics Data System (ADS)

    Tang, Mingxue; Sarou-Kanian, Vincent; Melin, Philippe; Leriche, Jean-Bernard; Ménétrier, Michel; Tarascon, Jean-Marie; Deschamps, Michaël; Salager, Elodie

    2016-11-01

    Li-ion batteries are invaluable for portable electronics and vehicle electrification. A better knowledge of compositional variations within the electrodes during battery operation is, however, still needed to keep improving their performance. Although essential in the medical field, magnetic resonance imaging of solid paramagnetic battery materials is challenging due to the short lifetime of their signals. Here we develop the scanning image-selected in situ spectroscopy approach, using the strongest commercially available magnetic field gradient. We demonstrate the 7Li magnetic resonance spectroscopic image of a 5 mm-diameter operating battery with a resolution of 100 μm. The time-resolved image-spectra enable the visualization in situ of the displacement of lithiation fronts inside thick paramagnetic electrodes during battery operation. Such observations are critical to identify the key limiting parameters for high-capacity and fast-cycling batteries. This non-invasive technique also offers opportunities to study devices containing paramagnetic materials while operating.

  8. 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

  9. 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.

  10. 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.

  11. In situ imaging of microstructure formation in electronic interconnections

    PubMed Central

    Salleh, M. A. A. Mohd; Gourlay, C. M.; Xian, J. W.; Belyakov, S. A.; Yasuda, H.; McDonald, S. D.; Nogita, K.

    2017-01-01

    The development of microstructure during melting, reactive wetting and solidification of solder pastes on Cu-plated printed circuit boards has been studied by synchrotron radiography. Using Sn-3.0Ag-0.5Cu/Cu and Sn-0.7Cu/Cu as examples, we show that the interfacial Cu6Sn5 layer is present within 0.05 s of wetting, and explore the kinetics of flux void formation at the interface between the liquid and the Cu6Sn5 layer. Quantification of the nucleation locations and anisotropic growth kinetics of primary Cu6Sn5 crystals reveals a competition between the nucleation of Cu6Sn5 in the liquid versus growth of Cu6Sn5 from the existing Cu6Sn5 layer. Direct imaging confirms that the β-Sn nucleates at/near the Cu6Sn5 layer in Sn-3.0Ag-0.5Cu/Cu joints. PMID:28079120

  12. In situ imaging of microstructure formation in electronic interconnections

    NASA Astrophysics Data System (ADS)

    Salleh, M. A. A. Mohd; Gourlay, C. M.; Xian, J. W.; Belyakov, S. A.; Yasuda, H.; McDonald, S. D.; Nogita, K.

    2017-01-01

    The development of microstructure during melting, reactive wetting and solidification of solder pastes on Cu-plated printed circuit boards has been studied by synchrotron radiography. Using Sn-3.0Ag-0.5Cu/Cu and Sn-0.7Cu/Cu as examples, we show that the interfacial Cu6Sn5 layer is present within 0.05 s of wetting, and explore the kinetics of flux void formation at the interface between the liquid and the Cu6Sn5 layer. Quantification of the nucleation locations and anisotropic growth kinetics of primary Cu6Sn5 crystals reveals a competition between the nucleation of Cu6Sn5 in the liquid versus growth of Cu6Sn5 from the existing Cu6Sn5 layer. Direct imaging confirms that the β-Sn nucleates at/near the Cu6Sn5 layer in Sn-3.0Ag-0.5Cu/Cu joints.

  13. In situ imaging of microstructure formation in electronic interconnections.

    PubMed

    Salleh, M A A Mohd; Gourlay, C M; Xian, J W; Belyakov, S A; Yasuda, H; McDonald, S D; Nogita, K

    2017-01-12

    The development of microstructure during melting, reactive wetting and solidification of solder pastes on Cu-plated printed circuit boards has been studied by synchrotron radiography. Using Sn-3.0Ag-0.5Cu/Cu and Sn-0.7Cu/Cu as examples, we show that the interfacial Cu6Sn5 layer is present within 0.05 s of wetting, and explore the kinetics of flux void formation at the interface between the liquid and the Cu6Sn5 layer. Quantification of the nucleation locations and anisotropic growth kinetics of primary Cu6Sn5 crystals reveals a competition between the nucleation of Cu6Sn5 in the liquid versus growth of Cu6Sn5 from the existing Cu6Sn5 layer. Direct imaging confirms that the β-Sn nucleates at/near the Cu6Sn5 layer in Sn-3.0Ag-0.5Cu/Cu joints.

  14. Image processing for identification and quantification of filamentous bacteria in in situ acquired images.

    PubMed

    Dias, Philipe A; Dunkel, Thiemo; Fajado, Diego A S; Gallegos, Erika de León; Denecke, Martin; Wiedemann, Philipp; Schneider, Fabio K; Suhr, Hajo

    2016-06-11

    In the activated sludge process, problems of filamentous bulking and foaming can occur due to overgrowth of certain filamentous bacteria. Nowadays, these microorganisms are typically monitored by means of light microscopy, commonly combined with staining techniques. As drawbacks, these methods are susceptible to human errors, subjectivity and limited by the use of discontinuous microscopy. The in situ microscope appears as a suitable tool for continuous monitoring of filamentous bacteria, providing real-time examination, automated analysis and eliminating sampling, preparation and transport of samples. In this context, a proper image processing algorithm is proposed for automated recognition and measurement of filamentous objects. This work introduces a method for real-time evaluation of images without any staining, phase-contrast or dilution techniques, differently from studies present in the literature. Moreover, we introduce an algorithm which estimates the total extended filament length based on geodesic distance calculation. For a period of twelve months, samples from an industrial activated sludge plant were weekly collected and imaged without any prior conditioning, replicating real environment conditions. Trends of filament growth rate-the most important parameter for decision making-are correctly identified. For reference images whose filaments were marked by specialists, the algorithm correctly recognized 72 % of the filaments pixels, with a false positive rate of at most 14 %. An average execution time of 0.7 s per image was achieved. Experiments have shown that the designed algorithm provided a suitable quantification of filaments when compared with human perception and standard methods. The algorithm's average execution time proved its suitability for being optimally mapped into a computational architecture to provide real-time monitoring.

  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. 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.

  17. 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.

  18. In-situ Multimodal Imaging and Spectroscopy of Mg Electrodeposition at Electrode-Electrolyte Interfaces

    DOE PAGES

    Wu, Yimin A.; Yin, Zuwei; Farmand, Maryam; ...

    2017-02-10

    We report the study of Mg cathodic electrochemical deposition on Ti and Au electrode using a multimodal approach by examining the sample area in-situ using liquid cell transmission electron microscopy (TEM), scanning transmission X-ray microscopy (STXM) and X-ray absorption spectroscopy (XAS). Magnesium Aluminum Chloride Complex was synthesized and utilized as electrolyte, where non-reversible features during in situ charging-discharging cycles were observed. During charging, a uniform Mg film was deposited on the electrode, which is consistent with the intrinsic non-dendritic nature of Mg deposition in Mg ion batteries. The Mg thin film was not dissolvable during the following discharge process. Wemore » found that such Mg thin film is hexacoordinated Mg compounds by in-situ STXM and XAS. This study provides insights on the non-reversibility issue and failure mechanism of Mg ion batteries. Also, our method provides a novel generic method to understand the in situ battery chemistry without any further sample processing, which can preserve the original nature of battery materials or electrodeposited materials. This multimodal in situ imaging and spectroscopy provides many opportunities to attack complex problems that span orders of magnitude in length and time scale, which can be applied to a broad range of the energy storage systems.« less

  19. In-situ Multimodal Imaging and Spectroscopy of Mg Electrodeposition at Electrode-Electrolyte Interfaces

    NASA Astrophysics Data System (ADS)

    Wu, Yimin A.; Yin, Zuwei; Farmand, Maryam; Yu, Young-Sang; Shapiro, David A.; Liao, Hong-Gang; Liang, Wen-I.; Chu, Ying-Hao; Zheng, Haimei

    2017-02-01

    We report the study of Mg cathodic electrochemical deposition on Ti and Au electrode using a multimodal approach by examining the sample area in-situ using liquid cell transmission electron microscopy (TEM), scanning transmission X-ray microscopy (STXM) and X-ray absorption spectroscopy (XAS). Magnesium Aluminum Chloride Complex was synthesized and utilized as electrolyte, where non-reversible features during in situ charging-discharging cycles were observed. During charging, a uniform Mg film was deposited on the electrode, which is consistent with the intrinsic non-dendritic nature of Mg deposition in Mg ion batteries. The Mg thin film was not dissolvable during the following discharge process. We found that such Mg thin film is hexacoordinated Mg compounds by in-situ STXM and XAS. This study provides insights on the non-reversibility issue and failure mechanism of Mg ion batteries. Also, our method provides a novel generic method to understand the in situ battery chemistry without any further sample processing, which can preserve the original nature of battery materials or electrodeposited materials. This multimodal in situ imaging and spectroscopy provides many opportunities to attack complex problems that span orders of magnitude in length and time scale, which can be applied to a broad range of the energy storage systems.

  20. In-situ Multimodal Imaging and Spectroscopy of Mg Electrodeposition at Electrode-Electrolyte Interfaces

    PubMed Central

    Wu, Yimin A.; Yin, Zuwei; Farmand, Maryam; Yu, Young-Sang; Shapiro, David A.; Liao, Hong-Gang; Liang, Wen-I; Chu, Ying-Hao; Zheng, Haimei

    2017-01-01

    We report the study of Mg cathodic electrochemical deposition on Ti and Au electrode using a multimodal approach by examining the sample area in-situ using liquid cell transmission electron microscopy (TEM), scanning transmission X-ray microscopy (STXM) and X-ray absorption spectroscopy (XAS). Magnesium Aluminum Chloride Complex was synthesized and utilized as electrolyte, where non-reversible features during in situ charging-discharging cycles were observed. During charging, a uniform Mg film was deposited on the electrode, which is consistent with the intrinsic non-dendritic nature of Mg deposition in Mg ion batteries. The Mg thin film was not dissolvable during the following discharge process. We found that such Mg thin film is hexacoordinated Mg compounds by in-situ STXM and XAS. This study provides insights on the non-reversibility issue and failure mechanism of Mg ion batteries. Also, our method provides a novel generic method to understand the in situ battery chemistry without any further sample processing, which can preserve the original nature of battery materials or electrodeposited materials. This multimodal in situ imaging and spectroscopy provides many opportunities to attack complex problems that span orders of magnitude in length and time scale, which can be applied to a broad range of the energy storage systems. PMID:28186175

  1. In-situ Multimodal Imaging and Spectroscopy of Mg Electrodeposition at Electrode-Electrolyte Interfaces.

    PubMed

    Wu, Yimin A; Yin, Zuwei; Farmand, Maryam; Yu, Young-Sang; Shapiro, David A; Liao, Hong-Gang; Liang, Wen-I; Chu, Ying-Hao; Zheng, Haimei

    2017-02-10

    We report the study of Mg cathodic electrochemical deposition on Ti and Au electrode using a multimodal approach by examining the sample area in-situ using liquid cell transmission electron microscopy (TEM), scanning transmission X-ray microscopy (STXM) and X-ray absorption spectroscopy (XAS). Magnesium Aluminum Chloride Complex was synthesized and utilized as electrolyte, where non-reversible features during in situ charging-discharging cycles were observed. During charging, a uniform Mg film was deposited on the electrode, which is consistent with the intrinsic non-dendritic nature of Mg deposition in Mg ion batteries. The Mg thin film was not dissolvable during the following discharge process. We found that such Mg thin film is hexacoordinated Mg compounds by in-situ STXM and XAS. This study provides insights on the non-reversibility issue and failure mechanism of Mg ion batteries. Also, our method provides a novel generic method to understand the in situ battery chemistry without any further sample processing, which can preserve the original nature of battery materials or electrodeposited materials. This multimodal in situ imaging and spectroscopy provides many opportunities to attack complex problems that span orders of magnitude in length and time scale, which can be applied to a broad range of the energy storage systems.

  2. Noble metal coated single-walled carbon nanotubes for applications in surface enhanced Raman scattering imaging and photothermal therapy.

    PubMed

    Wang, Xiaojing; Wang, Chao; Cheng, Liang; Lee, Shuit-Tong; Liu, Zhuang

    2012-05-02

    Single-walled carbon nanotubes (SWNTs) with various unique optical properties are interesting nanoprobes widely explored in biomedical imaging and phototherapies. Herein, DNA-functionalized SWNTs are modified with noble metal (Ag or Au) nanoparticles via an in situ solution phase synthesis method comprised of seed attachment, seeded growth, and surface modification with polyethylene glycol (PEG), yielding SWNT-Ag-PEG and SWNT-Au-PEG nanocomposites stable in physiological environments. With gold or silver nanoparticles decorated on the surface, the SWNT-metal nanocomposites gain an excellent concentration and excitation-source dependent surface-enhanced Raman scattering (SERS) effect. Using a near-infrared (NIR) laser as the excitation source, targeted Raman imaging of cancer cells labeled with folic acid (FA) conjugated SWNT-Au nanocomposite (SWNT-Au-PEG-FA) is realized, with images acquired in significantly shortened periods of time as compared to that of using nonenhanced SWNT Raman probes. Owing to the strong surface plasmon resonance absorption contributed by the gold shell, the SWNTs-Au-PEG-FA nanocomposite also offers remarkably improved photothermal cancer cell killing efficacy. This work presents a facile approach to synthesize water-soluble noble metal coated SWNTs with a strong SERS effect suitable for labeling and fast Raman spectroscopic imaging of biological samples, which has been rarely realized before. The SWNT-Au-PEG nanocomposite developed here may thus be an interesting optical theranostic probe for cancer imaging and therapy.

  3. 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.

  4. 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

  5. Data of low-dose phase-based X-ray imaging for in situ soft tissue engineering assessments

    PubMed Central

    Izadifar, Zohreh; Honaramooz, Ali; Wiebe, Sheldon; Belev, George; Chen, Xiongbiao; Chapman, Dean

    2016-01-01

    This article presents the data of using three phase-based X-ray imaging techniques to characterize biomaterial scaffold and soft tissues in situ, as reported in our study “Low-dose phase-based X-ray imaging techniques for in situ soft tissue engineering assessments” [1]. The examined parameters include the radiation dose, scan time, and image quality, which are all critical to longitudinal in situ live animal assessments. The data presented were obtained from three dimensional imaging of scaffolds in situ cartilage by means of synchrotron-based computed tomography-diffraction enhanced imaging (CT-DEI), analyzer based imaging (CT-ABI), and in-line phase contrast imaging (CT-PCI) at standard and low dose imaging modalities. PMID:26909381

  6. Raman Imaging of Dental Adhesive Diffusion

    NASA Astrophysics Data System (ADS)

    Wieliczka, D. M.; Kruger, M. B.; Spencer, P.

    1997-03-01

    In this project the dentin/adhesive interface was studied using micro-Raman spectroscopy in conjunction with laser light that is optimized to minimize the sample fluorescence. The commercial dentin adhesives Scotchbond Multi-Purpose Plus(3M) and Superbond (Sun Medical) were placed on coronal dentin substrates that were cut from extracted, unerupted third molars. The Raman spectra were obtained using a Dilor spectrometer with a resolution of 4 cm-1 over the spectral range of 100 to 2000 cm-1. All data were obtained using a Kr+ laser operating at 647 nm, a microscope with a 100x objective and with the sample mounted on a precision linear stage allowing for 0.5 (m positioning. Data were obtained from successive positions on the sample providing a spectral record of the interface from the pure adhesive to the pure dentin. Adhesive penetration into the dentin was determined by comparing the relative intensities of spectral bands attributable to the dentin versus the adhesive.

  7. Raman spectroscopy and imaging: promising optical diagnostic tools in pediatrics.

    PubMed

    Beleites, C; Bonifacio, A; Codrich, D; Krafft, C; Sergo, V

    2013-01-01

    This review focuses on the use of Raman spectroscopy, an analytical technique based on the inelastic scattering of harmless laser light with biological tissues, as an innovative diagnostic tool in pediatrics. After a brief introduction to explain the fundamental concepts behind Raman spectroscopy and imaging, a short summary is given of the most important and common issues arising when handling spectral data with multivariate statistics. Then, the most relevant papers in which Raman spectroscopy or imaging has been applied with diagnostic purposes to pediatric patients are reviewed, and grouped according to the type of pathology: neoplastic, inflammatory, allergic, malformative as well as other kinds. Raman spectroscopy has been used both in vivo, mostly using optical fibers for tissue illumination, as well as on ex vivo tissue sections in a microscopic imaging approach defined as "spectral histopathology". According to the results reported so far, this technique showed a huge potential for mini- or non-invasive real-time, bedside and intra-operatory diagnosis, as well as for an ex vivo imaging tool in support to pathologists. Despite many studies are limited by the small sample size, this technique is extremely promising in terms of sensitivity and specificity.

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

    USDA-ARS?s Scientific Manuscript database

    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...

  9. Line-scanning Raman imaging spectroscopy for detection of fingerprints.

    PubMed

    Deng, Sunan; Liu, Le; Liu, Zhiyi; Shen, Zhiyuan; Li, Guohua; He, Yonghong

    2012-06-10

    Fingerprints are the best form of personal identification for criminal investigation purposes. We present a line-scanning Raman imaging system and use it to detect fingerprints composed of β-carotene and fish oil on different substrates. Although the line-scanning Raman system has been used to map the distribution of materials such as polystyrene spheres and minerals within geological samples, this is the first time to our knowledge that the method is used in imaging fingerprints. Two Raman peaks of β-carotene (501.2, 510.3 nm) are detected and the results demonstrate that both peaks can generate excellent images with little difference between them. The system operates at a spectra resolution of about 0.4 nm and can detect β-carotene signals in petroleum ether solution with the limit of detection of 3.4×10(-9) mol/L. The results show that the line-scanning Raman imaging spectroscopy we have built has a high accuracy and can be used in the detection of latent fingerprints in the future.

  10. Mapping Chemical and Structural Composition of Pharmaceutical and Biological Samples by Raman, Surface-Enhanced Raman and Fluorescence Spectral Imaging

    NASA Astrophysics Data System (ADS)

    Chourpa, Igor; Cohen-Jonathan, Simone; Dubois, Pierre

    Raman spectroscopy is an analytical technique recognised for its structural and conformational specificity. The efficient discrimination of molecular species by Raman is particularly potent for multidimensional microscopic imaging of complex biological environment, as demonstrated in the present book. The commonly admitted problem of Raman, low sensitivity, can often be circumvented due to high output instruments and via approaches like RRS (resonance Raman scattering), SERS (surface-enhanced Raman scattering), TERS (tip-enhanced Raman scattering) or CARS (coherent anti-Stokes Raman scattering). In contrast to the latter, RRS and SERS are realizable with less sophisticated set-up based on common Raman systems. Although more invasive than RRS, SERS provides better sensitivity and quenching of fluorescence. SERRS (surface-enhanced resonance Raman scattering) spectroscopy can be used in coupling with fluorescence and competes in selectivity and sensitivity with spectrofluorimetry. In the chapter below, we use recent applications made in our group to illustrate the use of Raman and SERRS spectral imaging for characterization of biological samples (animal subcutaneous tissue, human cancer cells) and pharmaceutical samples (microparticles for drug delivery, fibres for wound dressing). After a brief description of experimental details on spectral imaging, the chapter will focus on results concerning (i) biocompatible pharmaceutical materials made of alginates and (ii) anticancer drugs in pharmaceutical forms and in biological systems.

  11. 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.

  12. 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)

  13. 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. Copyright © 2009 Elsevier B.V. All rights reserved.

  14. Surface phenomena revealed by in situ imaging: studies from adhesion, wear and cutting

    NASA Astrophysics Data System (ADS)

    Viswanathan, Koushik; Mahato, Anirban; Yeung, Ho; Chandrasekar, Srinivasan

    2017-03-01

    Surface deformation and flow phenomena are ubiquitous in mechanical processes. In this work we present an in situ imaging framework for studying a range of surface mechanical phenomena at high spatial resolution and across a range of time scales. The in situ framework is capable of resolving deformation and flow fields quantitatively in terms of surface displacements, velocities, strains and strain rates. Three case studies are presented demonstrating the power of this framework for studying surface deformation. In the first, the origin of stick-slip motion in adhesive polymer interfaces is investigated, revealing a intimate link between stick-slip and surface wave propagation. Second, the role of flow in mediating formation of surface defects and wear particles in metals is analyzed using a prototypical sliding process. It is shown that conventional post-mortem observation and inference can lead to erroneous conclusions with regard to formation of surface cracks and wear particles. The in situ framework is shown to unambiguously capture delamination wear in sliding. Third, material flow and surface deformation in a typical cutting process is analyzed. It is shown that a long-standing problem in the cutting of annealed metals is resolved by the imaging, with other benefits such as estimation of energy dissipation and power from the flow fields. In closure, guidelines are provided for profitably exploiting in situ observations to study large-strain deformation, flow and friction phenomena at surfaces that display a variety of time-scales.

  15. In situ calibration for wide-angle, three-dimensional stereoscopic image analysis.

    PubMed

    Choi, W C; Guezennec, Y G

    1997-10-10

    Accurate measurement of three-dimensional object coordinates from stereoscopic images is an essential element in various applications that require three-dimensional position information. Conventionally, optical ray tracing has been the measurement method of choice. However, it requires accurate knowledge of geometrical and optical parameters, such as the image distance, camera locations relative to the object field, and size, shape, and refractive index of intervening elements, such as apparatus windows. On the other hand, all these parameters need not be known if an optical transformation method based on an in situ calibration experiment is used. Furthermore, the use of in situ calibration not only increases the effective accuracy of the measured three-dimensional object coordinates but also reduces significantly the computational time compared with conventional optical ray tracing. The computational efficiency of the technique used is essential, especially when the application requires multiple determinations of a large number of three-dimensional coordinates, such as is the case with three-dimensional particle-tracking velocimetry. The basic concept and formulation of an optical transformation method based on an in situ calibration experiment is introduced. The technique is first demonstrated with synthetic data, then case studies with actual in situ calibration data are discussed.

  16. Live-Cell Pyrophosphate Imaging by in Situ Hot-Spot Generation.

    PubMed

    Li, Mingmin; Li, Jin; Di, Huixia; Liu, Huiqiao; Liu, Dingbin

    2017-03-21

    Controlling the electromagnetic hot-spot generation is essential for surface-enhanced Raman scattering (SERS) assays. Current hot-spot-based SERS assays have been extensively studied in solutions or on substrates. However, probing biospecies by controlling the hot-spot assembly in living systems has not been demonstrated thus far. Herein, we report a background-free SERS probe for imaging pyrophosphate (PPi), a biochemically significant anion, in living cells. Intracellular PPi is able to induce the nanoparticle dimerization, thus creating an intense electromagnetic hot spot and dramatically enhancing the signal of the Raman reporters residing in the hot spot. More impressively, the reporter we used in this study provides a strong and sharp single peak in the cellular Raman-silent region (1800-2800 cm(-1)), thus eliminating the possible background interference. This strategy could be readily extended to detect other biomarkers by only replacing the recognition ligands.

  17. Volumetric chemical imaging by stimulated Raman projection microscopy and tomography

    PubMed Central

    Chen, Xueli; Zhang, Chi; Lin, Peng; Huang, Kai-Chih; Liang, Jimin; Tian, Jie; Cheng, Ji-Xin

    2017-01-01

    Volumetric imaging allows global understanding of three-dimensional (3D) complex systems. Light-sheet fluorescence microscopy and optical projection tomography have been reported to image 3D volumes with high resolutions and at high speeds. Such methods, however, usually rely on fluorescent labels for chemical targeting, which could perturb the biological functionality in living systems. We demonstrate Bessel-beam-based stimulated Raman projection (SRP) microscopy and tomography for label-free volumetric chemical imaging. Our SRP microscope enables fast quantitation of chemicals in a 3D volume through a two-dimensional lateral scan. Furthermore, combining SRP and sample rotation, we demonstrate the SRP tomography that can reconstruct the 3D distribution of chemical compositions with optical spatial resolution at a higher speed than the Gaussian-beam-based stimulated Raman scattering sectioning imaging can. We explore the potential of our SRP technology by mapping polymer particles in 3D volumes and lipid droplets in adipose cells. PMID:28436473

  18. Volumetric chemical imaging by stimulated Raman projection microscopy and tomography

    NASA Astrophysics Data System (ADS)

    Chen, Xueli; Zhang, Chi; Lin, Peng; Huang, Kai-Chih; Liang, Jimin; Tian, Jie; Cheng, Ji-Xin

    2017-04-01

    Volumetric imaging allows global understanding of three-dimensional (3D) complex systems. Light-sheet fluorescence microscopy and optical projection tomography have been reported to image 3D volumes with high resolutions and at high speeds. Such methods, however, usually rely on fluorescent labels for chemical targeting, which could perturb the biological functionality in living systems. We demonstrate Bessel-beam-based stimulated Raman projection (SRP) microscopy and tomography for label-free volumetric chemical imaging. Our SRP microscope enables fast quantitation of chemicals in a 3D volume through a two-dimensional lateral scan. Furthermore, combining SRP and sample rotation, we demonstrate the SRP tomography that can reconstruct the 3D distribution of chemical compositions with optical spatial resolution at a higher speed than the Gaussian-beam-based stimulated Raman scattering sectioning imaging can. We explore the potential of our SRP technology by mapping polymer particles in 3D volumes and lipid droplets in adipose cells.

  19. Facile in Situ Synthesis of Silver Nanoparticles on the Surface of Metal-Organic Framework for Ultrasensitive Surface-Enhanced Raman Scattering Detection of Dopamine.

    PubMed

    Jiang, Zhongwei; Gao, Pengfei; Yang, Lin; Huang, Chengzhi; Li, Yuanfang

    2015-12-15

    Surface-enhanced Raman scattering (SERS) signals are intensively dominated by the Raman hot spots and distance between analyte molecules and metallic nanostructures. Herein, an efficient SERS substrate was developed by in situ synthesis of silver nanoparticles (AgNPs) on the surface of MIL-101 (Fe), a typical metal-organic framework (MOF). The as-prepared SERS substrate combines the numerous Raman hot spots between the high-density Ag NPs and the excellent adsorption performance of MOFs, making it an excellent SERS substrate for highly sensitive SERS detection by effectively concentrating analytes in close proximity to the Raman hot spots domains between the adjacent AgNPs. The resulting hybrid material was used for ultrasensitive SERS detection of dopamine based on the peroxidase-like activity of MIL-101 (Fe) by utilizing the enzyme-linked immunosorbent assay (ELISA) colorimetric substrate, 2,2'-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) diammonium salt (ABTS) as a SERS marker. This new developed method showed good linearity in the range from 1.054 pM to 210.8 nM for dopamine with the correlation coefficient of 0.992, detection limit of approximately 0.32 pM [signal-to-noise ratio (S/N) = 3], and acceptable recoveries ranging from 99.8% to 108.0% in human urine. These results predict that the proposed SERS system may open up a new opportunity for chemical and biological assay applications.

  20. 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.

  1. Raman imaging of biofilms using gold sputtered fiber optic probes

    NASA Astrophysics Data System (ADS)

    Christopher, Christina Grace Charlet; Manoharan, Hariharan; Subrahmanyam, Aryasomayajula; Sai, V. V. Raghavendra

    2016-12-01

    In this work we report characterization of bacterial biofilm using gold sputtered optical fiber probe as substrates for confocal Raman spectroscopy measurements. The chemical composition and the heterogeneity of biofilms in the extracellular polymeric substances (EPS) was evaluated. The spatial distribution of bacterial biofilm on the substrates during their growth phase was studied using Raman imaging. Further, the influence of substrate's surface on bacterial adhesion was investigated by studying growth of biofilms on surfaces with hydrophilic and hydrophobic coatings. This study validates the use of gold sputtered optical fiber probes as SERS substrates in confocal microscopic configuration to identify and characterize clinically relevant biofilms.

  2. 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

  3. In Situ Imaging during Compression of Plastic Bonded Explosives for Damage Modeling

    PubMed Central

    Manner, Virginia W.; Yeager, John D.; Patterson, Brian M.; Walters, David J.; Stull, Jamie A.; Cordes, Nikolaus L.; Luscher, Darby J.; Henderson, Kevin C.; Schmalzer, Andrew M.; Tappan, Bryce C.

    2017-01-01

    The microstructure of plastic bonded explosives (PBXs) is known to influence behavior during mechanical deformation, but characterizing the microstructure can be challenging. For example, the explosive crystals and binder in formulations such as PBX 9501 do not have sufficient X-ray contrast to obtain three-dimensional data by in situ, absorption contrast imaging. To address this difficulty, we have formulated a series of PBXs using octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) crystals and low-density binder systems. The binders were hydroxyl-terminated polybutadiene (HTPB) or glycidyl azide polymer (GAP) cured with a commercial blend of acrylic monomers/oligomers. The binder density is approximately half of the HMX, allowing for excellent contrast using in situ X-ray computed tomography (CT) imaging. The samples were imaged during unaxial compression using micro-scale CT in an interrupted in situ modality. The rigidity of the binder was observed to significantly influence fracture, crystal-binder delamination, and flow. Additionally, 2D slices from the segmented 3D images were meshed for finite element simulation of the mesoscale response. At low stiffness, the binder and crystal do not delaminate and the crystals move with the material flow; at high stiffness, marked delamination is noted between the crystals and the binder, leading to very different mechanical properties. Initial model results exhibit qualitatively similar delamination. PMID:28772998

  4. Visible and near-infrared imaging spectrometer (VNIS) for in-situ lunar surface measurements

    NASA Astrophysics Data System (ADS)

    He, Zhiping; Xu, Rui; Li, Chunlai; Lv, Gang; Yuan, Liyin; Wang, Binyong; Shu, Rong; Wang, Jianyu

    2015-10-01

    The Visible and Near-Infrared Imaging Spectrometer (VNIS) onboard China's Chang'E 3 lunar rover is capable of simultaneously in situ acquiring full reflectance spectra for objects on the lunar surface and performing calibrations. VNIS uses non-collinear acousto-optic tunable filters and consists of a VIS/NIR imaging spectrometer (0.45-0.95 μm), a shortwave IR spectrometer (0.9-2.4 μm), and a calibration unit with dust-proofing functionality. To been underwent a full program of pre-flight ground tests, calibrations, and environmental simulation tests, VNIS entered into orbit around the Moon on 6 December 2013 and landed on 14 December 2013 following Change'E 3. The first operations of VNIS were conducted on 23 December 2013, and include several explorations and calibrations to obtain several spectral images and spectral reflectance curves of the lunar soil in the Imbrium region. These measurements include the first in situ spectral imaging detections on the lunar surface. This paper describes the VNIS characteristics, lab calibration, in situ measurements and calibration on lunar surface.

  5. In situ imaging during compression of plastic bonded explosives for damage modeling

    DOE PAGES

    Manner, Virginia Warren; Yeager, John David; Patterson, Brian M.; ...

    2017-06-10

    Here, the microstructure of plastic bonded explosives (PBXs) is known to influence behavior during mechanical deformation, but characterizing the microstructure can be challenging. For example, the explosive crystals and binder in formulations such as PBX 9501 do not have sufficient X-ray contrast to obtain three-dimensional data by in situ, absorption contrast imaging. To address this difficulty, we have formulated a series of PBXs using octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) crystals and low-density binder systems. The binders were hydroxyl-terminated polybutadiene (HTPB) or glycidyl azide polymer (GAP) cured with a commercial blend of acrylic monomers/oligomers. The binder density is approximately half of the HMX, allowingmore » for excellent contrast using in situ X-ray computed tomography (CT) imaging. The samples were imaged during unaxial compression using micro-scale CT in an interrupted in situ modality. The rigidity of the binder was observed to significantly influence fracture, crystal-binder delamination, and flow. Additionally, 2D slices from the segmented 3D images were meshed for finite element simulation of the mesoscale response. At low stiffness, the binder and crystal do not delaminate and the crystals move with the material flow; at high stiffness, marked delamination is noted between the crystals and the binder, leading to very different mechanical properties. Initial model results exhibit qualitatively similar delamination.« less

  6. 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.

  7. Correlative confocal Raman Imaging for 2D materials

    NASA Astrophysics Data System (ADS)

    Yang, Jianyong; Liu, Wei; Dieing, Thomas; Fischer, Harald; Henrich, Marius; Hollricher, Olaf

    2015-03-01

    Graphene was one of the first two-dimensional materials which soon after its first mono-layer production received much attention by many researchers worldwide. Its properties vastly differ from bulk graphite and its potential for applications ranges from transistors to transparent conducting electrodes and solar cell applications. While Graphene is arguably the most prominent two-dimensional material there are to this date many more that are subject to current research such as MoS2, WS2 or MoSe2. Graphene has been already and still is extensively studied using a variety of characterization techniques. Raman spectroscopy and more importantly still, Raman imaging proved to be of great value due to the clearly different spectra obtained from single, double, triple and multi-layered Graphene. This and more information that can be extracted from Raman spectroscopy and imaging can well be complemented with other techniques such as various forms of atomic force microscopy (AFM), Scanning Nearfield Optical Microscopy (SNOM), and scanning electron microscopy (SEM). In this contribution we illustrate the benefit of correlating said techniques with confocal Raman imaging in order to deepen the understanding of the samples in question.

  8. RNA Imaging with Multiplexed Error-Robust Fluorescence In Situ Hybridization (MERFISH).

    PubMed

    Moffitt, J R; Zhuang, X

    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.

  9. 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.

  10. 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.

  11. Toward surface-enhanced Raman imaging of latent fingerprints.

    PubMed

    Connatser, R Maggie; Prokes, Sharka M; Glembocki, Orest J; Schuler, Rebecca L; Gardner, Charles W; Lewis, Samuel A; Lewis, Linda A

    2010-11-01

    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.

  12. 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.

  13. Advanced Applications of Raman Imaging for Deeper Understanding and Better Quality Control of Formulations.

    PubMed

    Moriyama, Kei

    2016-01-01

    The importance of using the Raman imaging technique is increasing in pharmaceutical sciences, particularly in the quality control of active pharmaceutical ingredients, formulation design, and manufacturing development. Formulation design based on Raman imaging data is important for achieving quality by design. Recently, several novel Raman imaging measurement and analytical techniques have been reported. It is undoubtedly essential for pharmaceutical researchers and manufacturing engineers to use modern Raman imaging technology to produce the best quality pharmaceutical products. This short review seeks to inform researchers and engineers about recent developments in Raman imaging techniques applicable to formulation design and manufacturing.

  14. In situ imaging of detergent-resistant membranes by atomic force microscopy.

    PubMed

    Giocondi, M C; Vié, V; Lesniewska, E; Goudonnet, J P; Le Grimellec, C

    2000-07-01

    Purified detergent-resistant membranes (DRMs) are powerful tools for the biochemical study of plasma membrane domains. To what extent these isolated DRMs correspond to native membrane domains remains, however, a matter of debate. The most immediate question to be answered concerns the in situ size range of DRMs, a determination that escapes classical microscopy techniques. In this study we show that in situ three-dimensional images of a material as fragile as Triton X-100-treated cells can be obtained, in buffer, by tapping mode atomic force microscopy. These images establish that, prior to the isolation procedure, the detergent plasma membrane fragments form domains whose size frequently exceeds 15-20 microm(2). This DRMs size range is about 1 order of magnitude higher than that estimated for the larger microdomains of living cells, which strongly suggests that membrane microdomains rearrange into larger DRMs during Triton X-100 treatment. Concomitantly, the images also reveal the presence of the cytoskeleton, which is resistant to detergent extraction, and suggest that, in situ, DRMs are associated with the membrane cytoskeleton. Copyright 2000 Academic Press.

  15. 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.

  16. 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.

  17. Use of magnetic resonance imaging for detecting clinically and mammographically occult ductal carcinoma in situ.

    PubMed

    Lo, G; Cheung, Polly S Y

    2008-06-01

    We report on two cases where breast magnetic resonance imaging examination changed clinical management. Breast magnetic resonance imaging is now recognised as an indispensable adjunctive examination to mammography and ultrasound. In each of the two cases described, breast magnetic resonance imaging revealed unsuspected, extensive, and mammographically and ultrasonologically occult, ductal carcinoma in situ. In each of these cases, planned breast conserving surgery was changed to mastectomy. The success of breast conservation treatment depends on removal of all tumour with clear margins at the time of surgery. Magnetic resonance imaging is now considered the most sensitive method for evaluating the extent of breast cancer. Breast magnetic resonance imaging has a very high sensitivity for invasive carcinoma (near 100%), and recent studies show its specificity in high-risk patients is between 93 and 99%. Magnetic resonance imaging may well be proven an important adjunctive examination in patients who have dense breasts or extensive fibrocystic change.

  18. In-situ Raman Spectroscopic Investigation of Sulfur, Sulfur-Water, and Sulfur-Methane-Water Systems Between 22 and 450 °C

    NASA Astrophysics Data System (ADS)

    Yuan, S.; Chou, I.; Li, J.; Burruss, R. C.

    2009-12-01

    Previous investigations have used native sulfur as a catalyst for thermochemical sulfate reduction (TSR) experiments, but the mechanisms for the TSR processes are still not clear. In order to establish possible mechanisms, we investigated the sulfur, sulfur-water, and sulfur-water-methane systems in the fused silica capillary capsules (FSCC) by using the USGS-type heating-cooling stage and in-situ Raman spectroscopy between 22 and 450 °C. Samples were loaded in the FSCC (0.3 mm OD, 0.1 mm ID, and 10 to 25 mm long) using the method of Chou et al. (2008, Geochim. Cosmochim. Acta, 72, 5217). Raman spectra were collected with a JY/Horiba LabRam HR Raman system using 532.06 nm laser excitation. In the sulfur system, we observed (1) the melting of native sulfur at 115.5 °C; (2) the breaking of S8 rings during heating as indicated by the gradual reduction in intensity of Raman signals near 219 and 473 cm-1; (3) the formation of new sulfur-bearing species indicated by the presence of Raman bands near 1440, 1250 cm-1, and other signals between 200 and 550 cm-1; and (4) the reappearance of S8 bands and the reduction of the signals near 1440 and 1250 cm-1 at room temperature (RT). In the sulfur-water system, we observed (1) the Raman bands near 1440 and 1250 cm-1 in the aqueous, vapor, and liquid sulfur phases during heating; (2) the presence of H2S (~2592 cm-1) and HS- (~2575 cm-1) in the aqueous phase above about 260 °C; (3) the disproportionation reaction of S to H2S and SO2/bisulfate, which occurred after L-V homogenization at about 369 °C, and was indicated by the presence of HSO4- (~1045 cm-1) and SO2 (~1149 cm-1); (4) the presence of intermediate species indicated by the Raman signals between 200 and 720 cm-1 during heating; (5) the reduction of Raman band intensities of SO2 and H2S during cooling and the disappearance of SO2 below 310 °C; and (6) the detection of SO42- (~980 cm-1) and H2S (~2590 cm-1) in the aqueous phase and H2S (~2611 cm-1) in vapor phase one

  19. Gold nano-popcorn-based targeted diagnosis, nanotherapy treatment, and in situ monitoring of photothermal therapy response of prostate cancer cells using surface-enhanced Raman spectroscopy.

    PubMed

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

    2010-12-29

    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 United States. Current treatments are mostly ineffective against advanced-stage prostate cancer and are often associated with severe side effects. Driven by these factors, we report a 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 cells, multifunctional popcorn-shaped gold nanoparticles form several hot spots and provide a significant enhancement of the Raman signal intensity by several orders of magnitude (2.5 × 10(9)). As a result, it can recognize human prostate cancer cells at the 50-cells level. Our results indicate that the localized heating that occurs during near-infrared irradiation can cause irreparable cellular damage to the prostate cancer cells. Our in situ time-dependent results demonstrate for the first time that, by monitoring SERS intensity changes, one can monitor photothermal nanotherapy response during the therapy process. Possible mechanisms and operating principles of our SERS assay are discussed. Ultimately, this nanotechnology-driven assay could have enormous potential applications in rapid, on-site targeted sensing, nanotherapy treatment, and monitoring of the nanotherapy process, which are critical to providing effective treatment of cancer.

  20. 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

  1. 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

  2. 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.

  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. Raman imaging at biological interfaces: applications in breast cancer diagnosis

    PubMed Central

    2013-01-01

    Background One of the most important areas of Raman medical diagnostics is identification and characterization of cancerous and noncancerous tissues. The methods based on Raman scattering has shown significant potential for probing human breast tissue to provide valuable information for early diagnosis of breast cancer. A vibrational fingerprint from the biological tissue provides information which can be used to identify, characterize and discriminate structures in breast tissue, both in the normal and cancerous environment. Results The paper reviews recent progress in understanding structure and interactions at biological interfaces of the human tissue by using confocal Raman imaging and IR spectroscopy. The important differences between the noncancerous and cancerous human breast tissues were found in regions characteristic for vibrations of carotenoids, fatty acids, proteins, and interfacial water. Particular attention was paid to the role played by unsaturated fatty acids and their derivatives as well as carotenoids and interfacial water. Conclusions We demonstrate that Raman imaging has reached a clinically relevant level in regard to breast cancer diagnosis applications. The results presented in the paper may have serious implications on understanding mechanisms of interactions in living cells under realistically crowded conditions of biological tissue. PMID:23705882

  5. Alkyne-functionalized superstable graphitic silver nanoparticles for Raman imaging.

    PubMed

    Song, Zhi-Ling; Chen, Zhuo; Bian, Xia; Zhou, Li-Yi; Ding, Ding; Liang, Hao; Zou, Yu-Xiu; Wang, Shan-Shan; Chen, Long; Yang, Chao; Zhang, Xiao-Bing; Tan, Weihong

    2014-10-01

    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.

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

    PubMed

    Masia, Francesco; Karuna, Arnica; Borri, Paola; Langbein, Wolfgang

    2015-08-01

    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.

  7. 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

  8. Modern Raman Imaging: Vibrational Spectroscopy on the Micrometer and Nanometer Scales

    NASA Astrophysics Data System (ADS)

    Opilik, Lothar; Schmid, Thomas; Zenobi, Renato

    2013-06-01

    Raman microscopes are currently used in various fields of research because they allow for label-free sample investigation. Moreover, the inherently low scattering cross section of Raman spectroscopy, as well as its diffraction-limited lateral resolution, has been overcome by new Raman microscopy techniques. Nonlinear methods such as coherent anti-Stokes Raman spectroscopy and stimulated Raman spectroscopy reduce measurement times and improve z resolution, allowing for three-dimensional spectroscopic imaging of biological samples. Moreover, tip-enhanced Raman spectroscopy, a near-field optical technique that combines scanning-probe microscopy with the enhancement offered by surface-enhanced Raman scattering, enables Raman spectroscopic imaging far below the optical diffraction limit. We cover the theoretical and technical aspects of Raman microscopy and related new imaging techniques and review some very recent applications in graphene research and cell biology.

  9. A portable confocal hyperspectral microscope without any scan or tube lens and its application in fluorescence and Raman spectral imaging

    NASA Astrophysics Data System (ADS)

    Li, Jingwei; Cai, Fuhong; Dong, Yongjiang; Zhu, Zhenfeng; Sun, Xianhe; Zhang, Hequn; He, Sailing

    2017-06-01

    In this study, a portable confocal hyperspectral microscope is developed. In traditional confocal laser scanning microscopes, scan lens and tube lens are utilized to achieve a conjugate relationship between the galvanometer and the back focal plane of the objective, in order to achieve a better resolution. However, these lenses make it difficult to scale down the volume of the system. In our portable confocal hyperspectral microscope (PCHM), the objective is placed directly next to the galvomirror. Thus, scan lens and tube lens are not included in our system and the size of this system is greatly reduced. Furthermore, the resolution is also acceptable in many biomedical and food-safety applications. Through reducing the optical length of the system, the signal detection efficiency is enhanced. This is conducive to realizing both the fluorescence and Raman hyperspectral imaging. With a multimode fiber as a pinhole, an improved image contrast is also achieved. Fluorescent spectral images for HeLa cells/fingers and Raman spectral images of kumquat pericarp are present. The spectral resolution and spatial resolutions are about 0.4 nm and 2.19 μm, respectively. These results demonstrate that this portable hyperspectral microscope can be used in in-vivo fluorescence imaging and in situ Raman spectral imaging.

  10. 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

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

    USDA-ARS?s Scientific Manuscript database

    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...

  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. In situ imaging of hole shape evolution in ultrashort pulse laser drilling.

    PubMed

    Döring, Sven; Richter, Sören; Nolte, Stefan; Tünnermann, Andreas

    2010-09-13

    For the first time, in situ the hole shape evolution during ultrashort pulse laser drilling in semiconductor material is imaged. The trans-illumination of the sample at a wavelength of 1.06 µm is projected onto a standard CCD camera during the ablation, providing an image of the contour of the ablated structure perpendicular to the irradiation for drilling. This demonstrated technique enables a direct, high resolution investigation of the temporal evolution of the drilling process in the depth of the material without complex sample preparation or post processing.

  14. In situ 24 kHz coherent imaging of morphology change in laser percussion drilling.

    PubMed

    Webster, Paul J L; Yu, Joe X Z; Leung, Ben Y C; Anderson, Mitchell D; Yang, Victor X D; Fraser, James M

    2010-03-01

    We observe sample morphology changes in real time (24 kHz) during and between percussion drilling pulses by integrating a low-coherence microscope into a laser micromachining platform. Nonuniform cut speed and sidewall evolution in stainless steel are observed to strongly depend on assist gas. Interpulse morphology relaxation such as hole refill is directly imaged, showing dramatic differences in the material removal process dependent on pulse duration/peak power (micros/0.1 kW, ps/20 MW) and material (steel, lead zirconate titanate PZT). Blind hole depth precision is improved by over 1 order of magnitude using in situ feedback from the imaging system.

  15. Improving and Understanding Three Dimensional Spatial Resolution in a Confocal Raman Microscopy and Raman Hyperspectral Imaging I

    NASA Astrophysics Data System (ADS)

    Lee, Eunah; Roussel, Bernard; Froigneux, Emmanuel; Adar, Fran; Mamedov, Sergey; Whitley, Andrew

    2010-08-01

    Confocal Raman microscopy provides a high spatial resolution because it operates in short wavelength region and utilizes confocal optics. However, the spatial resolution of a confocal Raman microscopy is not well understood, and often confused with the smallest measurable sample size. When performing Raman hyperspectral imaging with a confocal Raman microscope, it is also confused with the smallest distance a mapping stage can step. While all these parameters are pertinent to record a good Raman spectrum or a good Raman map, they are not spatial resolution, and thus have different impacts to the data and results. In this and subsequent papers, we will begin with the theoretical definition, examine the instrumental implementations and present the empirical applications of these parameters with examples.

  16. 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.

  17. Fluorescence Image Analyzer - FLIMA: software for quantitative analysis of fluorescence in situ hybridization.

    PubMed

    Silva, H C M; Martins-Júnior, M M C; Ribeiro, L B; Matoso, D A

    2017-03-30

    The Fluorescence Image Analyzer (FLIMA) software was developed for the quantitative analysis of images generated by fluorescence in situ hybridization (FISH). Currently, the images of FISH are examined without a coefficient that enables a comparison between them. Through GD Graphics Library, the FLIMA software calculates the amount of pixels on image and recognizes each present color. The coefficient generated by the algorithm shows the percentage of marks (probes) hybridized on the chromosomes. This software can be used for any type of image generated by a fluorescence microscope and is able to quantify digoxigenin probes exhibiting a red color, biotin probes exhibiting a green color, and double-FISH probes (digoxigenin and biotin used together), where the white color is displayed.

  18. Self-preservation and structural transition of gas hydrates during dissociation below the ice point: an in situ study using Raman spectroscopy

    PubMed Central

    Zhong, Jin-Rong; Zeng, Xin-Yang; Zhou, Feng-He; Ran, Qi-Dong; Sun, Chang-Yu; Zhong, Rui-Qin; Yang, Lan-Ying; Chen, Guang-Jin; Koh, Carolyn A.

    2016-01-01

    The hydrate structure type and dissociation behavior for pure methane and methane-ethane hydrates at temperatures below the ice point and atmospheric pressure were investigated using in situ Raman spectroscopic analysis. The self-preservation effect of sI methane hydrate is significant at lower temperatures (268.15 to 270.15 K), as determined by the stable C-H region Raman peaks and AL/AS value (Ratio of total peak area corresponding to occupancies of guest molecules in large cavities to small cavities) being around 3.0. However, it was reduced at higher temperatures (271.15 K and 272.15 K), as shown from the dramatic change in Raman spectra and fluctuations in AL/AS values. The self-preservation effect for methane-ethane double hydrate is observed at temperatures lower than 271.15 K. The structure transition from sI to sII occurred during the methane-ethane hydrate decomposition process, which was clearly identified by the shift in peak positions and the change in relative peak intensities at temperatures from 269.15 K to 271.15 K. Further investigation shows that the selectivity for self-preservation of methane over ethane leads to the structure transition; this kind of selectivity increases with decreasing temperature. This work provides new insight into the kinetic behavior of hydrate dissociation below the ice point. PMID:27941857

  19. In situ Raman and pulse reaction study on the partial oxidation of methane to synthesis gas over a Pt/Al2O3 catalyst.

    PubMed

    Wang, Mei-Liu; Zheng, Hao-Zhuan; Li, Jian-Mei; Weng, Wei-Zheng; Xia, Wen-Sheng; Huang, Chuan-Jing; Wan, Hui-Lin

    2011-02-01

    Catalytic partial oxidation of methane (POM) to synthesis gas (syngas) over Pt/Al(2)O(3) was investigated by in situ microprobe Raman and pulse reaction methods with attention focused on the mechanism of syngas formation in the oxidation zone (i.e., the catalyst zone in which O(2) was still available in the reaction feed). It was found that the amount of platinum oxide in the catalyst under POM conditions was below the detection level of Raman spectroscopy. Raman bands of carbon species that originated from methane dissociation were detected at the entrance of the catalyst bed under working conditions. The results of the pulse reaction study on POM as well as steam and CO(2) reforming of methane at 700 °C with a contact time of less than 1 ms over the catalyst suggest that pyrolysis of methane on reduced platinum sites followed by coupling of two surface hydrogen atoms to H(2) and partial oxidation of surface carbon species to CO are the major reactions responsible for syngas formation in the oxidation zone. Under the experimental conditions, steam and CO(2) reforming of methane play only a minor role in syngas formation in the same reaction zone. The contribution of the last two reactions increases with increasing contact time.

  20. Self-preservation and structural transition of gas hydrates during dissociation below the ice point: an in situ study using Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Zhong, Jin-Rong; Zeng, Xin-Yang; Zhou, Feng-He; Ran, Qi-Dong; Sun, Chang-Yu; Zhong, Rui-Qin; Yang, Lan-Ying; Chen, Guang-Jin; Koh, Carolyn A.

    2016-12-01

    The hydrate structure type and dissociation behavior for pure methane and methane-ethane hydrates at temperatures below the ice point and atmospheric pressure were investigated using in situ Raman spectroscopic analysis. The self-preservation effect of sI methane hydrate is significant at lower temperatures (268.15 to 270.15 K), as determined by the stable C-H region Raman peaks and AL/AS value (Ratio of total peak area corresponding to occupancies of guest molecules in large cavities to small cavities) being around 3.0. However, it was reduced at higher temperatures (271.15 K and 272.15 K), as shown from the dramatic change in Raman spectra and fluctuations in AL/AS values. The self-preservation effect for methane-ethane double hydrate is observed at temperatures lower than 271.15 K. The structure transition from sI to sII occurred during the methane-ethane hydrate decomposition process, which was clearly identified by the shift in peak positions and the change in relative peak intensities at temperatures from 269.15 K to 271.15 K. Further investigation shows that the selectivity for self-preservation of methane over ethane leads to the structure transition; this kind of selectivity increases with decreasing temperature. This work provides new insight into the kinetic behavior of hydrate dissociation below the ice point.

  1. UV Raman studies on CVD diamond: New information and development of in situ monitor for diamond growth

    SciTech Connect

    Asher, S.A.; Bormett, R.; Witkowski, R.; Pettit, F.; Worthington, J.

    1995-12-31

    We have for the first time excited the Raman spectrum of diamond and chemical vapor deposition (CVD) diamond films in the UV within the diamond bandgap at 228.9 nm. The lack of fluorescence in the UV excited Raman spectrum of diamond and CVD diamond films allows Raman spectroscopy for the first time to monitor the carbon-hydrogen (C-H) stretching vibrations of the non-diamond components of the CVD film as well as the third order phonon bands of diamond. The relative intensity of the C-H stretching bands at ca. 2930 cm{sup -1} to the diamond first order phone band at 1332 cm{sup -1} is proportional to the atomic fraction of covalently bound hydrogen in the CVD diamond film. The third order phonon band intensity and frequency maxima are very sensitive to the size of the diamond crystallite, its intensity decreases and the maximum shifts to lower frequency as the size of the diamond crystallite decreases. We show here that UV Raman diamond measurements have significantly greater information content than visible Raman measurements.

  2. 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; ...

    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.

  3. 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.

  4. Raman spectrosopic characterization of human malignant tissues: implications for a percutaneous optical biopsy technique for in-situ tissue diagnosis

    NASA Astrophysics Data System (ADS)

    Redd, Douglas C. B.; Frank, Christopher J.; Feng, Zhe Chuan; Gansler, Ted S.; McCreery, Richard L.

    1994-01-01

    Recent advancements in the technique of Raman spectroscopy now make it possible to achieve rapid, minimally invasive and non-destructive characterization of tissues. In order to evaluate the efficacy of this technique for diagnosis, the Raman spectra of normal and neoplastic human tissues (e.g., breast, kidney, liver and colon) were obtained utilizing visible and near-IR excitation. Normal breast tissue and colon adenocarcinoma showed major Raman features due to the presence of carotenoids and lipids. In breast carcinoma, the features due to lipids were attenuated and as fibrosis (desmoplasia) increased, new spectral features attributable to collagen were observed. Samples of normal and neoplastic liver and kidney show unique spectral differences sufficient to permit tissue differentiation.

  5. Temperature behavior of the AlH3 polymorph by in situ investigation using high resolution Raman scattering.

    PubMed

    Giannasi, A; Colognesi, D; Fichtner, M; Röhm, E; Ulivi, L; Ziparo, C; Zoppi, M

    2011-02-10

    A Raman investigation of the AlH(3) polymorph has been carried out at a low temperature (20 K) under helium atmosphere (2 bar). The pristine material was composed of three polymorphs, namely, the α, β, and γ phases. The β phase has been removed by warming the sample to 70 °C, while further heating at 100 °C was used to remove the γ phase. This allowed us to evidence, on a purely experimental basis, the characteristic Raman spectrum for each phase. Raman spectra, for the three phases, have been also calculated using density functional theory, and the results have been compared to the present experimental data, allowing for a univocal assignment, to each phase, of its characteristic spectral features.

  6. 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

  7. Application of FT-Raman spectroscopy for in situ detection of microorganisms on the surface of textiles.

    PubMed

    Rygula, Anna; Jekiel, Katarzyna; Szostak-Kot, Jadwiga; Wrobel, Tomasz P; Baranska, Malgorzata

    2011-11-01

    In this work we present the usefulness of FT-Raman spectroscopy for microbiological analysis of textiles. This technique was used for non-destructive identification of Escherichia coli bacteria on cotton and polyester fabrics. It was possible to discriminate between infected and non-infected materials. Moreover, this technique allowed detection of detergent traces as well as investigation of the influence of microorganisms on different textiles. Raman analysis supported by chemometrics (cluster analysis and principal component analysis) was shown to be a method for identification of textiles with inoculum of microorganisms in a short time. The results can be potentially used in the fabric industry and related areas.

  8. In Situ 3D Synchrotron Imaging of Failure Processes in Engineering Materials

    NASA Astrophysics Data System (ADS)

    Mostafijur Rahman, K. M.; Szpunar, Jerzy; Belev, George

    2013-03-01

    The micrometer range resolution of Synchrotron Radiation Tomography has developed an important technique for characterizing the three dimensional (3D) microstructure of materials. This technique was used for imaging Aluminum-alumina composites, porous aluminum and AA 6061 alloy under different loading conditions. The experimental set-up was installed at the Biomedical Imaging and Therapy (BMIT)'s 05B1-1 beamline at Canadian Light Source (CLS). The experimental stage has been designed for conducting the in-situ experiments. The unique feature of this experimental stage is that the sample can be rotated torsion free for taking the images for Computed Tomography imaging during any loading conditions. The developed experimental system and technique allows deciphering the internal structures of composites, porous materials, multiphase alloys and to observe the failure processes such as crack initiation, crack propagation, void formation, void coalescence and the fracture process during loading of materials.

  9. A Dark-field Scanning In Situ Spectroscopy Platform for Broadband Imaging of Resected Tissue

    PubMed Central

    Krishnaswamy, Venkataramanan; Laughney, Ashley M.; Paulsen, Keith D.; Pogue, Brian W.

    2012-01-01

    A dark-field geometry spectral imaging system is presented to raster-scan thick tissue samples in situ in 1.5cm square sections, recovering full spectra from each 100 microns diameter pixel. This spot size provides adequate resolution for wide field scanning, while also facilitating scatter imaging without requiring sophisticated light-tissue transport modeling. The system is demonstrated showing accurate estimation of localized scatter parameters and the potential to recover absorption-based contrast from broadband reflectance data measured from 480nm up to 750nm in tissue phantoms. Results obtained from xenograft pancreas tumors show the ability to quantitatively image changes in localized scatter response in this fast imaging geometry. The polychromatic raster scan design allows the rapid scanning necessary for use in surgical/clinical applications where timely decisions are required about tissue pathology. PMID:21593932

  10. In situ image segmentation using the convexity of illumination distribution of the light sources.

    PubMed

    Zhang, Li

    2008-10-01

    When separating objects from a background in an image, we often meet difficulties in obtaining the precise output due to the unclear edges of the objects, as well as the poor or nonuniform illumination. In order to solve this problem, this paper presents an in situ segmentation method which takes advantages of the distribution feature of illumination of light sources, rather than analyzing the image pixels themselves. After analyzing the convexity of illumination distribution (CID) of point and linear light sources, the paper makes use of the CID features to find pixels belonging to the background. Then some background pixels are selected as control points to reconstruct the image background by means of B-spline; finally, by subtracting the reconstructed background from the original image, global thresholding can be employed to make the final segmentation. Quantitative evaluation experiments are made to test the performance of the method.

  11. 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.

  12. Beam-Scanning for Rapid Coherent Raman Hyperspectral Imaging

    PubMed Central

    Ryu, Ian Seungwan; Camp, Charles H.; Jin, Ying; Cicerone, Marcus T.; Lee, Young Jong

    2016-01-01

    Coherent Raman imaging requires high peak power laser pulses to maximize the nonlinear multiphoton signal generation, but accompanying photo-induced sample damage often poses a challenge to microscopic imaging studies. We demonstrate that beam-scanning by a 3.5-kHz resonant mirror in a broadband coherent anti-Stokes Raman scattering (BCARS) imaging system can reduce photo-induced damage without compromising the signal intensity. Additionally, beam-scanning enables slit-acquisition, in which spectra from a thin line of sample illumination are acquired in parallel during a single charge-coupled device (CCD) exposure. Reflective mirrors are employed in the beam-scanning assembly to minimize chromatic aberration and temporal dispersion. The combined approach of beam-scanning and slitacquisition is compared with the sample-scanning mode in terms of spatial resolution, photo-induced damage, and imaging speed at the maximum laser power below the sample damage threshold. We show that the beam-scanning BCARS imaging method can reduce photodamage probability in biological cells and tissues, enabling faster imaging speed by using higher excitation laser power than could be achieved without the beam-scanning. PMID:26670522

  13. Following lithiation fronts in paramagnetic electrodes with in situ magnetic resonance spectroscopic imaging

    PubMed Central

    Tang, Mingxue; Sarou-Kanian, Vincent; Melin, Philippe; Leriche, Jean-Bernard; Ménétrier, Michel; Tarascon, Jean-Marie; Deschamps, Michaël; Salager, Elodie

    2016-01-01

    Li-ion batteries are invaluable for portable electronics and vehicle electrification. A better knowledge of compositional variations within the electrodes during battery operation is, however, still needed to keep improving their performance. Although essential in the medical field, magnetic resonance imaging of solid paramagnetic battery materials is challenging due to the short lifetime of their signals. Here we develop the scanning image-selected in situ spectroscopy approach, using the strongest commercially available magnetic field gradient. We demonstrate the 7Li magnetic resonance spectroscopic image of a 5 mm-diameter operating battery with a resolution of 100 μm. The time-resolved image-spectra enable the visualization in situ of the displacement of lithiation fronts inside thick paramagnetic electrodes during battery operation. Such observations are critical to identify the key limiting parameters for high-capacity and fast-cycling batteries. This non-invasive technique also offers opportunities to study devices containing paramagnetic materials while operating. PMID:27808094

  14. 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.

  15. Following lithiation fronts in paramagnetic electrodes with in situ magnetic resonance spectroscopic imaging.

    PubMed

    Tang, Mingxue; Sarou-Kanian, Vincent; Melin, Philippe; Leriche, Jean-Bernard; Ménétrier, Michel; Tarascon, Jean-Marie; Deschamps, Michaël; Salager, Elodie

    2016-11-03

    Li-ion batteries are invaluable for portable electronics and vehicle electrification. A better knowledge of compositional variations within the electrodes during battery operation is, however, still needed to keep improving their performance. Although essential in the medical field, magnetic resonance imaging of solid paramagnetic battery materials is challenging due to the short lifetime of their signals. Here we develop the scanning image-selected in situ spectroscopy approach, using the strongest commercially available magnetic field gradient. We demonstrate the (7)Li magnetic resonance spectroscopic image of a 5 mm-diameter operating battery with a resolution of 100 μm. The time-resolved image-spectra enable the visualization in situ of the displacement of lithiation fronts inside thick paramagnetic electrodes during battery operation. Such observations are critical to identify the key limiting parameters for high-capacity and fast-cycling batteries. This non-invasive technique also offers opportunities to study devices containing paramagnetic materials while operating.

  16. Surface-enhanced Raman imaging of cell membrane by a highly homogeneous and isotropic silver nanostructure

    NASA Astrophysics Data System (ADS)

    Zito, Gianluigi; Rusciano, Giulia; Pesce, Giuseppe; Dochshanov, Alden; Sasso, Antonio

    2015-04-01

    Label-free chemical imaging of live cell membranes can shed light on the molecular basis of cell membrane functionalities and their alterations under membrane-related diseases. In principle, this can be done by surface-enhanced Raman scattering (SERS) in confocal microscopy, but requires engineering plasmonic architectures with a spatially invariant SERS enhancement factor G(x, y) = G. To this end, we exploit a self-assembled isotropic nanostructure with characteristics of homogeneity typical of the so-called near-hyperuniform disorder. The resulting highly dense, homogeneous and isotropic random pattern consists of clusters of silver nanoparticles with limited size dispersion. This nanostructure brings together several advantages: very large hot spot density (~104 μm-2), superior spatial reproducibility (SD < 1% over 2500 μm2) and single-molecule sensitivity (Gav ~ 109), all on a centimeter scale transparent active area. We are able to reconstruct the label-free SERS-based chemical map of live cell membranes with confocal resolution. In particular, SERS imaging is here demonstrated on red blood cells in vitro in order to use the Raman-resonant heme of the cell as a contrast medium to prove spectroscopic detection of membrane molecules. Numerical simulations also clarify the SERS characteristics of the substrate in terms of electromagnetic enhancement and distance sensitivity range consistently with the experiments. The large SERS-active area is intended for multi-cellular imaging on the same substrate, which is important for spectroscopic comparative analysis of complex organisms like cells. This opens new routes for in situ quantitative surface analysis and dynamic probing of living cells exposed to membrane-targeting drugs.Label-free chemical imaging of live cell membranes can shed light on the molecular basis of cell membrane functionalities and their alterations under membrane-related diseases. In principle, this can be done by surface-enhanced Raman

  17. Fiber optic cone penetrometer raman probe for in situ chemical characterization of the Hanford underground waste tanks

    SciTech Connect

    Kyle, K.R.; Brown, S.B.

    1997-03-03

    A field hardened fiber optic Raman probe has been developed for cone penetrometer deployment in the Hanford underground chemical waste storage tanks. The corrosive chemical environment of the tanks, as well as Hanford specific deployment parameters, provide unique challenges for the design of an optical probe.

  18. In situ quantitation of ring-conjugated ethylenic lignin-units in spruce thermomechanical pulps by FT-Raman spectroscopy

    Treesearch

    Umesh Agarwal; Sally A. Ralph

    2003-01-01

    With the objective of using FT-Raman to quantitatively analyze ethylenic units in lignin in thermomechanical pulps (TMPs), coniferyl alcohol, coniferin, coniferaldehyde, and G-DHP lignin models were used to first demonstrate that the technique was fully capable of quantifying ring conjugated ethylenic units. Based on this result, the amount of ethylenic units in TMP...

  19. Detection and imaging of quorum sensing in Pseudomonas aeruginosa biofilm communities by surface-enhanced resonance Raman scattering

    NASA Astrophysics Data System (ADS)

    Bodelón, Gustavo; Montes-García, Verónica; López-Puente, Vanesa; Hill, Eric H.; Hamon, Cyrille; Sanz-Ortiz, Marta N.; Rodal-Cedeira, Sergio; Costas, Celina; Celiksoy, Sirin; Pérez-Juste, Ignacio; Scarabelli, Leonardo; La Porta, Andrea; Pérez-Juste, Jorge; Pastoriza-Santos, Isabel; Liz-Marzán, Luis M.

    2016-11-01

    Most bacteria in nature exist as biofilms, which support intercellular signalling processes such as quorum sensing (QS), a cell-to-cell communication mechanism that allows bacteria to monitor and respond to cell density and changes in the environment. As QS and biofilms are involved in the ability of bacteria to cause disease, there is a need for the development of methods for the non-invasive analysis of QS in natural bacterial populations. Here, by using surface-enhanced resonance Raman scattering spectroscopy, we report rationally designed nanostructured plasmonic substrates for the in situ, label-free detection of a QS signalling metabolite in growing Pseudomonas aeruginosa biofilms and microcolonies. The in situ, non-invasive plasmonic imaging of QS in biofilms provides a powerful analytical approach for studying intercellular communication on the basis of secreted molecules as signals.

  20. Detection and imaging of quorum sensing in Pseudomonas aeruginosa biofilm communities by surface-enhanced resonance Raman scattering

    PubMed Central

    Bodelón, Gustavo; Montes-García, Verónica; López-Puente, Vanesa; Hill, Eric H.; Hamon, Cyrille; Sanz-Ortiz, Marta N.; Rodal-Cedeira, Sergio; Costas, Celina; Celiksoy, Sirin; Pérez-Juste, Ignacio; Scarabelli, Leonardo; Porta, Andrea La; Pérez-Juste, Jorge; Pastoriza-Santos, Isabel

    2016-01-01

    Most bacteria in nature exist as biofilms, which support intercellular signaling processes such as quorum sensing (QS), a cell-to-cell communication mechanism that allows bacteria to monitor and respond to cell density and changes in the environment. Because QS and biofilms are involved in the ability of bacteria to cause disease, there is a need for the development of methods for the non-invasive analysis of QS in natural bacterial populations. Here, by using surface-enhanced resonance Raman scattering spectroscopy, we report rationally designed nanostructured plasmonic substrates for the in-situ, label-free detection of a QS signaling metabolite in growing Pseudomonas aeruginosa biofilms and microcolonies. The in situ, non-invasive plasmonic imaging of QS in biofilms provides a powerful analytical approach for studying intercellular communication on the basis of secreted molecules as signals. PMID:27500808

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

    SciTech Connect

    Thapa, Bhaskar Bahadur

    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.

  2. 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.

  3. 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.

  4. Quantitative detection of benzoyl peroxide in wheat flour by line-scan macro-scale Raman chemical imaging

    USDA-ARS?s Scientific Manuscript database

    A high-throughput Raman chemical imaging method was developed for direct inspection of benzoyl peroxide (BPO) mixed in wheat flour. A 5 W 785 nm line laser (240 mm long and 1 mm wide) was used as a Raman excitation source in a push-broom Raman imaging system. Hyperspectral Raman images were collecte...

  5. Using in situ flow cytometry images of ciliates and dinoflagellates for aquatic system monitoring.

    PubMed

    Pereira, G C; Figueiredo, A R; Ebecken, N F F

    2017-08-17

    Short-period variability in plankton communities is poorly documented, especially for variations occurring in specific groups in the assemblage because traditional analysis is laborious and time-consuming. Moreover, it does not allow the high sampling frequency required for decision making. To overcome this limitation, we tested the submersible CytoSub flow cytometer. This device was anchored at a distance of approximately 10 metres from the low tide line at a depth of 1.5 metres for 12 hours to monitor the plankton at a site in the biological reserve of Barra da Tijuca beach, Rio de Janeiro. Data analysis was performed with two-dimensional scatter plots, individual pulse shapes and micro images acquisition. High-frequency monitoring results of two interesting groups are shown. The abundance and carbon biomass of ciliates were relatively stable, whereas those from dinoflagellates were highly variable along the day. The linear regression of biovolume measures between classical microscopy and in situ flow cytometry demonstrate high degree of adjustment. Despite the success of the trial and the promising results obtained, the large volume of images generated by the method also creates a need to develop pattern recognition models for automatic classification of in situ cytometric images.

  6. 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.

  7. 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.

  8. Diffraction imaging for in situ characterization of double-crystal X-ray monochromators

    SciTech Connect

    Stoupin, Stanislav; Liu, Zunping; Heald, Steve M.; Brewe, Dale; Meron, Mati

    2015-10-30

    In this paper, imaging of the Bragg-reflected X-ray beam is proposed and validated as an in situ method for characterization of the performance of double-crystal monochromators under the heat load of intense synchrotron radiation. A sequence of images is collected at different angular positions on the reflectivity curve of the second crystal and analyzed. The method provides rapid evaluation of the wavefront of the exit beam, which relates to local misorientation of the crystal planes along the beam footprint on the thermally distorted first crystal. The measured misorientation can be directly compared with the results of finite element analysis. Finally, the imaging method offers an additional insight into the local intrinsic crystal quality over the footprint of the incident X-ray beam.

  9. 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

  10. Diffraction imaging for in situ characterization of double-crystal X-ray monochromators

    DOE PAGES

    Stoupin, Stanislav; Liu, Zunping; Heald, Steve M.; ...

    2015-10-30

    In this paper, imaging of the Bragg-reflected X-ray beam is proposed and validated as an in situ method for characterization of the performance of double-crystal monochromators under the heat load of intense synchrotron radiation. A sequence of images is collected at different angular positions on the reflectivity curve of the second crystal and analyzed. The method provides rapid evaluation of the wavefront of the exit beam, which relates to local misorientation of the crystal planes along the beam footprint on the thermally distorted first crystal. The measured misorientation can be directly compared with the results of finite element analysis. Finally,more » the imaging method offers an additional insight into the local intrinsic crystal quality over the footprint of the incident X-ray beam.« less

  11. 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.

  12. 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.

  13. 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.

  14. Pressure-induced amorphization in Y{sub 2}(WO{sub 4}){sub 3}: in situ X-ray diffraction and Raman studies

    SciTech Connect

    Karmakar, S. . E-mail: sdak@magnum.barc.ernet.in; Deb, S.K.; Tyagi, A.K.; Sharma, Surinder M.

    2004-11-01

    The high-pressure behavior of Y{sub 2}(WO{sub 4}){sub 3} has been investigated at room temperature by in situ X-ray diffraction and Raman scattering measurements. Both the studies show that beyond {approx}3GPa, this compound smoothly transforms from the ambient orthorhombic phase to a disordered phase. The structural modifications are found to be reversible up to {approx}4GPa but become irreversible at higher pressures. Low pressures of transformation imply that these changes are intrinsic and not due to non-hydrostatic stresses. In addition, the correlation between the stability range of orthorhombic phase and counter cation size supports that this compound has a large field of negative thermal expansion in this family of compounds.

  15. 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.

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

    PubMed

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

    2017-08-29

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

  17. Extraction and comparison of gene expression patterns from 2D RNA in situ hybridization images.

    PubMed

    Mace, Daniel L; Varnado, Nicole; Zhang, Weiping; Frise, Erwin; Ohler, Uwe

    2010-03-15

    Recent advancements in high-throughput imaging have created new large datasets with tens of thousands of gene expression images. Methods for capturing these spatial and/or temporal expression patterns include in situ hybridization or fluorescent reporter constructs or tags, and results are still frequently assessed by subjective qualitative comparisons. In order to deal with available large datasets, fully automated analysis methods must be developed to properly normalize and model spatial expression patterns. We have developed image segmentation and registration methods to identify and extract spatial gene expression patterns from RNA in situ hybridization experiments of Drosophila embryos. These methods allow us to normalize and extract expression information for 78,621 images from 3724 genes across six time stages. The similarity between gene expression patterns is computed using four scoring metrics: mean squared error, Haar wavelet distance, mutual information and spatial mutual information (SMI). We additionally propose a strategy to calculate the significance of the similarity between two expression images, by generating surrogate datasets with similar spatial expression patterns using a Monte Carlo swap sampler. On data from an early development time stage, we show that SMI provides the most biologically relevant metric of comparison, and that our significance testing generalizes metrics to achieve similar performance. We exemplify the application of spatial metrics on the well-known Drosophila segmentation network. A Java webstart application to register and compare patterns, as well as all source code, are available from: http://tools.genome.duke.edu/generegulation/image_analysis/insitu uwe.ohler@duke.edu Supplementary data are available at Bioinformatics online.

  18. 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.

  19. 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.

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

    NASA Astrophysics Data System (ADS)

    Medvedev, S. A.; Barkalov, O. I.; Naumov, P.; Palasyuk, T.; Evers, J.; Klapötke, T. M.; Felser, C.

    2015-04-01

    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 CsN3 toward formation of covalent bonds at high pressures.

  1. [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.

  2. Coded-aperture Raman imaging for standoff explosive detection

    NASA Astrophysics Data System (ADS)

    McCain, Scott T.; Guenther, B. D.; Brady, David J.; Krishnamurthy, Kalyani; Willett, Rebecca

    2012-06-01

    This paper describes the design of a deep-UV Raman imaging spectrometer operating with an excitation wavelength of 228 nm. The designed system will provide the ability to detect explosives (both traditional military explosives and home-made explosives) from standoff distances of 1-10 meters with an interrogation area of 1 mm x 1 mm to 200 mm x 200 mm. This excitation wavelength provides resonant enhancement of many common explosives, no background fluorescence, and an enhanced cross-section due to the inverse wavelength scaling of Raman scattering. A coded-aperture spectrograph combined with compressive imaging algorithms will allow for wide-area interrogation with fast acquisition rates. Coded-aperture spectral imaging exploits the compressibility of hyperspectral data-cubes to greatly reduce the amount of acquired data needed to interrogate an area. The resultant systems are able to cover wider areas much faster than traditional push-broom and tunable filter systems. The full system design will be presented along with initial data from the instrument. Estimates for area scanning rates and chemical sensitivity will be presented. The system components include a solid-state deep-UV laser operating at 228 nm, a spectrograph consisting of well-corrected refractive imaging optics and a reflective grating, an intensified solar-blind CCD camera, and a high-efficiency collection optic.

  3. In situ diagnosis of the electrolyte solution in a laminate lithium ion battery by using ultrafine multi-probe Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Yamanaka, Toshiro; Nakagawa, Hiroe; Tsubouchi, Shigetaka; Domi, Yasuhiro; Doi, Takayuki; Abe, Takeshi; Ogumi, Zempachi

    2017-08-01

    Lithium ion batteries have attracted much attention due to their high power density. The change in concentration of salt in the electrolyte solution and local shortage of electrolyte solution in batteries cause serious degradation of battery performance. In this work, in situ Raman spectroscopy of the electrolyte solution at different positions in a laminate lithium ion battery (a typical practical battery) was simultaneously conducted by using ultrafine multi-probes. Eight probes were aligned in deep narrow spaces between two electrodes at intervals of about 2.5 mm in a plane parallel to the surfaces of electrodes. The concentration changed differently at the positions during charging and discharging. In addition, local dry up and local refilling of the electrolyte solution were observed. These phenomena were sometimes observed at the same time at the positions of two adjacent probes, indicating that the phenomena occurred in a millimeter scale. The method used in this study is useful for in situ analysis of the electrolyte solution in deep narrow spaces in other electrochemical devices under conditions close to those in practical devices.

  4. 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.

  5. Real-Time Investigation of Chemical Compositions and Hygroscopic Properties of Aerosols Generated from NaCl and Malonic Acid Mixture Solutions Using in Situ Raman Microspectrometry.

    PubMed

    Li, Xue; Gupta, Dhrubajyoti; Lee, Jisoo; Park, Geonhee; Ro, Chul-Un

    2017-01-03

    Recently, ambient sea spray aerosols (SSAs) have been reported to undergo reactions with dicarboxylic acids (DCAs). Several studies have examined the hygroscopic behavior and chemical reactivity of aerosols generated from NaCl-DCA mixture solutions, but the results have varied, especially for the NaCl-malonic acid (NaCl-MA) mixture system. In this work, in situ Raman microspectrometry (RMS) was used to simultaneously monitor the change in chemical composition, size, and phase as a function of the relative humidity, for individual aerosols generated from NaCl-MA solutions, during two hygroscopic measurement cycles, which were performed first through the dehydration process, followed by a humidification process, in each cycle. In situ RMS analysis for the aerosols showed that the chemical reaction between NaCl and MA occurred rapidly in the time scale of 1 h and considerably in the aqueous phase, mostly during the first dehydration process, and the chemical reaction occurs more rapidly when MA is more enriched in the aerosols. For example, the reaction between NaCl and MA for aerosols generated from solutions of NaCl:MA = 2:1 and 1:2 occurred by 81% and 100% at RH = 42% and 45%, respectively, during the first dehydration process. The aerosols generated from the solution of NaCl:MA = 2:1 revealed single efflorescence and deliquescence transitions repeatedly during two hygroscopic cycles. The aerosols from NaCl:MA = 1:1 and 1:2 solutions showed just an efflorescence transition during the first dehydration process and no efflorescence and deliquescence transition during the hygroscopic cycles, respectively. The observed different hygroscopic behavior was due to the different contents of NaCl, MA, and monosodium malonate in the aerosols, which were monitored real-time by in situ RMS.

  6. Mineral dust observed with AERONET Sun photometer, Raman lidar, and in situ instruments during SAMUM 2006: Shape-independent particle properties

    NASA Astrophysics Data System (ADS)

    Müller, D.; Weinzierl, B.; Petzold, A.; Kandler, K.; Ansmann, A.; Müller, T.; Tesche, M.; Freudenthaler, V.; Esselborn, M.; Heese, B.; Althausen, D.; Schladitz, A.; Otto, S.; Knippertz, P.

    2010-04-01

    Aerosol Robotic Network (AERONET) Sun photometer observations were carried out at Ouarzazate, Morocco, during the Saharan Mineral Dust Experiment (SAMUM) 2006. Data from one measurement day, 19 May 2006, are used to derive particle optical and microphysical parameters with AERONET's latest version of light-scattering model for non-spherical particle geometry. In our analysis we also make use of a novel measurement channel at 1638 nm wavelength. We compare the results to data products obtained by airborne high-spectral-resolution lidar, several ground-based Raman lidar, and airborne and ground-based in situ measurement platforms. We chose that specific measurement day because the dust plume was vertically well mixed. Extinction coefficients from AERONET Sun photometer and lidar observations and in situ measurements agree well. Ångström exponents from Sun photometer and lidar are in close agreement, too. Airborne in situ measurements of dust particle size distributions show larger effective radii than inferred from the AERONET data. Complex refractive indices that are derived with the AERONET algorithm differ from the values obtained with different independent techniques employed in our study. The single-scattering albedo was derived from the airborne observations of particle size distributions and complex refractive indices. Single-scattering albedo differs to the value inferred from the AERONET data. The differences may be attributed to the different effective radii that we obtained from the various techniques. The differences between the data products from the various measurement platforms, however, cannot be generalized, as we could only test data for one measurement day. An analysis of additional measurements is under way.

  7. 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.

  8. In-Situ Studies of Structure Transformation and Al Coordination of KAl(MoO₄)₂ during Heating by High Temperature Raman and (27)Al NMR Spectroscopies.

    PubMed

    Wang, Min; You, Jinglin; Sobol, Alexander; Lu, Liming; Wang, Jian; Xie, Yingfang

    2017-03-17

    Recent interest in optimizing composition and synthesis conditions of functional crystals, and the further exploration of new possible candidates for tunable solid-state lasers, has led to significant research on compounds in this family M(I)M(III)(M(VI)O₄)₂ (M(I) = alkali metal, M(III) = Al, In, Sc, Fe, Bi, lanthanide; M(VI) = Mo, W). The vibrational modes, structure transformation, and Al coordination of crystalline, glassy, and molten states of KAl(MoO₄)₂ have been investigated by in-situ high temperature Raman scattering and (27)Al magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy, together with first principles density functional simulation of room temperature Raman spectrum. The results showed that, under the present fast quenching conditions, Al is present predominantly in [AlO₆] octahedra in both KAl(MoO₄)₂ glass and melt, with the tetrahedrally coordinated Al being minor at approximately 2.7%. The effect of K⁺, from ordered arrangement in the crystal to random distribution in the melt, on the local chemical environment of Al, was also revealed. The distribution and quantitative analysis of different Al coordination subspecies are final discussed and found to be dependent on the thermal history of the glass samples.

  9. Characteristic of pargasitic amphibole at high pressure by in situ μ-Raman, μ-FTIR spectroscopy and synchrotron X-ray diffraction

    NASA Astrophysics Data System (ADS)

    SU, W.; Zhou, Q.; Liu, X.

    2013-12-01

    Hydrous silicate mineral such as amphibole occurs in wide range of pressure-temperature conditions including igneous (Sato et al., 1997; Beard & Day, 1986), metamorphic rocks (Winter, 2001; Su et al., 2009) and meteorites (Olsen, 1967; Karlsson et al., 1992; Brearley, 1997). Instability of hydrous silicate phases such as amphibole and mica have been used to explain the low-velocity zones. The composition of the natural pargasitic amphibole is determined by electron microprobe: (Na0.625K0.1) (Ca1.997Na0.003) (Mg4.197Mn0.004Fe3+0.025Al0.703 Ti0.071) (Si6.369Al1.631)O22 [Cl0.007F0.236(OH)1.757]. Here, we investigate stability of a natural pargasitic amphibole by Raman, mid-infrared spectra and synchrotron X-ray diffraction in situ in a diamond-anvil cell (DAC) as a function of pressure (up to 40 GPa): pressure dependences of defect structures, IR/Raman frequencies, relative energies, crystal structure, etc. We also discuss effects of pressure on hydrous amphibole phases. This study will advance our understanding of stability of amphiboles and circle of hydrous phases in the subduction. Reference (omit).

  10. Predictive value of the surface-enhanced resonance Raman scattering-based MTT assay: a rapid and ultrasensitive method for cell viability in situ.

    PubMed

    Mao, Zhu; Liu, Zhuo; Chen, Lei; Yang, Jin; Zhao, Bing; Jung, Young Mee; Wang, Xu; Zhao, Chun

    2013-08-06

    SERRS (surface-enhanced resonance Raman scattering) has been used to develop and optimize a novel and quantitative MTT assay for living cell viability. This highly sensitive method derives from two factors for formazan signal enhancing: the addition of Au nanoparticles and the resonance effect by 632.8 nm of excitation. The results show that the background elements, such as excessive MTT residues, serum, and the drug, did not interfere with the detection of formazan. Moreover, the detection limit of formazan is as low as 1 ng/mL. With the use of this method to quantify metabolically viable cells, dose-response curves of treated and untreated cells with the drug were constructed on the human lung cancer cell A549. The results also show that the Raman signal generated is dependent on the degree of activation of the cells. In comparison to the traditional method, the main advantages of this method are its rapidity (30 min), high-selectivity, high-precision, and cost-effectiveness (0.1 mg/mL MTT) without time-consuming steps and any modifying or labeling procedure. This work reports on an improved research tool that may help researchers apply this method for in situ cell assays.

  11. 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.

  12. 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

  13. In situ detection of histone variants and modifications in mouse brain using imaging mass spectrometry.

    PubMed

    Lahiri, Shibojyoti; Sun, Na; Solis-Mezarino, Victor; Fedisch, Andreas; Ninkovic, Jovica; Feuchtinger, Annette; Götz, Magdalena; Walch, Axel; Imhof, Axel

    2016-02-01

    Histone posttranslational modifications and histone variants control the epigenetic regulation of gene expression and affect a wide variety of biological processes. A complex pattern of such modifications and variants defines the identity of cells within complex organ systems and can therefore be used to characterize cells at a molecular level. However, their detection and identification in situ has been limited so far due to lack of specificity, selectivity, and availability of antihistone antibodies. Here, we describe a novel MALDI imaging MS based workflow, which enables us to detect and characterize histones by their intact mass and their correlation with cytological properties of the tissue using novel statistical and image analysis tools. The workflow allows us to characterize the in situ distribution of the major histone variants and their modification in the mouse brain. This new analysis tool is particularly useful for the investigation of expression patterns of the linker histone H1 variants for which suitable antibodies are so far not available. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. 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.

  15. Underwater reflectance transformation imaging: a technology for in situ underwater cultural heritage object-level recording

    NASA Astrophysics Data System (ADS)

    Selmo, David; Sturt, Fraser; Miles, James; Basford, Philip; Malzbender, Tom; Martinez, Kirk; Thompson, Charlie; Earl, Graeme; Bevan, George

    2017-01-01

    There is an increasing demand for high-resolution recording of in situ underwater cultural heritage. Reflectance transformation imaging (RTI) has a proven track record in terrestrial contexts for acquiring high-resolution diagnostic data at small scales. The research presented here documents the first adaptation of RTI protocols to the subaquatic environment, with a scuba-deployable method designed around affordable off-the-shelf technologies. Underwater RTI (URTI) was used to capture detail from historic shipwrecks in both the Solent and the western Mediterranean. Results show that URTI can capture submillimeter levels of qualitative diagnostic detail from in situ archaeological material. In addition, this paper presents the results of experiments to explore the impact of turbidity on URTI. For this purpose, a prototype fixed-lighting semisubmersible RTI photography dome was constructed to allow collection of data under controlled conditions. The signal-to-noise data generated reveals that the RGB channels of underwater digital images captured in progressive turbidity degraded faster than URTI object geometry calculated from them. URTI is shown to be capable of providing analytically useful object-level detail in conditions that would render ordinary underwater photography of limited use.

  16. Tissue imaging of myocardial infarct regions by a slit-scanning Raman microscope

    NASA Astrophysics Data System (ADS)

    Ogawa, Mitsugu; Harada, Yoshinori; Yamaoka, Yoshihisa; Fujita, Katsumasa; Takamatsu, Tetsuro

    2009-02-01

    Estimating the distribution of myocardial fibrosis after myocardial infarct is important for appropriate therapeutic planning. Here, we applied a Raman confocal microscope equipped with slit scanner for molecular tissue imaging of rat infarcted hearts. Raman spectra of the cytoplasm of cardiomyocytes included the resonance Raman bands at 751, 1130 and 1582 cm-1 arising mainly from reduced b- and c- type cytochromes. Raman spectra of fibrotic tissues at the borderzone of old myocardial infarct were highly consistent with that of collagen type I. Based on these findings, we successfully obtained Raman tissue images of a cardiomyocyte and surrounding collagen at the cellular level.

  17. 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.

  18. 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.

  19. Raman imaging from microscopy to macroscopy: Quality and safety control of biological materials

    USDA-ARS?s Scientific Manuscript database

    Raman imaging can analyze biological materials by generating detailed chemical images. Over the last decade, tremendous advancements in Raman imaging and data analysis techniques have overcome problems such as long data acquisition and analysis times and poor sensitivity. This review article introdu...

  20. 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.

  1. Wide-field Raman imaging for bone detection in tissue

    PubMed Central

    Papour, Asael; Kwak, Jin Hee; Taylor, Zach; Wu, Benjamin; Stafsudd, Oscar; Grundfest, Warren

    2015-01-01

    Inappropriate bone growth in soft tissue can occur after trauma to a limb and can cause a disruption to the healing process. This is known as Heterotopic Ossification (HO) in which regions in the tissue start to mineralize and form microscopic bone-like structures. These structures continue to calcify and develop into large, non-functional bony masses that cause pain, limit limb movement, and expose the tissue to reoccurring infections; in the case of open wounds this can lead to amputation as a result of a failed wound. Both Magnetic Resonance Imaging (MRI) and X-ray imaging have poor sensitivity and specificity for the detection of HO, thus delaying therapy and leading to poor patient outcomes. We present a low-power, fast (1 frame per second) optical Raman imaging system with a large field of view (1 cm2) that can differentiate bone tissue from soft tissue without spectroscopy, this in contrast to conventional Raman microscopy systems. This capability may allow for the development of instrumentation which permits bedside diagnosis of HO. PMID:26504639

  2. Wide-field Raman imaging for bone detection in tissue.

    PubMed

    Papour, Asael; Kwak, Jin Hee; Taylor, Zach; Wu, Benjamin; Stafsudd, Oscar; Grundfest, Warren

    2015-10-01

    Inappropriate bone growth in soft tissue can occur after trauma to a limb and can cause a disruption to the healing process. This is known as Heterotopic Ossification (HO) in which regions in the tissue start to mineralize and form microscopic bone-like structures. These structures continue to calcify and develop into large, non-functional bony masses that cause pain, limit limb movement, and expose the tissue to reoccurring infections; in the case of open wounds this can lead to amputation as a result of a failed wound. Both Magnetic Resonance Imaging (MRI) and X-ray imaging have poor sensitivity and specificity for the detection of HO, thus delaying therapy and leading to poor patient outcomes. We present a low-power, fast (1 frame per second) optical Raman imaging system with a large field of view (1 cm(2)) that can differentiate bone tissue from soft tissue without spectroscopy, this in contrast to conventional Raman microscopy systems. This capability may allow for the development of instrumentation which permits bedside diagnosis of HO.

  3. Live-cell stimulated Raman scattering imaging of alkyne-tagged biomolecules.

    PubMed

    Hong, Senlian; Chen, Tao; Zhu, Yuntao; Li, Ang; Huang, Yanyi; Chen, Xing

    2014-06-02

    Alkynes can be metabolically incorporated into biomolecules including nucleic acids, proteins, lipids, and glycans. In addition to the clickable chemical reactivity, alkynes possess a unique Raman scattering within the Raman-silent region of a cell. Coupling this spectroscopic signature with Raman microscopy yields a new imaging modality beyond fluorescence and label-free microscopies. The bioorthogonal Raman imaging of various biomolecules tagged with an alkyne by a state-of-the-art Raman imaging technique, stimulated Raman scattering (SRS) microscopy, is reported. This imaging method affords non-invasiveness, high sensitivity, and molecular specificity and therefore should find broad applications in live-cell imaging. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. 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.

  5. In situ Silver Spot Preparation and on-Plate Surface-Enhanced Raman Scattering Detection in Thin Layer Chromatography Separation

    NASA Astrophysics Data System (ADS)

    Herman, K.; Mircescu, N. E.; Szabo, L.; Leopold, L. F.; Chiş, V.; Leopold, N.

    2013-05-01

    An improved approach for surface-enhanced Raman scattering (SERS) detection of mixture constituents after thin layer chromatography (TLC) separation is presented. A SERS active silver substrate was prepared under open air conditions, directly on the thin silica film by photo-reduction of silver nitrate, allowing the detection of binary mixtures of cresyl violet, bixine, crystal violet, and Cu(II) complex of 4-(2-pyridylazo)resorcinol. The recorded SERS spectrum provides a unique spectral fingerprint for each molecule; therefore the use of analyte standards is avoided, thus rendering the presented procedure advantageous compared to the conventional detection methodology in TLC.

  6. Raman imaging of lignin and cellulose distribution in black spruce wood (Picea mariana) cell walls

    Treesearch

    Umesh P. Agarwal

    2005-01-01

    A detailed understanding of wood cell wall structure and organization is important from both fundamental and practical point of views. A state-of- the-art 633-nm laser based confocal Raman microscope was used in situ to investigate the cell wall organization of black spruce wood. Chemical information on lignin and cellulose from morphologically distinct cell wall...

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

    PubMed

    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

    2016-06-01

    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.

  8. In Situ Multimodal 3D Chemical Imaging of a Hierarchically Structured Core@Shell Catalyst.

    PubMed

    Sheppard, Thomas L; Price, Stephen W T; Benzi, Federico; Baier, Sina; Klumpp, Michael; Dittmeyer, Roland; Schwieger, Wilhelm; Grunwaldt, Jan-Dierk

    2017-06-14

    A Cu/ZnO/Al2O3@ZSM-5 core@shell catalyst active for one-step conversion of synthesis gas to dimethyl ether (DME) was imaged simultaneously and in situ using synchrotron-based micro X-ray fluorescence (μ-XRF), X-ray diffraction (μ-XRD), and scanning transmission X-ray microscopy (STXM) computed tomography (CT) with micrometer spatial resolution. An identical sample volume was imaged stepwise, first under oxidizing and reducing atmospheres (imitating calcination and activation processes), and then under model reaction conditions for DME synthesis (H2:CO:CO2 ratio of 16:8:1, up to 250 °C). The multimodal imaging methods offered insights into the active metal structure and speciation within the catalyst, and allowed imaging of both the catalyst core and zeolite shell in a single acquisition. Dispersion of nanosized Cu species was observed in the catalyst core during reduction, with formation of a metastable Cu(+) phase at the core-shell interface. Under DME reaction conditions at 1 bar, the coexistence of Cu(0) in the active catalyst core together with partially oxidized Cu species was unraveled. The zeolite shell and core-shell interface remained stable under all conditions, preserving the bifunctional nature of the catalyst. These observations are inaccessible using standard bulk techniques like X-ray absorption spectroscopy (XAS) and XRD, demonstrating the potential of multimodal in situ X-ray CT for characterization of hierarchically designed materials, which stand to benefit tremendously from such 3D spatially resolved measurements.

  9. 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

  10. 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.

  11. 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.

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

    NASA Astrophysics Data System (ADS)

    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.

  13. In Situ Super-Resolution Imaging of Genomic DNA with OligoSTORM and OligoDNA-PAINT.

    PubMed

    Beliveau, Brian J; Boettiger, Alistair N; Nir, Guy; Bintu, Bogdan; Yin, Peng; Zhuang, Xiaowei; Wu, C-Ting

    2017-01-01

    OligoSTORM and OligoDNA-PAINT meld the Oligopaint technology for fluorescent in situ hybridization (FISH) with, respectively, Stochastic Optical Reconstruction Microscopy (STORM) and DNA-based Point Accumulation for Imaging in Nanoscale Topography (DNA-PAINT) to enable in situ single-molecule super-resolution imaging of nucleic acids. Both strategies enable ≤20 nm resolution and are appropriate for imaging nanoscale features of the genomes of a wide range of species, including human, mouse, and fruit fly (Drosophila).

  14. Correlated Imaging with C60-SIMS and Confocal Raman Microscopy: Visualization of Cell-Scale Molecular Distributions in Bacterial Biofilms

    PubMed Central

    2014-01-01

    Secondary ion mass spectrometry (SIMS) and confocal Raman microscopy (CRM) are combined to analyze the chemical composition of cultured Pseudomonas aeruginosa biofilms, providing complementary chemical information for multiple analytes within the sample. Precise spatial correlation between SIMS and CRM images is achieved by applying a chemical microdroplet array to the sample surface which is used to navigate the sample, relocate regions of interest, and align image data. CRM is then employed to nondestructively detect broad molecular constituent classes—including proteins, carbohydrates, and, for the first time, quinolone signaling molecules—in Pseudomonas-derived biofilms. Subsequent SIMS imaging at the same location detects quinolone distributions in excellent agreement with the CRM, discerns multiple quinolone species which differ slightly in mass, resolves subtle differences in their distributions, and resolves ambiguous compound assignments from CRM by determining specific molecular identities via in situ tandem MS. PMID:25268906

  15. Label-Free Neurosurgical Pathology with Stimulated Raman Imaging

    PubMed Central

    Lu, Fa-Ke; Calligaris, David; Olubiyi, Olutayo I.; Norton, Isaiah; Yang, Wenlong; Santagata, Sandro; Xie, X. Sunney; Golby, Alexandra J.; Agar, Nathalie Y. R.

    2016-01-01

    The goal of brain tumor surgery is to maximize tumor removal without injuring critical brain structures. Achieving this goal is challenging since it can be difficult to distinguish tumor from non-tumor tissue. While standard histopathology provides information that could assist tumor delineation, it cannot be performed iteratively during surgery as freezing, sectioning, and staining of the tissue require too much time. Stimulated Raman scattering (SRS) microscopy is a powerful label-free chemical imaging technology that enables rapid mapping of lipids and proteins within a fresh specimen. This information can be rendered into pathology-like images. Although this approach has been used to assess the density of glioma cells in murine orthotopic xenografts models and human brain tumors, tissue heterogeneity in clinical brain tumors has not yet been fully evaluated with SRS imaging. Here we profile 41 specimens resected from 12 patients with a range of brain tumors. By evaluating large-scale stimulated Raman imaging data and correlating this data with current clinical gold standard of histopathology for 4,422 fields of view, we capture many essential diagnostic hallmarks for glioma classification. Notably, in fresh tumor samples we observe additional features, not seen by conventional methods, including extensive lipid droplets within glioma cells, collagen deposition in gliosarcoma, and irregularity and disruption of myelinated fibers in areas infiltrated by oligodendroglioma cells. This data is freely available in a public resource to foster diagnostic training and to permit additional interrogation. Our work establishes the methodology and provides a significant collection of reference images for label-free neurosurgical pathology. PMID:27197198

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

    PubMed

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

    2014-04-07

    A novel microfluidic reactor for biofilm growth and in situ characterization using time-of-flight secondary ion mass spectrometry (ToF-SIMS) was constructed to enable two-dimensional chemical imaging of hydrated biofilms. We demonstrate the detection of characteristic fatty acid fragments from microfluidic reactor-grown biofilms and illustrate advantages of hydrated-state ToF-SIMS imaging.

  17. Visualizing 3D objects from 2D cross sectional images displayed in-situ versus ex-situ.

    PubMed

    Wu, Bing; Klatzky, Roberta L; Stetten, George

    2010-03-01

    The present research investigates how mental visualization of a 3D object from 2D cross sectional images is influenced by displacing the images from the source object, as is customary in medical imaging. Three experiments were conducted to assess people's ability to integrate spatial information over a series of cross sectional images in order to visualize an object posed in 3D space. Participants used a hand-held tool to reveal a virtual rod as a sequence of cross-sectional images, which were displayed either directly in the space of exploration (in-situ) or displaced to a remote screen (ex-situ). They manipulated a response stylus to match the virtual rod's pitch (vertical slant), yaw (horizontal slant), or both. Consistent with the hypothesis that spatial colocation of image and source object facilitates mental visualization, we found that although single dimensions of slant were judged accurately with both displays, judging pitch and yaw simultaneously produced differences in systematic error between in-situ and ex-situ displays. Ex-situ imaging also exhibited errors such that the magnitude of the response was approximately correct but the direction was reversed. Regression analysis indicated that the in-situ judgments were primarily based on spatiotemporal visualization, while the ex-situ judgments relied on an ad hoc, screen-based heuristic. These findings suggest that in-situ displays may be useful in clinical practice by reducing error and facilitating the ability of radiologists to visualize 3D anatomy from cross sectional images.

  18. High-resolution Fiber-optic Microendoscopy for in situ Cellular Imaging

    PubMed Central

    Pierce, Mark; Yu, Dihua; Richards-Kortum, Rebecca

    2011-01-01

    Many biological and clinical studies require the longitudinal study and analysis of morphology and function with cellular level resolution. Traditionally, multiple experiments are run in parallel, with individual samples removed from the study at sequential time points for evaluation by light microscopy. Several intravital techniques have been developed, with confocal, multiphoton, and second harmonic microscopy all demonstrating their ability to be used for imaging in situ 1. With these systems, however, the required infrastructure is complex and expensive, involving scanning laser systems and complex light sources. Here we present a protocol for the design and assembly of a high-resolution microendoscope which can be built in a day using off-the-shelf components for under US$5,000. The platform offers flexibility in terms of image resolution, field-of-view, and operating wavelength, and we describe how these parameters can be easily modified to meet the specific needs of the end user. We and others have explored the use of the high-resolution microendoscope (HRME) in in vitro cell culture 2-5, in excised 6 and living animal tissues 2,5, and in human tissues in vivo 2,7. Users have reported the use of several different fluorescent contrast agents, including proflavine 2-4, benzoporphyrin-derivative monoacid ring A (BPD-MA) 5, and fluoroscein 6,7, all of which have received full, or investigational approval from the FDA for use in human subjects. High-resolution microendoscopy, in the form described here, may appeal to a wide range of researchers working in the basic and clinical sciences. The technique offers an effective and economical approach which complements traditional benchtop microscopy, by enabling the user to perform high-resolution, longitudinal imaging in situ. PMID:21248707

  19. High-resolution fiber-optic microendoscopy for in situ cellular imaging.

    PubMed

    Pierce, Mark; Yu, Dihua; Richards-Kortum, Rebecca

    2011-01-11

    Many biological and clinical studies require the longitudinal study and analysis of morphology and function with cellular level resolution. Traditionally, multiple experiments are run in parallel, with individual samples removed from the study at sequential time points for evaluation by light microscopy. Several intravital techniques have been developed, with confocal, multiphoton, and second harmonic microscopy all demonstrating their ability to be used for imaging in situ. With these systems, however, the required infrastructure is complex and expensive, involving scanning laser systems and complex light sources. Here we present a protocol for the design and assembly of a high-resolution microendoscope which can be built in a day using off-the-shelf components for under US$5,000. The platform offers flexibility in terms of image resolution, field-of-view, and operating wavelength, and we describe how these parameters can be easily modified to meet the specific needs of the end user. We and others have explored the use of the high-resolution microendoscope (HRME) in in vitro cell culture, in excised and living animal tissues, and in human tissues in vivo. Users have reported the use of several different fluorescent contrast agents, including proflavine, benzoporphyrin-derivative monoacid ring A (BPD-MA), and fluoroscein, all of which have received full, or investigational approval from the FDA for use in human subjects. High-resolution microendoscopy, in the form described here, may appeal to a wide range of researchers working in the basic and clinical sciences. The technique offers an effective and economical approach which complements traditional benchtop microscopy, by enabling the user to perform high-resolution, longitudinal imaging in situ.

  20. Deep-UV resonance Raman imaging of a cell (Conference Presentation)

    NASA Astrophysics Data System (ADS)

    Kumamoto, Yasuaki

    2016-09-01

    Raman microscopy enables a sensitive, label-free molecular imaging of cells. Employing deep-UV (DUV) light for Raman excitation allows selective measurement of nucleotide bases and aromatic amino acids in a cell, without spectral overlapping of components with a large quantity (i.e. lipid, peptide), because their Raman scattering are specifically enhanced due to the resonance effect. To implement DUV resonance Raman imaging of cells, I previously established a home-built Raman microscope equipped with a DUV laser (λ = 257.2 nm). Raman image representing the distribution of cellular nucleic acid can be reconstructed with the intensity of a Raman band selectively assigned to adenine and guanine. Unfortunately, DUV resonance Raman imaging of cells is severely hindered by molecular photodegradation that occurs after a molecule absorbs DUV light during Raman measurement, precluding a high signal-to-noise ratio and repetitive measurement. To address this issue, I developed a technique for molecular protection under DUV exposure; the trivalent ions of lanthanide group including terbium, europium, and thulium could significantly suppress the molecular photodegradation by relaxing the DUV-excited molecules. The buffer solution containing any of these lanthanide ions with the concentration of 100 µM or higher could provide less destruction of the cellular structures, including nucleotide bases, than the one without the ions, under DUV exposure. Utilizing such protective effects of the lanthanide ions, I successfully achieved a twice higher signal-to-noise ratio and repetitive DUV Raman imaging of cells.

  1. SERS imaging of cell-surface biomolecules metabolically labeled with bioorthogonal Raman reporters.

    PubMed

    Xiao, Ming; Lin, Liang; Li, Zefan; Liu, Jie; Hong, Senlian; Li, Yaya; Zheng, Meiling; Duan, Xuanming; Chen, Xing

    2014-08-01

    Live imaging of biomolecules with high specificity and sensitivity as well as minimal perturbation is essential for studying cellular processes. Here, we report the development of a bioorthogonal surface-enhanced Raman scattering (SERS) imaging approach that exploits small Raman reporters for visualizing cell-surface biomolecules. The cells were cultured and imaged by SERS microscopy on arrays of Raman-enhancing nanoparticles coated on silicon wafers or glass slides. The Raman reporters including azides, alkynes, and carbondeuterium bonds are small in size and spectroscopically bioorthogonal (background-free). We demonstrated that various cell-surface biomolecules including proteins, glycans, and lipids were metabolically incorporated with the corresponding precursors bearing a Raman reporter and visualized by SERS microscopy. The coupling of SERS microscopy with bioorthogonal Raman reporters expands the capabilities of live-cell microscopy beyond the modalities of fluorescence and label-free imaging. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. 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.

  3. In situ, simultaneous thermal imaging and infrared molecular emission studies of solid oxide fuel cell electrodes

    NASA Astrophysics Data System (ADS)

    Kirtley, J. D.; Qadri, S. N.; Steinhurst, D. A.; Owrutsky, J. C.

    2016-12-01

    Various in situ probes of solid oxide fuel cells (SOFCs) have advanced recently to provide detailed, real time data regarding materials and chemical processes that relate to device performance and degradation. These techniques offer insights into complex fuel chemistry at the anode in particular, especially in the context of model predictions. However, cell-to-cell variations can hinder mechanistic interpretations of measurements from separate, independent techniques. The present study describes an in situ technique that for the first time simultaneously measures surface temperature changes using near infrared thermal imaging and gas species using Fourier-transform infrared emission spectra at the anodes of operating SOFCs. Electrolyte-supported SOFCs with Ni-based anodes are operated at 700 °C with internal, dry-reformed methane at 75% maximum current and at open circuit voltage (OCV) while electrochemical and optical measurements are collected. At OCV, more cooling is observed coincident with more CO reforming products. Under load, CO decreases while the anode cools less, especially near the current collectors. The extent of cooling is more sensitive to polarization for electrolyte-supported cells because their anodes are thinner relative to anode-supported cells. This study exemplifies how this duplex technique can be a useful probe of electrochemical processes in SOFCs.

  4. (7)Li in situ 1D NMR imaging of a lithium ion battery.

    PubMed

    Klamor, S; Zick, K; Oerther, T; Schappacher, F M; Winter, M; Brunklaus, G

    2015-02-14

    The spatial distribution of charge carriers in lithium ion batteries during current flow is of fundamental interest for a detailed understanding of transport properties and the development of strategies for future improvements of the electrolyte-electrode interface behaviour. In this work we explored the potential of (7)Li 1D in situ NMR imaging for the identification of concentration gradients under constant current load in a battery cell. An electrochemical cell based on PTFE body and a stack of glass microfiber discs that are soaked with a technically relevant electrolyte suitable for high-temperature application and squeezed between a Li metal and a nano-Si-graphite composite electrode was assembled to acquire (7)Li 1D in situ NMR profiles with an improved NMR pulse sequence as function of time and state of charge, thereby visualizing the course of ion concentration during charge and discharge. Surface localized changes of Li concentration were attributed to processes such as solid electrolyte interphase formation or full lithiation of the composite electrode. The method allows the extraction of lithium ion transport properties.

  5. 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.

  6. Raman and Infrared Microspectral Imaging of Mitotic Cells

    PubMed Central

    MATTHÄUS, CHRISTIAN; BOYDSTON-WHITE, SUSIE; MILJKOVIĆ, MILOŠ; ROMEO, MELISSA; DIEM, MAX

    2009-01-01

    We report the first ever Raman and infrared microspectroscopic images of human cells at different stages of mitosis. These spectroscopic methods monitor the distribution of condensed nuclear chromatin, and other biochemical components, utilizing inherent protein and DNA spectral markers, and, therefore, do not require the use of any stains. In conjunction with previously reported data from the G1, S, and G2 phases of the cell cycle, the complete cell division cycle has now been mapped by spectroscopic methods. Although the results reported here do not offer new insights into the distribution of biochemical components during mitosis, the recognition of cell division without the use of stains, and the possibility of doing so on living cells, may be useful for an automatic, spectroscopic determination of the proliferation rates of cells and tissues. Spectral images were constructed by plotting spectral intensities of DNA or protein versus the coordinates from which spectra were recorded. We found that both Raman and infrared intensities depend on the overall chromatin density variation among the individual subphases of mitosis. PMID:16454901

  7. Design, operation and applications of a visible-light confocal scanning Fourier transform Raman microscope for volumetric Raman spectrochemical imaging

    NASA Astrophysics Data System (ADS)

    Brenan, Colin John Herbert

    A new type of confocal Raman microscope called a Fourier transform confocal Raman microscope (FT-CRM) was designed, built and characterized with respect to its spatio-spectral imaging properties. Several different applications of the FT-CRM are presented that take advantage of its unique spectral and spatial imaging characteristics. The instrument combines focused illumination with spatially-filtered detection in a confocal optical configuration to collect photons scattered from a diffraction-limited volume in the sample (typically [<]5×10-18/ m3) and reject photons from outside that region. The molecular vibrational information encoded in the inelastic, or Raman, spectral component of light scattered from the confocal volume is measured with a visible light Fourier transform Raman spectrometer. By scanning the sample relative to the confocal volume, a volumetric Raman spectrochemical image of the sample can be constructed. Raman scattering is an inherently inefficient process; hence an optimal radius pinhole must be found that balances the FT-CRM optical throughput against the microscope spatial resolution and image contrast. Detailed experimental measurements mapped out the FT-CRM spatial response (axial and lateral), optical throughput and image signal-to-background and signal-to-noise ratios as a function of pinhole radius. Excellent agreement was found between these measurements and the predictions of a theoretical microscope model also developed as part of this thesis. Several applications of the FT-CRM included volumetric compositional imaging of three-dimensional chemically inhomogeneous materials such as cellulose and polyester fibers in water or two immiscible optically- similar liquids, water and trichloroehthylene, in a porous quartz sandstone matrix. The potential of the FT- CRM for non-invasive spectrochemical detection and imaging through a turbid tissue-like medium was demonstrated and a new spectral estimator, Fast Orthogonal Search, was evaluated

  8. 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

  9. 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

  10. Topographic Study on Staging Transition in H2SO4-Graphite Intercalation Compound by in situ Raman Scattering Measurements

    NASA Astrophysics Data System (ADS)

    Nishitani, Ryusuke; Sasaki, Yoshiro; Nishina, Yuichiro

    1987-03-01

    The staging kinetics in H2SO4-GIC’s has been investigated experimentally by time-and space-dependent Raman scattering measurements. The stage transition from stage n to n-1 begins at the interface between the intercalant reservoir and the a-face of the graphite crystal. The lower stage-(n-1) domains emerge at the interface and proceed toward the inner region of the crystal. A narrow phase-boundary between different stage domains exists in the localized region and move toward the inner region as the stage transformation progresses. The present results support the model [R. Nishitani, Y. Uno and H. Suematsu: Synth. Met. 7 (1983) 13] that the stage transformation proceeds via propagation of the boundary between well-staged regions. The origin of the stage disorder is also discussed.

  11. Degree of conversion of two-step etch-and-rinse adhesives: In situ micro-Raman analysis.

    PubMed

    Navarra, Chiara Ottavia; Breschi, Lorenzo; Turco, Gianluca; Diolosà, Marina; Fontanive, Luca; Manzoli, Lucia; Di Lenarda, Roberto; Cadenaro, Milena

    2012-09-01

    DC of three commercial two-step etch-and-rinse adhesives across the dentine-adhesive interface was investigated using micro-Raman spectroscopy. The hypothesis tested was that no difference in DC would exist among the adhesives tested. Adper Scotchbond 1XT (3M ESPE), Prime&Bond NT (Dentsply DeTrey), and Ambar (FGM) were applied on human dentine disks (n=9). Composite increments of 2mm were then applied on the adhesive surface. Raman spectra were collected along the dentine-adhesive interface. The relative intensities of the peaks associated with the mineral (PO(4)(3-) at 960cm(-1)) and the adhesive (CC at 1640cm(-1); phenyl CC at 1610cm(-1)) were used to identify the adhesive within the hybrid layer and calculate its DC. Adper Scotchbond 1XT and Ambar showed similar DC (79±7% and 77±7%, respectively), while a lower DC was found for Prime&Bond NT (70±7%; p<0.05). The hypothesis tested was rejected because differences were found among the adhesives tested. The difference in DC among the three adhesive systems can be attributed to different monomer compositions and solvents. Further studies are needed to correlate DC with other mechanical properties of these adhesives. Insufficient polymerization of an adhesive can result in a weak hybrid layer, and the presence of unreacted monomers may result in degradation of the polymeric network, decreasing the strength and longevity of the bond. In the present study, Adper Scotchbond 1XT and Ambar performed significantly better than Prime&Bond NT. Copyright © 2012 Elsevier Ltd. All rights reserved.

  12. Quantitative volumetric Raman imaging of three dimensional cell cultures

    PubMed Central

    Kallepitis, Charalambos; Bergholt, Mads S.; Mazo, Manuel M.; Leonardo, Vincent; Skaalure, Stacey C.; Maynard, Stephanie A.; Stevens, Molly M.

    2017-01-01

    The ability to simultaneously image multiple biomolecules in biologically relevant three-dimensional (3D) cell culture environments would contribute greatly to the understanding of complex cellular mechanisms and cell–material interactions. Here, we present a computational framework for label-free quantitative volumetric Raman imaging (qVRI). We apply qVRI to a selection of biological systems: human pluripotent stem cells with their cardiac derivatives, monocytes and monocyte-derived macrophages in conventional cell culture systems and mesenchymal stem cells inside biomimetic hydrogels that supplied a 3D cell culture environment. We demonstrate visualization and quantification of fine details in cell shape, cytoplasm, nucleus, lipid bodies and cytoskeletal structures in 3D with unprecedented biomolecular specificity for vibrational microspectroscopy. PMID:28327660

  13. Quantitative volumetric Raman imaging of three dimensional cell cultures

    NASA Astrophysics Data System (ADS)

    Kallepitis, Charalambos; Bergholt, Mads S.; Mazo, Manuel M.; Leonardo, Vincent; Skaalure, Stacey C.; Maynard, Stephanie A.; Stevens, Molly M.

    2017-03-01

    The ability to simultaneously image multiple biomolecules in biologically relevant three-dimensional (3D) cell culture environments would contribute greatly to the understanding of complex cellular mechanisms and cell-material interactions. Here, we present a computational framework for label-free quantitative volumetric Raman imaging (qVRI). We apply qVRI to a selection of biological systems: human pluripotent stem cells with their cardiac derivatives, monocytes and monocyte-derived macrophages in conventional cell culture systems and mesenchymal stem cells inside biomimetic hydrogels that supplied a 3D cell culture environment. We demonstrate visualization and quantification of fine details in cell shape, cytoplasm, nucleus, lipid bodies and cytoskeletal structures in 3D with unprecedented biomolecular specificity for vibrational microspectroscopy.

  14. Combining hyperspectral imaging and Raman spectroscopy for remote chemical sensing

    NASA Astrophysics Data System (ADS)

    Ingram, John M.; Lo, Edsanter

    2008-04-01

    The Photonics Research Center at the United States Military Academy is conducting research to demonstrate the feasibility of combining hyperspectral imaging and Raman spectroscopy for remote chemical detection over a broad area of interest. One limitation of future trace detection systems is their ability to analyze large areas of view. Hyperspectral imaging provides a balance between fast spectral analysis and scanning area. Integration of a hyperspectral system capable of remote chemical detection will greatly enhance our soldiers' ability to see the battlefield to make threat related decisions. It can also queue the trace detection systems onto the correct interrogation area saving time and reconnaissance/surveillance resources. This research develops both the sensor design and the detection/discrimination algorithms. The one meter remote detection without background radiation is a simple proof of concept.

  15. Fiber-delivered picosecond source for coherent Raman scattering imaging

    PubMed Central

    Wang, Ke; Xu, Chris

    2013-01-01

    We demonstrate a two-color, fiber-delivered picosecond source for coherent Raman scattering (CRS) imaging. The wavelength-tunable picosecond pump is generated by nonlinear spectral compression of a prechirped femtosecond pulse from a mode-locked titanium:sapphire (Ti:S) laser. The 1064 nm picosecond Stokes pulse is generated by an all-fiber time-lens source that is synchronized to the Ti:S laser. The pump and Stokes beams are combined in an optical fiber coupler, which serves not only as the delivery fiber but also as the nonlinear medium for spectral compression of the femtosecond pulse. CRS imaging of mouse skin is performed to demonstrate the practicality of this source. PMID:22048375

  16. Electrical imaging of subsurface nanoparticle propagation for in-situ groundwater remediation

    NASA Astrophysics Data System (ADS)

    Flores Orozco, Adrián; Gallistl, Jakob; Schmid, Doris; Micic Batka, Vesna; Bücker, Matthias; Hofmann, Thilo

    2017-04-01

    Application of nanoparticles has emerged as a promising in situ remediation technology for the remediation of contaminated groundwater, particularly for areas difficult to access by other remediation techniques. The performance of nanoparticle injections, as a foremost step within this technology, is usually assessed through the geochemical analysis of soil and groundwater samples. This approach is not well suited for a real-time monitoring, and often suffers from a poor spatio-temporal resolution and only provides information from areas close to the sampling points. To overcome these limitations we propose the application of non-invasive Induced Polarization (IP) imaging, a geophysical method that provides information on the electrical properties of the subsurface. The analysis of temporal changes in the electrical images allows tracking the propagation of the injected nanoparticle suspension and detection of the induced bio-geochemical changes in the subsurface. Here, we present IP monitoring results for data collected during the injection of Nano-Goethite particles (NGP) used for simulation of biodegradation of a BTEX plume (i.e., benzene, toluene, ethylbenzene, and xylene) at the Spolchemie II site, CZ. Frequency-domain IP measurements were collected parallel to the groundwater flow direction and centred on the NGP injection point. Pre-injection imaging results revealed high electrical conductivities (> 10 S/m) and negligible polarization effects in the BTEX-contaminated part of the saturated zone (below 5 m depth). The apparently contradictory observation - BTEX compounds are poor electrical conductors - can be explained by the release of carbonic acids (a metabolic by-product of the biodegradation of hydrocarbons), which leads to an increase of the electrical conductivity. Post-injection images revealed a significant decrease (> 50%) of the electrical conductivity, with even larger changes in the proximity of the injection points, most likely due to the

  17. 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 employe