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Sample records for vacuum-ultraviolet circular dichroism

  1. Conformation of membrane-bound proteins revealed by vacuum-ultraviolet circular-dichroism and linear-dichroism spectroscopy.

    Science.gov (United States)

    Matsuo, Koichi; Maki, Yasuyuki; Namatame, Hirofumi; Taniguchi, Masaki; Gekko, Kunihiko

    2016-03-01

    Knowledge of the conformations of a water-soluble protein bound to a membrane is important for understanding the membrane-interaction mechanisms and the membrane-mediated functions of the protein. In this study we applied vacuum-ultraviolet circular-dichroism (VUVCD) and linear-dichroism (LD) spectroscopy to analyze the conformations of α-lactalbumin (LA), thioredoxin (Trx), and β-lactoglobulin (LG) bound to phosphatidylglycerol liposomes. The VUVCD analysis coupled with a neural-network analysis showed that these three proteins have characteristic helix-rich conformations involving several helical segments, of which two amphiphilic or hydrophobic segments take part in interactions with the liposome. The LD analysis predicted the average orientations of these helix segments on the liposome: two amphiphilic helices parallel to the liposome surface for LA, two hydrophobic helices perpendicular to the liposome surface for Trx, and a hydrophobic helix perpendicular to and an amphiphilic helix parallel to the liposome surface for LG. This sequence-level information about the secondary structures and orientations was used to formulate interaction models of the three proteins at the membrane surface. This study demonstrates the validity of a combination of VUVCD and LD spectroscopy in conformational analyses of membrane-binding proteins, which are difficult targets for X-ray crystallography and nuclear magnetic resonance spectroscopy. © 2016 Wiley Periodicals, Inc.

  2. Experimental and theoretical studies of vacuum-ultraviolet electronic circular dichroism of hydroxy acids in aqueous solution.

    Science.gov (United States)

    Fukuyama, Takayuki; Matsuo, Koichi; Gekko, Kunihiko

    2011-01-01

    The electronic circular dichroism (ECD) spectra of three L-hydroxy acids (L-lactic acid, (+)-(S)-2-hydroxy-3-methylbutyric acid, and (-)-(S)-2-hydroxyisocaproic acid) were measured down to 160 nm in aqueous solution using a vacuum-ultraviolet ECD spectrophotometer. To assign the two positive peaks around 210 and 175 nm and the one negative peak around 190 nm in the observed spectra, the ECD spectrum of L-lactic acid was calculated using time-dependent density functional theory (DFT) for the optimized structures by DFT and a continuum model. The observed ECD spectrum was successfully reproduced as the average spectrum for four optimized structures with seven water molecules that localized around the COO(-) and OH groups of L-lactic acid. The positive peak around 210 nm and the negative peak around 185 nm in the calculated spectrum were attributable to the nπ* transition of the carboxyl group, with the latter peak also being influenced by the ππ* transition of the carboxyl group; however, the positive peak around 165 nm involved unassignable higher energy transitions. The comparison of the calculated ECD spectra for L-lactic acid and L-alanine revealed that the network with loose hydrogen bonding around the COO(-) and OH groups is responsible for the flexible conformation of hydroxy acids and complicated side-chain dependence of ECD spectra relative to amino acids. Copyright © 2011 Wiley Periodicals, Inc.

  3. Toroidal circular dichroism

    Science.gov (United States)

    Raybould, T. A.; Fedotov, V. A.; Papasimakis, N.; Kuprov, I.; Youngs, I. J.; Chen, W. T.; Tsai, D. P.; Zheludev, N. I.

    2016-07-01

    We demonstrate that the induced toroidal dipole, represented by currents flowing on the surface of a torus, makes a distinct and indispensable contribution to circular dichroism. We show that toroidal circular dichroism supplements the well-known mechanism involving electric dipole and magnetic dipole transitions. We illustrate this with rigorous analysis of the experimentally measured polarization-sensitive transmission spectra of an artificial metamaterial, constructed from elements of toroidal symmetry. We argue that toroidal circular dichroism will be found in large biomolecules with elements of toroidal symmetry and should be taken into account in the interpretation of circular dichroism spectra of organics.

  4. Vacuum ultraviolet circularly polarized coherent femtosecond pulses from laser seeded relativistic electrons

    Directory of Open Access Journals (Sweden)

    N. Čutić

    2011-03-01

    Full Text Available We have demonstrated the generation of circularly polarized coherent light pulses at 66 nm wavelength by combining laser seeding at 263 nm of a 375 MeV relativistic electron bunch with subsequent coherent harmonic generation from an elliptical undulator of APPLE-II type. Coherent pulses at higher harmonics in linear polarization have been produced and recorded up to the sixth order (44 nm. The duration of the generated pulses depends on the temporal overlap of the initial seed laser pulse and the electron bunch and was on the order of 200 fs. Currently, this setup is the only source worldwide producing coherent fs-light pulses with variable polarization in the vacuum ultraviolet.

  5. Circular dichroism techniques: biomolecular and nanostructural analyses- a review.

    Science.gov (United States)

    Ranjbar, Bijan; Gill, Pooria

    2009-08-01

    This paper reviews the best known techniques using circular dichroism spectroscopy such as conventional circular dichroism (i.e. electronic circular dichroism), magnetic circular dichroisms (magnetic vibrational circular dichroism, x-ray magnetic circular dichroism), fluorescence detected circular dichroism, near-infrared circular dichroism, vibrational circular dichroism, Fourier transform infrared circular dichroism, high pressure liquid chromatography circular dichroism, stopped-flow circular dichroism, and synchrotron radiation circular dichroism. Also, we have described here the most important applications of circular dichroism spectroscopy in structural biochemistry and nanoscience.

  6. Gauge-Invariant Formulation of Circular Dichroism.

    Science.gov (United States)

    Raimbault, Nathaniel; de Boeij, Paul L; Romaniello, Pina; Berger, J A

    2016-07-12

    Standard formulations of magnetic response properties, such as circular dichroism spectra, are plagued by gauge dependencies, which can lead to unphysical results. In this work, we present a general gauge-invariant and numerically efficient approach for the calculation of circular dichroism spectra from the current density. First we show that in this formulation the optical rotation tensor, the response function from which circular dichroism spectra can be obtained, is independent of the origin of the coordinate system. We then demonstrate that its trace is independent of the gauge origin of the vector potential. We also show how gauge invariance can be retained in practical calculations with finite basis sets. As an example, we explain how our method can be applied to time-dependent current-density-functional theory. Finally, we report gauge-invariant circular dichroism spectra obtained using the adiabatic local-density approximation. The circular dichroism spectra we thus obtain are in good agreement with experiment.

  7. Circular dichroism spectroscopy of fluorescent proteins

    NARCIS (Netherlands)

    Visser, N.V.; Hink, M.A.; Borst, J.W.; Krogt, van der G.N.M.; Visser, A.J.W.G.

    2002-01-01

    Circular dichroism (CD) spectra have been obtained from several variants of green fluorescent protein: blue fluorescent protein (BFP), enhanced cyan fluorescent protein (CFP), enhanced green fluorescent protein (GFP), enhanced yellow fluorescent protein (YFP), all from Aequorea victoria, and the red

  8. Exciton circular dichroism in channelrhodopsin.

    Science.gov (United States)

    Pescitelli, Gennaro; Kato, Hideaki E; Oishi, Satomi; Ito, Jumpei; Maturana, Andrés Daniel; Nureki, Osamu; Woody, Robert W

    2014-10-16

    Channelrhodopsins (ChRs) are of great interest currently because of their important applications in optogenetics, the photostimulation of neurons. The absorption and circular dichroism (CD) spectra of C1C2, a chimera of ChR1 and ChR2 of Chlamydomonas reinhardtii, have been studied experimentally and theoretically. The visible absorption spectrum of C1C2 shows vibronic fine structure in the 470 nm band, consistent with the relatively nonpolar binding site. The CD spectrum has a negative band at 492 nm (Δε(max) = -6.17 M(-1) cm(-1)) and a positive band at 434 nm (Δε(max) = +6.65 M(-1) cm(-1)), indicating exciton coupling within the C1C2 dimer. Time-dependent density functional theory (TDDFT) calculations are reported for three models of the C1C2 chromophore: (1) the isolated protonated retinal Schiff base (retPSB); (2) an ion pair, including the retPSB chromophore, two carboxylate side chains (Asp 292, Glu 162), modeled by acetate, and a water molecule; and (3) a hybrid quantum mechanical/molecular mechanical (QM/MM) model depicting the binding pocket, in which the QM part consists of the same ion pair as that in (2) and the MM part consists of the protein residues surrounding the ion pair within 10 Å. For each of these models, the CD of both the monomer and the dimer was calculated with TDDFT. For the dimer, DeVoe polarizability theory and exciton calculations were also performed. The exciton calculations were supplemented by calculations of the coupling of the retinal transition with aromatic and peptide group transitions. For the dimer, all three methods and three models give a long-wavelength C2-axis-polarized band, negative in CD, and a short-wavelength band polarized perpendicular to the C2 axis with positive CD, differing in wavelength by 1-5 nm. Only the retPSB model gives an exciton couplet that agrees qualitatively with experiment. The other two models give a predominantly or solely positive band. We further analyze an N-terminal truncated mutant

  9. Circular Phonon Dichroism in Weyl Semimetals

    Science.gov (United States)

    Liu, Donghao; Shi, Junren

    2017-08-01

    We derive the phonon dynamics of magnetic metals in the presence of strong spin-orbit coupling. We show that both a dissipationless viscosity and a dissipative viscosity arise in the dynamics. While the dissipationless viscosity splits the dispersion of left-handed and right-handed circularly polarized phonons, the dissipative viscosity damps them differently, inducing circular phonon dichroism. The effect offers a new degree of manipulation of phonons, i.e., the control of the phonon polarization. We investigate the effect in Weyl semimetals. We find that there exists strong circular phonon dichroism in Weyl semimetals breaking both the time-reversal and the inversion symmetry, making them potential materials for realizing the acoustic circular polarizer.

  10. All-dielectric metasurface circular dichroism waveplate.

    Science.gov (United States)

    Hu, Jingpei; Zhao, Xiaonan; Lin, Yu; Zhu, Aijiao; Zhu, Xiaojun; Guo, Peiji; Cao, Bing; Wang, Chinhua

    2017-01-31

    We propose and experimentally demonstrate a high efficient circularly polarizing dichroism waveplate (CPDW) using a Si-based all-dielectric 2Dchiral metasurface. We demonstrate that the CPDW exhibits a unique dichroism in that it functions as a transmissive quarter waveplate for one of either left-or right-handed circularly polarized incident lightand a reflective mirror for the opposite polarization. The circular polarization dichroism (CPD = IRCP - ILCP) in transmission at wavelength ~1.5 μm reaches 97% and the extinction ratio (ER = IRCP/ILCP) is as high as 345:1. Experimental fabrications and measurements of the proposed all-dielectric metasurface are implemented and found to be in excellent agreement with the simulations. The proposed all-dielectric chiral metasurface is of advantages of high-dichroism, easy-fabrication and standard semiconductor fabrication techniques compatible, which could lead to enhanced security in fiber and free-space communications, as well as imaging and sensing applications for circularly polarized light with a highly integrated photonic platform.

  11. PCDDB: the protein circular dichroism data bank, a repository for circular dichroism spectral and metadata

    OpenAIRE

    Whitmore, Lee; Woollett, Benjamin; Miles, Andrew J.; Klose, D.P.; Janes, R.W.; Wallace, Bonnie A.

    2011-01-01

    The Protein Circular Dichroism Data Bank (PCDDB) is a public repository that archives and freely distributes circular dichroism (CD) and synchrotron radiation CD (SRCD) spectral data and their associated experimental metadata. All entries undergo validation and curation procedures to ensure completeness, consistency and quality of the data included. A web-based interface enables users to browse and query sample types, sample conditions, experimental parameters and provides spectra in both gra...

  12. Chiral Surface Waves for Enhanced Circular Dichroism

    CERN Document Server

    Pellegrini, Giovanni; Celebrano, Michele; Duò, Lamberto; Biagioni, Paolo

    2016-01-01

    We present a novel chiral sensing platform that combines a one-dimensional photonic crystal design with a birefringent surface defect. The platform sustains simultaneous transverse electric and transverse magnetic surface modes, which are exploited to generate chiral surface waves. The present design provides homogeneous and superchiral fields of both handednesses over arbitrarily large areas in a wide spectral range, resulting in the enhancement of the circular dichroism signal by two orders of magnitude, thus paving the road toward the successful combination of surface-enhanced spectroscopies and electromagnetic superchirality.

  13. Synchrotron radiation circular dichroism spectroscopy of proteins and applications in structural and functional genomics.

    Science.gov (United States)

    Miles, Andrew J; Wallace, B A

    2006-01-01

    The technique of Synchrotron Radiation Circular Dichroism (SRCD) spectroscopy and its advantages over conventional circular dichroism spectroscopy are described in this tutorial review, as well as recent applications of the technique in structural and functional genomics. Circular dichroism (CD) spectroscopy is a well-established method in biological chemistry and structural biology, but its utility can be limited by the low flux of the light source in the far ultraviolet and vacuum ultraviolet wavelength regions in conventional CD instruments. The development of synchrotron radiation circular dichroism (SRCD), using the intense light of a synchrotron beam, has greatly expanded the utility of the method, especially as a tool for both structural and functional genomics. These applications take advantage of the enhanced features of SRCD relative to conventional CD: the ability to measure lower wavelength data containing more electronic transitions and hence more structural information, the higher signal-to-noise hence requiring smaller samples, the higher intensity enabling measurements in absorbing buffers and in the presence of lipids and detergents, and the ability to do faster measurements enabling high throughput and time-resolved spectroscopy.This article discusses recent developments in SRCD instrumentation, software, sample preparation and methods of analyses, with particular emphasis on their applications to the study of proteins. These advances have led to new applications in structural genomics (SG), including the potential for fold recognition as a means of target selection and the examination of membrane proteins, a class of proteins usually excluded from SG programmes. Other SG uses include detection of macromolecular interactions as a screen for complex formation, and examination of glycoproteins and sugar components. In functional genomics (FG) new applications include screening for ligand binding as a means of identifying function, and examination of

  14. Photoelectron circular dichroism in different ionization regimes

    Science.gov (United States)

    Wollenhaupt, Matthias

    2016-12-01

    Photoelectron circular dichroism (PECD) describes an asymmetry in the photoelectron angular distribution (PAD) from photoionization of randomly oriented enantiomers with circularly polarized light. Beaulieu et al present a comprehensive set of measured PADs from multiphoton ionization of limonene and fenchone in different ionization regimes (multiphoton and tunneling) and analyze the resulting PECD (Beaulieu et al 2016 New J. Phys. 18 102002). From their observations the authors conclude that the PECD is universal in the sense that the molecular chirality is encoded in the PAD independent of the ionization regime. The analysis is supplemented by a classical model based on electron scattering in a chiral potential. The paper presents beautiful data and is an important step towards a more complete physical picture of PECD. The results and their interpretation stimulate the ongoing vivid debate on the role of resonances in multiphoton PECD.

  15. Conformational effects in photoelectron circular dichroism

    Science.gov (United States)

    Turchini, S.

    2017-12-01

    Photoelectron circular dichroism (PECD) is a novel type of spectroscopy, which presents surprising sensitivity to conformational effects in chiral systems. While classical photoelectron spectroscopy mainly responds to conformational effects in terms of energy level shifts, PECD provides a rich and detailed response to tiny changes in electronic and structural properties by means of the intensity dispersion of the circular dichroism as a function of photoelectron kinetic energy. In this work, the basics of PECD will be outlined, emphasizing the role of interference from the l,l+/- 1 outgoing partial wave of the photoelectron in the PECD transition matrix element, which is responsible for the extreme sensitivity to conformational effects. Examples using molecular systems and interfaces will shed light on the powerful application of PECD to classical conformational effects such as group substitution, isomerism, conformer population and clustering. Moreover, the PECD results will be reported in challenging new fields where conformations play a key role, such as vibrational effects, transient chirality and time- resolved experiments. To date, PECD has mostly been based on synchrotron radiation facilities, but it also has a future as a table-top lab experiment by means of multiphoton ionization. An important application of PECD as an analytical tool will be reported. The aim of this review is to illustrate that in PECD, the presence of conformational effects is essential for understanding a wide range of effects from a new perspective, making it different from classical spectroscopy.

  16. Circular Dichroism for the Analysis of Protein-DNA Interactions.

    Science.gov (United States)

    Scarlett, Garry; Siligardi, Giuliano; Kneale, Geoffrey G

    2015-01-01

    The aim of this chapter is to provide information on the practical aspects of circular dichroism (CD) and synchrotron radiation circular dichroism (SRCD) in protein-nucleic acids interaction solution studies. The chapter will describe the guidelines appropriate to designing experiments and conducting correct data interpretation, the use of both benchtop and synchrotron CD approaches is discussed and the advantages of SRCD outlined. Further information and a good general review of the field a can be found in Gray (Circular Dichroism of protein-nucleic acid interactions. In: Fasman GD (ed) Circular dichroism and the conformational analysis of biomolecules. Plenum Press, New York. pp 469-500, 1996).

  17. Circular Dichroism Microscopy Free from Commingling Linear Dichroism via Discretely Modulated Circular Polarization.

    Science.gov (United States)

    Narushima, Tetsuya; Okamoto, Hiromi

    2016-10-20

    In this work, we developed a circular dichroism (CD) imaging microscope with a device to suppress the commingling of linear birefringence (LB) and linear dichroism (LD) signals. CD signals are, in principle, free from the commingling influence of LD and LB if the sample is illuminated with pure circularly polarized light, with no linear polarization contribution. Based on this idea, we here propose a novel circular polarization modulation method to suppress the contribution of linear polarization, which enables high-sensitivity CD detection (10(-4) level in optical density unit or mdeg level in ellipticity) for microscopic imaging at a nearly diffraction limited spatial resolution (sub-μm level). The highly sensitive, diffraction-limited local CD detection will make direct analyses of chiral structures and spatial mappings of optical activity feasible for μm- to sub-μm-sized materials and may yield a number of applications as a unique optical imaging method.

  18. Circular Dichroism Studies on Plasmonic Nanostructures.

    Science.gov (United States)

    Wang, Xiaoli; Tang, Zhiyong

    2017-01-01

    In recent years, optical chirality of plasmonic nanostructures has aroused great interest because of innovative fundamental understanding as well as promising potential applications in optics, catalysis and sensing. Herein, state-of-the-art studies on circular dichroism (CD) characteristics of plasmonic nanostructures are summarized. The hybrid of achiral plasmonic nanoparticles (NPs) and chiral molecules is explored to generate a new CD response at the plasmon resonance as well as the enhanced CD intensity of chiral molecules in the UV region, owing to the Coulomb static and dynamic dipole interactions between plasmonic NPs and chiral molecules. As for chiral assembly of plasmonic NPs, plasmon-plasmon interactions between the building blocks are found to induce generation of intense CD response at the plasmon resonance. Three-dimensional periodical arrangement of plasmonic NPs into macroscale chiral metamaterials is further introduced from the perspective of negative refraction and photonic bandgap. A strong CD signal is also discerned in achiral planar plasmonic nanostructures under illumination of circular polarized plane wave at oblique incidence or input vortex beam at normal incidence. Finally perspectives, especially on future investigation of time-resolved CD responses, are presented. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Vacuum ultraviolet spectroscopy I

    CERN Document Server

    Samson, James A; Lucatorto, Thomas

    1998-01-01

    This volume is for practitioners, experimentalists, and graduate students in applied physics, particularly in the fields of atomic and molecular physics, who work with vacuum ultraviolet applications and are in need of choosing the best type of modern instrumentation. It provides first-hand knowledge of the state-of-the-art equipment sources and gives technical information on how to use it, along with a broad reference bibliography.Key Features* Aimed at experimentalists who are in need of choosing the best type of modern instrumentation in this applied field* Contains a detailed chapter on la

  20. Circular dichroism of green bacterial chlorosomes

    Energy Technology Data Exchange (ETDEWEB)

    Brune, D.C.; Olson, J.M. (Odense Univ. (Denmark)); Gerola, P.D. (Univ. della Calabria, Cosenza (Italy))

    1990-01-01

    Positive and negative bands in previously measured circular dichroism (CD) spectra of Chlorobium limicola chlorosomes appeared to be sign-reversed relative to those of Chloroflexus aurantiacus chlorosomes in the 740-750 nm spectral region where bacteriochlorophyll (BChl) c absorbs maximally. It was not clear, however, whether this difference was intrinsic to the chlorosomes or was due to differences in the procedures used to prepare them. The authors therefore repeated the CD measurements using chlorosomes isolated from both Cb. limicola f. thiosulfatophilum and Cf. aurantiacus using the method of Gerola and Olson. Contrary to the earlier results, both types of chlorosomes had very similar CD spectra, suggesting that both have similar arrangements of BChl c molecules. The previously reported difference between the CD spectra of Chlorobium and Chloroflexus chlorosomes is due to the instability of Chlorobium chlorosomes, which can undergo a hypsochromic shift in the near infrared absorption maximum accompanied by an apparent inversion in their near infrared CD spectrum during isolation. Treating isolated chlorosomes with the strong ionic detergent sodium dodecylsulfate, which removes BChl a, does not alter the arrangement of BChl c molecules in either Chloroflexus or Chlorobium chlorosomes, as indicated by the lack of an effect on their CD spectra.

  1. Anisotropic elliptical dichroism and influence of imperfection of circular polarization upon anisotropic circular dichroism

    Energy Technology Data Exchange (ETDEWEB)

    Wakabayashi, Masamitsu [Department of Biomolecular Engineering, Tokyo Institute of Technology, 4259 Nagatsuta-cho, Midori-ku, Yokohama, Kanagawa 226-8501 (Japan); RIKEN, Research Cluster for Innovation, Nakamura Lab, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan); Yokojima, Satoshi, E-mail: yokojima@toyaku.ac.jp [Tokyo University of Pharmacy and Life Sciences, 1432-1 Horinouchi, Hachiouji-shi, Tokyo 192-0392 (Japan); RIKEN, Research Cluster for Innovation, Nakamura Lab, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan); Fukaminato, Tuyoshi [Research Institute for Electronic Science, Hokkaido University, N20, W10, Kita-ku, Sapporo 001-0020 (Japan); PRESTO, Japan Science and Technology Agency (JST), Sanbancho, Chiyoda-ku, Tokyo 102-0075 (Japan); Ohtani, Hiroyuki [Department of Biomolecular Engineering, Tokyo Institute of Technology, 4259 Nagatsuta-cho, Midori-ku, Yokohama, Kanagawa 226-8501 (Japan); Nakamura, Shinichiro, E-mail: snakamura@riken.jp [RIKEN, Research Cluster for Innovation, Nakamura Lab, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan)

    2015-04-21

    In spite of the importance of anisotropic circular dichroism, in practice, it is difficult to get rid of the artifacts that arise from the imperfection of the circular polarization. Undesirable linear dichroism, interference of two orthogonal polarization states, and linear birefringence prevent us from making accurate measurements. We propose a theoretical method for evaluating the contributions of the first two, which are thought to be the main artifacts when specimens are not thick enough. Using the time-dependent perturbation theory and taking into account the direction of light propagation toward an orientationally fixed molecule, we formulated the transition probability of systems perturbed by arbitrarily polarized light and the absorption difference associated with two kinds of polarized light. We also formulated, as an extension of the dissymmetry factor of circular dichroism, a newly defined dissymmetry factor associated with two arbitrary polarization states. Furthermore, we considered a mixed-state of photon ensemble in which polarization states distribute at a certain width around a certain average. Although the purity of polarization and ellipticity does not correspond immediately, by considering the mixed state it is possible to treat them consistently. We used quantum statistical mechanics to describe the absorption difference for two kinds of photon ensembles and applied the consequent formula to examine the reported experimental results of single-molecule chiroptical responses under discussion in the recent past. The artifacts are theoretically suggested to be sensitive to the incident direction of elliptically polarized light and to the oriented systems, the ellipticity, and the orientation of ellipse. The mixed state has little, if any, effect when the polarization state distribution is narrow.

  2. Anisotropic elliptical dichroism and influence of imperfection of circular polarization upon anisotropic circular dichroism.

    Science.gov (United States)

    Wakabayashi, Masamitsu; Yokojima, Satoshi; Fukaminato, Tuyoshi; Ohtani, Hiroyuki; Nakamura, Shinichiro

    2015-04-21

    In spite of the importance of anisotropic circular dichroism, in practice, it is difficult to get rid of the artifacts that arise from the imperfection of the circular polarization. Undesirable linear dichroism, interference of two orthogonal polarization states, and linear birefringence prevent us from making accurate measurements. We propose a theoretical method for evaluating the contributions of the first two, which are thought to be the main artifacts when specimens are not thick enough. Using the time-dependent perturbation theory and taking into account the direction of light propagation toward an orientationally fixed molecule, we formulated the transition probability of systems perturbed by arbitrarily polarized light and the absorption difference associated with two kinds of polarized light. We also formulated, as an extension of the dissymmetry factor of circular dichroism, a newly defined dissymmetry factor associated with two arbitrary polarization states. Furthermore, we considered a mixed-state of photon ensemble in which polarization states distribute at a certain width around a certain average. Although the purity of polarization and ellipticity does not correspond immediately, by considering the mixed state it is possible to treat them consistently. We used quantum statistical mechanics to describe the absorption difference for two kinds of photon ensembles and applied the consequent formula to examine the reported experimental results of single-molecule chiroptical responses under discussion in the recent past. The artifacts are theoretically suggested to be sensitive to the incident direction of elliptically polarized light and to the oriented systems, the ellipticity, and the orientation of ellipse. The mixed state has little, if any, effect when the polarization state distribution is narrow.

  3. Anisotropic elliptical dichroism and influence of imperfection of circular polarization upon anisotropic circular dichroism

    Science.gov (United States)

    Wakabayashi, Masamitsu; Yokojima, Satoshi; Fukaminato, Tuyoshi; Ohtani, Hiroyuki; Nakamura, Shinichiro

    2015-04-01

    In spite of the importance of anisotropic circular dichroism, in practice, it is difficult to get rid of the artifacts that arise from the imperfection of the circular polarization. Undesirable linear dichroism, interference of two orthogonal polarization states, and linear birefringence prevent us from making accurate measurements. We propose a theoretical method for evaluating the contributions of the first two, which are thought to be the main artifacts when specimens are not thick enough. Using the time-dependent perturbation theory and taking into account the direction of light propagation toward an orientationally fixed molecule, we formulated the transition probability of systems perturbed by arbitrarily polarized light and the absorption difference associated with two kinds of polarized light. We also formulated, as an extension of the dissymmetry factor of circular dichroism, a newly defined dissymmetry factor associated with two arbitrary polarization states. Furthermore, we considered a mixed-state of photon ensemble in which polarization states distribute at a certain width around a certain average. Although the purity of polarization and ellipticity does not correspond immediately, by considering the mixed state it is possible to treat them consistently. We used quantum statistical mechanics to describe the absorption difference for two kinds of photon ensembles and applied the consequent formula to examine the reported experimental results of single-molecule chiroptical responses under discussion in the recent past. The artifacts are theoretically suggested to be sensitive to the incident direction of elliptically polarized light and to the oriented systems, the ellipticity, and the orientation of ellipse. The mixed state has little, if any, effect when the polarization state distribution is narrow.

  4. Broadband circularly polarizing dichroism with high efficient plasmonic helical surface.

    Science.gov (United States)

    Hu, Jingpei; Zhao, Xiaonan; Li, Ruibin; Zhu, Aijiao; Chen, Linghua; Lin, Yu; Cao, Bing; Zhu, Xiaojun; Wang, Chinhua

    2016-05-16

    We propose and experimentally demonstrate a broadband and high efficient circularly polarizing dichroism using a simple single-cycle and single-helical plasmonic surface array arranged in square lattice. Two types of helical surface structures (partially or completely covered with a gold film) are investigated. It is shown that the circular polarization dichroism in the mid-IR range (3µm - 5µm) can reach 80% (when the surface is partially covered with gold) or 65% (when the surface is completely covered with gold) with a single-cycle and single-helical surface. Experimental fabrications of the proposed helical plasmonic surface are implemented with direct 3D laser writing followed by electron beam evaporation deposition of gold. The experimental evaluations of the circular polarization dichroism are in excellent agreement with the simulation. The proposed helical surface structure is of advantages of easy-fabrication, high-dichroism and scalable to other frequencies as a high efficient broadband circular polarizer.

  5. SIMULTANEOUS MEASUREMENT OF CIRCULAR DICHROISM AND FLUORESCENCE POLARIZATION ANISOTROPY.

    Energy Technology Data Exchange (ETDEWEB)

    SUTHERLAND,J.C.

    2002-01-19

    Circular dichroism and fluorescence polarization anisotropy are important tools for characterizing biomolecular systems. Both are used extensively in kinetic experiments involving stopped- or continuous flow systems as well as titrations and steady-state spectroscopy. This paper presents the theory for determining circular dichroism and fluorescence polarization anisotropy simultaneously, thus insuring the two parameters are recorded under exactly the same conditions and at exactly the same time in kinetic experiments. The approach to measuring circular dichroism is that used in almost all conventional dichrographs. Two arrangements for measuring fluorescence polarization anisotropy are described. One uses a single fluorescence detector and signal processing with a lock-in amplifier that is similar to the measurement of circular dichroism. The second approach uses classic ''T'' format detection optics, and thus can be used with conventional photon-counting detection electronics. Simple extensions permit the simultaneous measurement of the absorption and excitation intensity corrected fluorescence intensity.

  6. Circular dichroism induced by Fano resonances in planar chiral oligomers

    CERN Document Server

    Hopkins, Ben; Miroshnichenko, Andrey E; Kivshar, Yuri S

    2016-01-01

    We present a general theory of circular dichroism induced in planar chiral nanostructures with rotational symmetry. It is demonstrated, analytically, that the handedness of the incident field's polarization can control whether a nanostructure induces either absorption or scattering losses, even when the total loss (extinction) is polarization-independent. We then show that this effect is a consequence of modal interference so that strong circular dichroism in absorption and scattering can be engineered by combining Fano resonances with chiral nanoparticle clusters.

  7. Modeling Electronic Circular Dichroism within the Polarizable Embedding Approach

    DEFF Research Database (Denmark)

    Nørby, Morten S; Olsen, Jógvan Magnus Haugaard; Steinmann, Casper

    2017-01-01

    We present a systematic investigation of the key components needed to model single chromophore electronic circular dichroism (ECD) within the polarizable embedding (PE) approach. By relying on accurate forms of the embedding potential, where especially the inclusion of local field effects...... sampling. We show that a significant number of snapshots are needed to avoid artifacts in the calculated electronic circular dichroism parameters due to insufficient configurational sampling, thus highlighting the efficiency of the PE model....

  8. Circular dichroism beamline B23 at the Diamond Light Source.

    Science.gov (United States)

    Hussain, Rohanah; Jávorfi, Tamás; Siligardi, Giuliano

    2012-01-01

    Synchrotron radiation circular dichroism (SRCD) is a well established technique in structural biology. The first UV-VIS beamline, dedicated to circular dichroism, at Diamond Light Source Ltd, a third-generation synchrotron facility in south Oxfordshire, UK, has recently become operational and it is now available for the user community. Herein the main characteristics of the B23 SRCD beamline, the ancillary facilities available for users, and some of the recent advances achieved are summarized.

  9. A Vibrational Circular Dichroism Microsampling Accessory: Mapping Enhanced Vibrational Circular Dichroism in Amyloid Fibril Films.

    Science.gov (United States)

    Lu, Xuefang; Li, Honggang; Nafie, Jordan W; Pazderka, Tomáš; Pazderková, Markéta; Dukor, Rina K; Nafie, Laurence A

    2017-06-01

    We report the first vibrational circular dichroism (VCD) measurement of spatial heterogeneity in a sample using infrared (IR) microsampling. Vibrational circular dichroism spectra are typically measured using a standard IR cell with an IR beam diameter of 10 mm or greater making it impossible to investigate the spatial heterogeneity of a solid film sample. We have constructed a VCD sampling assembly with either 3 mm or 1 mm spatial resolution. An XY-translation stage was used to measure spectra at different spatial locations producing IR and VCD maps of the sample. In addition, a rotating sample stage was employed using a dual photoelastic modulator (PEM) setup to suppress artifacts due to linear birefringence in solid-phase or film samples. Infrared and VCD mapping of an insulin fibril film has been carried out at both 3 and 1 mm spatial resolution, and lysozyme films were mapped at 1 mm resolution. The IR spectra of different spots vary in intensity due primarily to sample thickness. The changes in the VCD intensity across the map largely correlate to corresponding changes in the IR map. Closer inspection of the insulin map revealed changes in the relative intensities of the VCD spectra not present in the parent IR spectra, which indicated differences in the degree of supramolecular chirality of the fibrils in the various spatial regions. For lysozyme films, in addition to different degrees of supramolecular chirality, reversal of the net fibril chirality was observed. The large signal-to-noise ratio observed at 1 mm resolution implies the feasibility of further increasing the spatial resolution by one or two orders of magnitude for protein fibril film samples.

  10. Enhanced circular dichroism via slow light in dispersive structured media

    DEFF Research Database (Denmark)

    Pedersen, Jesper Goor; Mortensen, Asger

    2007-01-01

    Circular dichroism (CD) is in widespread use as a means of determining enantiomeric excess. We show how slow-light phenomena in dispersive structured media allow for a reduction in the required optical path length of an order of magnitude. The same ideas may be used to enhance the sensitivity of CD...

  11. Circular Dichroism Method for Heat Capacity Determination of Proteins

    Science.gov (United States)

    Jones, Cecil L.; Bailey, Chris; Bheemarti, Kiran Kumar

    2006-01-01

    Circular dichroism spectroscopy was used to measure the thermal unfolding of bovine pancreatic ribonuclease A (RNase A) with various concentrations of guanidine hydrochloride (GuHCl). A red shift in transition midpoint temperatures, T[subscript m], occurred with increasing concentration of the strong protein denaturant. van Hoff enthalpy changes,…

  12. Visible Spectrum Circular Dichroism in Extrinsic Chirality Metamaterials

    CERN Document Server

    Lee, Seoungjun; Feng, Cheng; Jiao, Jiao; Khan, Ashfaq; Li, Lin

    2012-01-01

    We present the new planar extrinsic chirality metamaterial (ECM) design that manifests giant circular dichroism (CD) in the visible spectrum range rather than usual near-infrared and terahertz range. Effects of incident beam angles and meta-molecules unit sizes on the CD spectrums were theoretically analyzed; Physical mechanism was illustrated in new figures of asymmetrical current excitation in neighboring unit cells.

  13. Circular dichroism in photoelectron images from aligned nitric oxide molecules.

    Science.gov (United States)

    Sen, Ananya; Pratt, S T; Reid, K L

    2017-07-07

    We have used velocity map photoelectron imaging to study circular dichroism of the photoelectron angular distributions (PADs) of nitric oxide following two-color resonance-enhanced two-photon ionization via selected rotational levels of the A (2)Σ(+), v(')=0 state. By using a circularly polarized pump beam and a counter-propagating, circularly polarized probe beam, cylindrical symmetry is preserved in the ionization process, and the images can be reconstructed using standard algorithms. The velocity map imaging set up enables individual ion rotational states to be resolved with excellent collection efficiency, rendering the measurements considerably simpler to perform than previous measurements conducted with a conventional photoelectron spectrometer. The results demonstrate that circular dichroism is observed even when cylindrical symmetry is maintained, and serve as a reminder that dichroism is a general feature of the multiphoton ionization of atoms and molecules. The observed PADs are in good agreement with calculations based on parameters extracted from previous experimental results obtained by using a time-of-flight electron spectrometer.

  14. Determination of absolute configuration of an isopimarane-type diterpenoid by experimental and theoretical electronic circular dichroism and vibrational circular dichroism

    Science.gov (United States)

    Wang, Zhi-Qiang; Wu, Cheng-Jun; Wang, Zhen-Hui; Huang, Chao; Huang, Jian; Wang, Jin-Hui; Sun, Tie-Min

    2017-10-01

    In this study, the stereochemistry of a new isopimarane-type diterpenoid isolated from the Callicarpa macrophylla Vahl, Callicapene M3, was studied by experimental electronic circular dichroism and vibrational circular dichroism with the aid of TDDFT theoretical calculations. The good consistence between the experimental and simulated circular dichroism has clearly confirmed the absolute configuration of the title compound as (4S, 5S, 9S, 10S, 13S, 14S)-14α-hydroxy-7,15-isopimaradien-18-oic acid.

  15. X-ray natural circular dichroism in copper metaborate

    Energy Technology Data Exchange (ETDEWEB)

    Ovchinnikova, E. N. [Moscow State University (Russian Federation); Rogalev, A.; Wilhelm, F. [European Synchrotron Radiation Facility (France); Kozlovskaya, K. A.; Oreshko, A. P., E-mail: ap.oreshko@physics.msu.ru [Moscow State University (Russian Federation); Dmitrienko, V. E. [Russian Academy of Sciences, Shubnikov Institute of Crystallography (Russian Federation)

    2016-07-15

    The local electronic structure of copper ions in a copper metaborate CuB{sub 2}O{sub 4} crystal is studied on the ESRF synchrotron using X-ray absorption polarization-dependent spectroscopy. The X-ray natural circular dichroism near the K absorption edge of copper is measured in the direction that is perpendicular to crystal axis c. The data obtained indicate the presence of hybridized p–d electronic states of copper. Theoretical calculations are used to separate the contributions of the two crystallographically nonequivalent positions of copper atoms in the unit cell of CuB{sub 2}O{sub 4} to the absorption and X-ray circular dichroism spectra of the crystal.

  16. Electronic and vibrational circular dichroism spectra of (R)-(-)-apomorphine

    Energy Technology Data Exchange (ETDEWEB)

    Abbate, Sergio, E-mail: abbate@med.unibs.it [Dipartimento di Scienze Biomediche e Biotecnologie, Universita di Brescia, Viale Europa 11, 25123 Brescia (Italy); CNISM, Consorzio Interuniversitario Scienze Fisiche della Materia, Via della Vasca Navale 84, 00146 Roma (Italy); Longhi, Giovanna; Lebon, France [Dipartimento di Scienze Biomediche e Biotecnologie, Universita di Brescia, Viale Europa 11, 25123 Brescia (Italy); CNISM, Consorzio Interuniversitario Scienze Fisiche della Materia, Via della Vasca Navale 84, 00146 Roma (Italy); Tommasini, Matteo [Dipartimento di Chimica, Materiali e Ingegneria Chimica ' G. Natta' , Politecnico di Milano, Piazza Leonardo da Vinci 32, 20133 Milano (Italy); Consorzio Interuniversitario per la Scienza e Tecnologia dei Materiali (INSTM), Unita di Ricerca del Politecnico di Milano (Dip. CMIC), Piazza Leonardo da Vinci 32, 20133 Milano (Italy)

    2012-09-11

    Highlights: Black-Right-Pointing-Pointer ECD and VCD Spectra of (R)-(-)-apomorphine measured in various solvents. Black-Right-Pointing-Pointer DFT calculations allow to study the protonation state and conformations. Black-Right-Pointing-Pointer Contributions from catechol OH vibrations to the VCD spectra is studied. -- Abstract: Apomorphine is a chiral drug molecule; notwithstanding its extraordinary importance, little attention has been paid to the characterization of its chiroptical properties. Here we report on its electronic circular dichroism (ECD) spectra, recorded in methanol and water, and vibrational circular dichroism (VCD) in methanol and dimethyl sulfoxide (DMSO) solutions. Density functional theory (DFT) calculations have allowed us to interpret the spectra and to evaluate the role of possible conformations, charge-states and interactions with counter ions.

  17. Amplifying vibrational circular dichroism by manipulation of the electronic manifold.

    Science.gov (United States)

    Domingos, Sérgio R; Panman, Matthijs R; Bakker, Bert H; Hartl, Frantisek; Buma, Wybren J; Woutersen, Sander

    2012-01-11

    Vibrational circular dichroism is a powerful technique to study the stereochemistry of chiral molecules, but often suffers from small signal intensities. Electrochemical modulation of the energies of the electronically excited state manifold is now demonstrated to lead to an order of magnitude enhancement of the differential absorption. Quantum-chemical calculations show that increased mixing between ground and excited states is at the origin of this amplification. This journal is © The Royal Society of Chemistry 2012

  18. Emitter-site selective photoelectron circular dichroism of trifluoromethyloxirane

    OpenAIRE

    Ilchen, M.; Hartmann, G.; Schmidt, Ph.; Wolf, T. J. A.; Ehresmann, A.; Moeller, S.; Knie, A.; Demekhin, Ph. V.; Rupprecht, P.; Artemyev, A. N.; Coffee, R N; Li, Z; Ohldag, H.; Ogasawara, H.; Osipov, T.

    2017-01-01

    The angle-resolved inner-shell photoionization of R-trifluoromethyloxirane, C3H3F3O, is studied experimentally and theoretically. Thereby, we investigate the photoelectron circular dichroism (PECD) for nearly-symmetric O 1s and F 1s electronic orbitals, which are localized on different molecular sites. The respective dichroic $\\beta_{1}$ and angular distribution $\\beta_{2}$ parameters are measured at the photoelectron kinetic energies from 1 to 16 eV by using variably polarized synchrotron ra...

  19. DichroCalc--circular and linear dichroism online.

    Science.gov (United States)

    Bulheller, Benjamin M; Hirst, Jonathan D

    2009-02-15

    Circular dichroism (CD) is widely used in studies of protein folding. The CD spectrum of a protein can be estimated from its structure alone, using the well-established matrix method. In the last decade, a related spectroscopy, linear dichroism (LD), has been increasingly applied to study the orientation of proteins in solution. However, matrix method calculations of LD spectra have not been presented before. DichroCalc makes both CD and LD calculations available in an easy-to-use fashion. DichroCalc can be used without registration and calculates CD and LD spectra using a variety of matrix method parameters. PDB files can be uploaded as input or retrieved via their PDB code and a Perl-based parser is offered for easy handling of PDB files. http://comp.chem.nottingham.ac.uk/dichrocalc and http://comp.chem.nottingham.ac.uk/parsepdb.

  20. Twisting dirac fermions: circular dichroism in bilayer graphene

    Science.gov (United States)

    Suárez Morell, E.; Chico, Leonor; Brey, Luis

    2017-09-01

    Twisted bilayer graphene is a chiral system which has been recently shown to present circular dichroism. In this work we show that the origin of this optical activity is the rotation of the Dirac fermions’ helicities in the top and bottom layer. Starting from the Kubo formula, we obtain a compact expression for the Hall conductivity that takes into account the dephasing of the electromagnetic field between the top and bottom layers and gathers all the symmetries of the system. Our results are based in both a continuum and a tight-binding model, and they can be generalized to any two-dimensional Dirac material with a chiral stacking between layers.

  1. Magnetic Circular Dichroism in X-Ray Emission from Ferromagnets

    Science.gov (United States)

    Inami, Toshiya

    2017-09-01

    The existence of novel magnetic circular dichroism in core-level x-ray emission is reported. By means of circular polarization analysis, the dichroic effect of the Fe Kα 1 emission spectrum is measured on an Fe single crystal. The observed dichroic effect (12%) is remarkably large, if one takes into account the small dichroic effect (about 0.5%) in the conventional K -edge absorption spectroscopy of 3 d transition metal elements. The mechanism is ascribed to exchange splitting of the 2 p level possessing large spin-orbit coupling. This new magnetooptical effect enables us to explore a variety of new research subjects in the magnetism of 3 d transition metals and their compounds by fully utilizing its large dichroic effect, the true bulk sensitivity of hard x rays, and the element selectivity of core-level spectroscopy.

  2. Characterization of Quadruplex DNA Structure by Circular Dichroism.

    Science.gov (United States)

    Del Villar-Guerra, Rafael; Gray, Robert D; Chaires, Jonathan B

    2017-03-02

    Circular dichroism (CD) is a phenomenon that arises from the differential absorption of left- and right-handed circularly polarized light, and may be seen with optically active molecules. CD spectroscopy provides useful spectral signatures for biological macromolecules in solution, and provides low-resolution structural information about macromolecular conformation. CD spectroscopy is particularly useful for monitoring conformational changes in macromolecules upon environmental perturbations. G-quadruplex structures show unique CD spectral signatures, and CD is an important tool for characterizing their formation and global structure. This protocol offers step-by-step methods for determining reliable and reproducible CD spectra of quadruplex structures and normalizing the spectra for presentation. CD spectra properly normalized with respect to quadruplex concentration and path length are required to facilitate accurate comparison of results among laboratories. The standard operating procedures proposed are recommended to make such comparison accurate and informative. © 2017 by John Wiley & Sons, Inc. Copyright © 2017 John Wiley & Sons, Inc.

  3. PCDDB: new developments at the Protein Circular Dichroism Data Bank.

    Science.gov (United States)

    Whitmore, Lee; Miles, Andrew John; Mavridis, Lazaros; Janes, Robert W; Wallace, B A

    2017-01-04

    The Protein Circular Dichroism Data Bank (PCDDB) has been in operation for more than 5 years as a public repository for archiving circular dichroism spectroscopic data and associated bioinformatics and experimental metadata. Since its inception, many improvements and new developments have been made in data display, searching algorithms, data formats, data content, auxillary information, and validation techniques, as well as, of course, an increase in the number of holdings. It provides a site (http://pcddb.cryst.bbk.ac.uk) for authors to deposit experimental data as well as detailed information on methods and calculations associated with published work. It also includes links for each entry to bioinformatics databases. The data are freely available to accessors either as single files or as complete data bank downloads. The PCDDB has found broad usage by the structural biology, bioinformatics, analytical and pharmaceutical communities, and has formed the basis for new software and methods developments. © The Author(s) 2016. Published by Oxford University Press on behalf of Nucleic Acids Research.

  4. Generation of bright circularly-polarized extreme ultraviolet high harmonics for magnetic circular dichroism spectroscopy

    CERN Document Server

    Kfir, Ofer; Turgut, Emrah; Knut, Ronny; Zusin, Dmitriy; Popmintchev, Dimitar; Popmintchev, Tenio; Nembach, Hans; Shaw, Justin M; Fleicher, Avner; Kapteyn, Henry; Murnane, Margaret; Cohen, Oren

    2014-01-01

    Circularly-polarized extreme UV and X-ray radiation provides valuable access to the structural, electronic and magnetic properties of materials. To date, such experiments have been possible only using large-scale free-electron lasers or synchrotrons. Here we demonstrate the first bright extreme UV circularly-polarized high harmonics and use this new light source for magnetic circular dichroism measurements at the M-shell absorption edges of cobalt. This work paves the way towards element-specific imaging and spectroscopy of multiple elements simultaneously in magnetic and other chiral media with very high spatio-temporal resolution, all on a tabletop.

  5. Enantioselective femtosecond laser photoionization spectrometry of limonene using photoelectron circular dichroism

    NARCIS (Netherlands)

    Rafiee Fanood, M.M.; Janssen, M.H.M.; Powis, I.

    2015-01-01

    Limonene is ionized by circularly polarized 420 nm femtosecond laser pulses. Ion mass and photoelectron energy spectra identify the dominant (2 + 1) multiphoton ionization mechanism, aided by TDDFT calculations of the Rydberg excitations. Photoelectron circular dichroism measurements on pure

  6. Absolute configuration assignment of (+)-fluralaner using vibrational circular dichroism.

    Science.gov (United States)

    Kong, John; Joyce, Leo A; Liu, Jinchu; Jarrell, Tiffany M; Culberson, J Chris; Sherer, Edward C

    2017-12-01

    The absolute configurations of the separated enantiomers of fluralaner, a racemic animal health product used to prevent fleas and ticks, have been assigned using vibrational circular dichroism (VCD). The crystallographic structure of the active enantiomer (+)-fluralaner has previously been shown to have the (S) configuration using small molecule crystallography. We sought a faster analytical method to determine the absolute configuration of the separated enantiomers. When comparing the measured IR (infrared) and VCD spectra, it is apparent that the amide carbonyl groups appear in the IR but are nearly absent in the VCD. Computational work to calculate the VCD and IR using in vacuo models, implicit solvation, and explicitly solvated complexes has implicated conformational averaging of the carbonyl VCD intensities. © 2017 Wiley Periodicals, Inc.

  7. Using circular dichroism spectra to estimate protein secondary structure

    Science.gov (United States)

    Greenfield, Norma J.

    2009-01-01

    Circular dichroism (CD) is an excellent tool for rapid determination of the secondary structure and folding properties of proteins that have been obtained using recombinant techniques or purified from tissues. The most widely used applications of protein CD are to determine whether an expressed, purified protein is folded, or if a mutation affects its conformation or stability. In addition, it can be used to study protein interactions. This protocol details the basic steps of obtaining and interpreting CD data and methods for analyzing spectra to estimate the secondary structural composition of proteins. CD has the advantage that it is that measurements may be made on multiple samples containing 20 µg or less of proteins in physiological buffers in a few hours. However, it does not give the residue-specific information that can be obtained by X-ray crystallography or NMR. PMID:17406547

  8. Dielectric tuned circular dichroism of L-shaped plasmonic metasurface

    Science.gov (United States)

    Qu, Yu; Zhang, Zhidong; Fu, Tong; Wang, Gang; Wang, Tiankun; Wang, Mingyan; Bai, Yu; Zhang, Zhongyue

    2017-12-01

    In this paper, a dielectric layer is introduced to tune circular dichroism (CD) of chiral plasmonic metasurfaces. The dielectric layer is used to control the optical phase of electric diploes in Born–Kuhn configurations. To prove our assumption, an L-shaped plasmonic metasurface consisting of two metallic slices is prepared by glancing angle deposition, and then an SiO2 slice is deposited on one arm of the L-shaped metasurface. Experimental results reveal that CD of the L-shaped plasmonic metasurface can be tuned by the thickness of the SiO2 slice. These findings not only contribute to a better understanding of the CD physical mechanism, but also can be used in nanophotonic metasurfaces because of the concise fabrication process.

  9. G-quadruplex secondary structure from circular dichroism spectroscopy.

    Science.gov (United States)

    Del Villar-Guerra, Rafael; Trent, John O; Chaires, Jonathan B

    2017-10-26

    A curated library of circular dichroism spectra of 23 G-quadruplexes of known structure was built and analyzed. The goal of this study was to use this reference library to develop an algorithm to derive quantitative estimates of the secondary structure content of quadruplexes from their experimental CD spectra. Principal component analysis and singular value decomposition were used to characterize the reference spectral library. CD spectra were successfully fit to obtain estimates of the amounts of base steps in anti-anti, syn-anti or anti-syn conformations, in diagonal or lateral loops or in other conformations. The results show that CD spectra of nucleic acids can be analyzed to obtain quantitative structural information about secondary structure content in an analogous way to methods used to analyze protein CD spectra. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Electrically controlled magnetic circular dichroism and Faraday rotation in graphene

    Science.gov (United States)

    Kuzmenko, Alexey; Poumirol, Jean-Marie; Liu, Peter Q. Liu; Slipchenko, Tetiana; Nikitin, Alexey; Martin-Moreno, Luis; Faist, Jerome

    Magnetic circular dichroism (MCD) and Faraday rotation (FR) are the fundamental phenomena of great practical importance arising from the breaking of the time reversal symmetry by a magnetic field. In most materials the strength and the sign of these effects can be only controlled by the field value and its orientation. Using broadband terahertz magneto-electro-optical spectroscopy, we demonstrate that in graphene both the MCD and the FR can be modulated in intensity, tuned in frequency and, importantly, inverted using only electrostatic doping at a fixed magnetic field due to the unique properties of the Dirac fermions. Our results indicate the fundamental possibility of compact, efficient, electrically invertible and wavelength-tunable non-reciprocal passive terahertz elements based on graphene operating at ambient temperature.

  11. Supramolecular Chemistry: Induced Circular Dichroism to Study Host-Guest Geometry

    Science.gov (United States)

    Mendicuti, Francisco; Gonzalez-Alvarez, Maria Jose

    2010-01-01

    In this laboratory experiment, students obtain information about the structure of a host-guest complex from the interpretation of circular dichroism measurements. The value and sign of the induced circular dichroism (ICD) on an achiral chromophore guest when it complexes with a cyclodextrin can be related to the guest penetration and its…

  12. Microsecond Time-Resolved Circular Dichroism of Rhodopsin Photointermediates†

    Science.gov (United States)

    Thomas, Yiren Gu; Szundi, Istvan; Lewis, James W.; Kliger, David S.

    2009-01-01

    Time-resolved circular dichroism measurements, over a spectral range from 300 to 700 nm, were made at delays of 5, 100 and 500 μs after room temperature photoexcitation of bovine rhodopsin in lauryl maltoside suspension. The purpose was to provide more structural information about intermediate states in the activation of rhodopsin and other G protein-coupled receptors. In particular, information was sought about photointermediates that are isochromic or nearly isochromic in their unpolarized absorbance. The circular dichroism spectrum of lumirhodopsin, obtained after correcting the 5 μs difference CD data for the rhodopsin bleached, was in reasonable agreement with the lumirhodopsin CD spectrum obtained previously by thermal trapping at -76°C. Similarly, the metarhodopsin II spectrum obtained at 500 μs delay was also in agreement with the results of previous work on the temperature trapped form of metarhodopsin II. However, the CD of the mixture formed at 100 μs delay after photoexcitation, whose only visible absorbing component is lumirhodopsin, could not be accounted for near 480 nm in terms of the initially formed, 5 μs lumirhodopsin CD spectrum. Thus, the CD spectrum of lumirhodopsin changes on the time scale from 5 to 100 μs, showing reduced rotational strength in its visible band, possibly associated with either a process responsible for a small spectral shift that occurs in the lumirhodopsin absorbance spectrum at earlier times or the Schiff base deprotonation-reprotonation which occurs during equilibration of lumirhodopsin with the Meta I380 photointermediate. Either explanation suggests a chromophore conformation change closely associated with deprotonation which could be the earliest direct trigger of activation. PMID:19905009

  13. Three-dimensional structural imaging of starch granules by second-harmonic generation circular dichroism.

    Science.gov (United States)

    Zhuo, G-Y; Lee, H; Hsu, K-J; Huttunen, M J; Kauranen, M; Lin, Y-Y; Chu, S-W

    2014-03-01

    Chirality is one of the most fundamental and essential structural properties of biological molecules. Many important biological molecules including amino acids and polysaccharides are intrinsically chiral. Conventionally, chiral species can be distinguished by interaction with circularly polarized light, and circular dichroism is one of the best-known approaches for chirality detection. As a linear optical process, circular dichroism suffers from very low signal contrast and lack of spatial resolution in the axial direction. It has been demonstrated that by incorporating nonlinear interaction with circularly polarized excitation, second-harmonic generation circular dichroism can provide much higher signal contrast. However, previous circular dichroism and second-harmonic generation circular dichroism studies are mostly limited to probe chiralities at surfaces and interfaces. It is known that second-harmonic generation, as a second-order nonlinear optical effect, provides excellent optical sectioning capability when combined with a laser-scanning microscope. In this work, we combine the axial resolving power of second-harmonic generation and chiral sensitivity of second-harmonic generation circular dichroism to realize three-dimensional chiral detection in biological tissues. Within the point spread function of a tight focus, second-harmonic generation circular dichroism could arise from the macroscopic supramolecular packing as well as the microscopic intramolecular chirality, so our aim is to clarify the origins of second-harmonic generation circular dichroism response in complicated three-dimensional biological systems. The sample we use is starch granules whose second-harmonic generation-active molecules are amylopectin with both microscopic chirality due to its helical structure and macroscopic chirality due to its crystallized packing. We found that in a starch granule, the second-harmonic generation for right-handed circularly polarized excitation is

  14. Angular momentum-induced circular dichroism in non-chiral nanostructures.

    Science.gov (United States)

    Zambrana-Puyalto, Xavier; Vidal, Xavier; Molina-Terriza, Gabriel

    2014-09-12

    Circular dichroism, that is, the differential absorption of a system to left and right circularly polarized light, is one of the only techniques capable of providing morphological information of certain samples. In biology, for instance, circular dichroism spectroscopy is widely used to study the structure of proteins. More recently, it has also been used to characterize metamaterials and plasmonic structures. Typically, circular dichorism can only be observed in chiral objects. Here we present experimental results showing that a non-chiral sample such as a subwavelength circular nanoaperture can produce giant circular dichroism when a vortex beam is used to excite it. These measurements can be understood by studying the symmetries of the sample and the total angular momentum that vortex beams carry. Our results show that circular dichroism can provide a wealth of information about the sample when combined with the control of the total angular momentum of the input field.

  15. Some aspects of vacuum ultraviolet radiation physics

    CERN Document Server

    Damany, Nicole; Vodar, Boris

    2013-01-01

    Some Aspects of Vacuum Ultraviolet Radiation Physics presents some data on the state of research in vacuum ultraviolet radiation in association with areas of physics. Organized into four parts, this book begins by elucidating the optical properties of solids in the vacuum ultraviolet region (v.u.v.), particularly the specific methods of determination of optical constants in v.u.v., the properties of metals, and those of ionic insulators. Part II deals with molecular spectroscopy, with emphasis on the spectra of diatomic and simple polyatomic molecules, paraffins, and condensed phases. Part III

  16. Circular dichroism in laser-assisted proton-hydrogen collisions

    Science.gov (United States)

    Niederhausen, Thomas; Feuerstein, Bernold; Thumm, Uwe

    2004-08-01

    We investigate the effects of a strong laser field on the dynamics of electron capture and emission in ion-atom collisions within a reduced dimensionality model of the scattering system in which the motion of the active electron and the laser electric field vector are confined to the scattering plane. We examine the probabilities for electron capture and ionization as a function of the laser intensity, the projectile impact parameter b , and the laser phase ϕ that determines the orientation of the laser electric field with respect to the internuclear axis at the time of closest approach between target and projectile. Our results for the b -dependent ionization and capture probabilities show a strong dependence on both ϕ and the helicity of the circularly polarized laser light. For intensities above 5×1012W/cm2 our model predicts a noticeable circular dichroism in the capture probability for slow proton-hydrogen collisions, which persists after averaging over ϕ . Capture and electron emission probabilities defer significantly from results for laser-unassisted collisions. Furthermore, we find evidence for a charge-resonance-enhanced ionization mechanism that may enable the measurement of the absolute laser phase ϕ .

  17. Vacuum-Ultraviolet Photovoltaic Detector.

    Science.gov (United States)

    Zheng, Wei; Lin, Richeng; Ran, Junxue; Zhang, Zhaojun; Ji, Xu; Huang, Feng

    2018-01-23

    Over the past two decades, solar- and astrophysicists and material scientists have been researching and developing new-generation semiconductor-based vacuum ultraviolet (VUV) detectors with low power consumption and small size for replacing traditional heavy and high-energy-consuming microchannel-detection systems, to study the formation and evolution of stars. However, the most desirable semiconductor-based VUV photovoltaic detector capable of achieving zero power consumption has not yet been achieved. With high-crystallinity multistep epitaxial grown AlN as a VUV-absorbing layer for photogenerated carriers and p-type graphene (with unexpected VUV transmittance >96%) as a transparent electrode to collect excited holes, we constructed a heterojunction device with photovoltaic detection for VUV light. The device exhibits an encouraging VUV photoresponse, high external quantum efficiency (EQE) and extremely fast tempera response (80 ns, 10 4 -10 6 times faster than that of the currently reported VUV photoconductive devices). This work has provided an idea for developing zero power consumption and integrated VUV photovoltaic detectors with ultrafast and high-sensitivity VUV detection capability, which not only allows future spacecraft to operate with longer service time and lower launching cost but also ensures an ultrafast evolution of interstellar objects.

  18. Enhancing circular dichroism by super chiral hot spots from a chiral metasurface with apexes

    Science.gov (United States)

    Wang, Zeng; Teh, Bing Hong; Wang, Yue; Adamo, Giorgio; Teng, Jinghua; Sun, Handong

    2017-05-01

    Manipulating light spin (or circular polarization) is an important research field and may find broad applications from sensors, display technology, to quantum computing and communication. To this end, planar metasurfaces with larger circular dichroism are strongly demanded. However, current planar chiral metasurface structures suffer from either fabrication challenge, especially from near-infrared to visible spectrum, or insufficient circular dichroism. Here, we report a chiral metasurface composed of achiral nanoholes which allow for precisely creating apexes in the designed structure. Our investigation indicates that the apexes act as super chiral hot spots and enable the highly concentrated near-field optical chirality leading to a remarkable enhancement of circular dichroism in the far-field. A 4-fold enhancement of the circular dichroism and a strong optical activity of ˜15 degrees have been experimentally achieved. Besides the enhanced chirality, our design genuinely overcomes the nanofabrication challenge faced in existing planar chiral metasurfaces.

  19. A computational protocol for the study of circularly polarized phosphorescence and circular dichroism in spin-forbidden absorption

    DEFF Research Database (Denmark)

    Kaminski, Maciej; Cukras, Janusz; Pecul, Magdalena

    2015-01-01

    We present a computational methodology to calculate the intensity of circular dichroism (CD) in spinforbidden absorption and of circularly polarized phosphorescence (CPP) signals, a manifestation of the optical activity of the triplet–singlet transitions in chiral compounds. The protocol is based...... on the response function formalism and is implemented at the level of time-dependent density functional theory. It has been employed to calculate the spin-forbidden circular dichroism and circularly polarized phosphorescence signals of valence n - p* and n ’ p* transitions, respectively, in several chiral enones...

  20. Magnetic circular dichroism of porphyrin lanthanide M3+ complexes.

    Science.gov (United States)

    Andrushchenko, Valery; Padula, Daniele; Zhivotova, Elena; Yamamoto, Shigeki; Bouř, Petr

    2014-10-01

    Lanthanide complexes exhibit interesting spectroscopic properties yielding many applications as imaging probes, natural chirality amplifiers, and therapeutic agents. However, many properties are not fully understood yet. Therefore, we applied magnetic circular dichroism (MCD) spectroscopy, which provides enhanced information about the underlying electronic structure to a series of lanthanide compounds. The metals in the M(3+) state included Y, La, Eu, Tb, Dy, Ho, Er, Tm, Yb, and Lu; the spectra were collected for selected tetraphenylporphin (TPP) and octaethylporphin (OEP) complexes in chloroform. While the MCD and UV-VIS absorption spectra were dominated by the porphyrin signal, metal binding significantly modulated them. MCD spectroscopy was found to be better suited to discriminate between various species than absorption spectroscopy alone. The main features and trends in the lanthanide series observed in MCD and absorption spectra of the complexes could be interpreted at the Density Functional Theory (DFT) level, with effective core potentials on metal nuclei. The sum over state (SOS) method was used for simulation of the MCD intensities. The combination of the spectroscopy and quantum-chemical computations is important for understanding the interactions of the metals with the organic compounds. © 2014 Wiley Periodicals, Inc.

  1. Absolute configuration of verticillane diterpenoids by vibrational circular dichroism.

    Science.gov (United States)

    Cerda-García-Rojas, Carlos M; García-Gutiérrez, Hugo A; Hernandez-Hernandez, Juan D; Roman-Marín, Luisa U; Joseph-Nathan, Pedro

    2007-07-01

    Good agreement between theoretical and experimental vibrational circular dichroism curves of (1S,11S,12S)-(+)-verticilla-3E,7E-dien-12-ol (1) established the absolute configuration of this natural diterpene isolated from Bursera suntui. Molecular modeling of 1 was carried out using the Monte Carlo protocol followed by geometry optimization at the B3LYP 6-31G(d,p) level of theory. The 12-membered ring of 1 was found in a single preferred chair-chair-chair-chair conformation. In the six-membered ring a chair prevails over a distorted boat, and the C-OH bond rotation generates three predominant rotamers. Validation of the minimum energy conformation for 1 was achieved by comparison of theoretical and experimental infrared frequencies, vicinal 1H NMR coupling constants, and X-ray diffraction data. This study confirms that (+)-verticillol 1 isolated from Bursera species has the 1S,11S,12S absolute configuration that corresponds to the same enantiomeric series as verticillanes from Sciadopitys and Taxus, while verticillanes from Jackiella and Jungermannia have antipodal structures.

  2. Emitter-site-selective photoelectron circular dichroism of trifluoromethyloxirane

    Science.gov (United States)

    Ilchen, M.; Hartmann, G.; Rupprecht, P.; Artemyev, A. N.; Coffee, R. N.; Li, Z.; Ohldag, H.; Ogasawara, H.; Osipov, T.; Ray, D.; Schmidt, Ph.; Wolf, T. J. A.; Ehresmann, A.; Moeller, S.; Knie, A.; Demekhin, Ph. V.

    2017-05-01

    The angle-resolved inner-shell photoionization of R-trifluoromethyloxirane, C3H3F3O , is studied experimentally and theoretically. Thereby, we investigate the photoelectron circular dichroism (PECD) for nearly symmetric O 1 s and F 1 s electronic orbitals, which are localized on different molecular sites. The respective dichroic β1 and angular distribution β2 parameters are measured at the photoelectron kinetic energies from 1 to 16 eV by using variably polarized synchrotron radiation and velocity map imaging spectroscopy. The present experimental results are in good agreement with the outcome of ab initio electronic structure calculations. We report a sizable chiral asymmetry β1 of up to about 9% for the K -shell photoionization of oxygen atom. For the individual fluorine atoms, the present calculations predict asymmetries of similar size. However, being averaged over all fluorine atoms, it drops down to about 2%, as also observed in the present experiment. Our study demonstrates a strong emitter and site sensitivity of PECD in the one-photon inner-shell ionization of this chiral molecule.

  3. Surface plasmon resonance prism coupler for enhanced circular dichroism sensing.

    Science.gov (United States)

    Phan, Quoc-Hung; Lo, Yu-Lung; Huang, Chih-Ling

    2016-06-13

    A novel method for enhanced circular dichroism (CD) detection is proposed based on a surface plasmon resonance (SPR) prism coupler and a polarization scanning ellipsometry technique. An analytical model is derived to extract the CD and degree of polarization (DOP) properties of optical samples with and without scattering effects, respectively. The validity of the analytical model is confirmed by means of numerical simulations. The simulation results show that the proposed detection method has a sensitivity of 10-5~10-6 RIU (refractive index unit) for refractive indices in the range of 1.32~1.36 and 1.3100~1.3118. The practical feasibility of the proposed method is demonstrated by the experimental results for the sensitivity of the CD with the chlorophyllin samples with/without scattering effect. It is shown that for both types of sample, the extracted CD value increases linearly with the chlorophyll concentration over the considered range. In general, the results obtained in this study show that the measured CD response is highly sensitive to the polarization scanning angle. Consequently, the potential of polarization scanning ellipsometry for high-resolution CD detection is confirmed.

  4. Application of circular dichroism and magnetic circular dichroism for assessing biopharmaceuticals formulations photo-stability and small ligands binding properties.

    Science.gov (United States)

    Longo, Edoardo; Hussain, Rohanah; Siligardi, Giuliano

    2015-03-01

    Synchrotron radiation circular dichroism (SRCD) is a powerful tool for photo-stability assessment of proteins. Recently our research has been interested in applying SRCD to develop screening methodologies for accelerated photo-stability assessment of monoclonal antibody formulations. Despite it was proven to be reliable and applicable within a wide range of salts and excipients containing solutions, the presence of far-UV (<260nm) strong absorbing species (e.g., sodium chloride, histidine, arginine) in common formulations completely prevent the analysis. Herein, we propose a new method based on CD coupled with magnetic CD (MCD) to address the problem and offer an additional versatile tool for monitoring the photo-stability. This is done by assessing the stability of the samples by looking at the near-UV band, as well as giving insights in the denaturation mechanism. We applied this method to four mAbs formulations and correlated the results with dynamic light scattering data. Finally, we applied MCD in ligand interaction to key proteins such as lysozyme, comparing the human with the hen enzyme in the binding of N,N',N''-triacetylchitotriose. Copyright © 2015 The Authors. Published by Elsevier B.V. All rights reserved.

  5. Absolute configuration of an axially chiral sulfonate determined from its optical rotatory dispersion, electronic circular dichroism, and vibrational circular dichroism spectra.

    Science.gov (United States)

    Covington, Cody L; Raghavan, Vijay; Smuts, Jonathan P; Armstrong, Daniel W; Polavarapu, Prasad L

    2017-11-01

    The absolute configuration (AC) of an axially chiral sulfonate (aCSO), 3,5-dimethyl-2-(naphthalen-1-yl)-6-(naphthalen-1-yl)benzenesulfonate (labeled as aCSO5), was investigated using optical rotatory dispersion (ORD), electronic circular dichroism (ECD), and vibrational circular dichroism (VCD) spectroscopies. All three methods led to the same conclusion and the AC of aCSO5 is reliably determined to be (-)-(aR, aR), or conversely (+)-(aS, aS). © 2017 Wiley Periodicals, Inc.

  6. Structure and Absolute Configuration of Nyasol and Hinokiresinol via Synthesis and Vibrational Circular Dichroism Spectroscopy

    DEFF Research Database (Denmark)

    Lassen, Peter Rygaard

    2005-01-01

    The absolute configuration of the norlignan (+)-nyasol was determined to be S by comparison of the experimental vibrational circular dichroism data with first-principle calculations taking into account the eight lowest energy conformations. The established absolute configuration of (+)-nyasol...

  7. Experimental demonstration of the microscopic origin of circular dichroism in two-dimensional metamaterials.

    Science.gov (United States)

    Khanikaev, A B; Arju, N; Fan, Z; Purtseladze, D; Lu, F; Lee, J; Sarriugarte, P; Schnell, M; Hillenbrand, R; Belkin, M A; Shvets, G

    2016-06-22

    Optical activity and circular dichroism are fascinating physical phenomena originating from the interaction of light with chiral molecules or other nano objects lacking mirror symmetries in three-dimensional (3D) space. While chiral optical properties are weak in most of naturally occurring materials, they can be engineered and significantly enhanced in synthetic optical media known as chiral metamaterials, where the spatial symmetry of their building blocks is broken on a nanoscale. Although originally discovered in 3D structures, circular dichroism can also emerge in a two-dimensional (2D) metasurface. The origin of the resulting circular dichroism is rather subtle, and is related to non-radiative (Ohmic) dissipation of the constituent metamolecules. Because such dissipation occurs on a nanoscale, this effect has never been experimentally probed and visualized. Using a suite of recently developed nanoscale-measurement tools, we establish that the circular dichroism in a nanostructured metasurface occurs due to handedness-dependent Ohmic heating.

  8. Reversed Circular Dichroism of Isotropic Chiral Mediums with Negative Real permeability and permittivity

    OpenAIRE

    Lakhtakia, Akhlesh

    2002-01-01

    Negative real parts of the permittivity and permeability lead an isotropic chiral medium to exhibit circular dichroism that is reversed with respect to that exhibited by an identical medium but the real parts of whose permittivity and permeability are positive.

  9. Circular dichroism of cholesteric polymers and the orbital angular momentum of light

    CERN Document Server

    Löffler, W; Woerdman, J P

    2011-01-01

    We explore experimentally if the light's orbital angular momentum (OAM) interacts with chiral nematic polymer films. Specifically, we measure the circular dichroism of such a material using light beams with different OAM. We investigate the case of strongly focussed, non-paraxial light beams, where the spatial and polarization degrees of freedom are coupled. Within the experimental accuracy, we cannot find any influence of the OAM on the circular dichroism of the cholesteric polymer.

  10. DNA electronic circular dichroism on the inter-base pair scale

    DEFF Research Database (Denmark)

    Di Meo, Florent; Nørby, Morten Steen; Rubio-Magnieto, Jenifer

    2015-01-01

    A successful elucidation of the near-ultraviolet electronic circular dichroism spectrum of a short double-stranded DNA is reported. Time-dependent density functional theory methods are shown to accurately predict spectra and assign bands on the microscopic base-pair scale, a finding that opens...... the field for using circular dichroism spectroscopy as a sensitive nanoscale probe of DNA to reveal its complex interactions with the environment. (Chemical Equation Presented)....

  11. Theoretical Prediction of Vibrational Circular Dichroism of Hexoses in Linear Form

    Science.gov (United States)

    1992-06-01

    D. Zeroka, G. R. Famini , J. 0. Jensen, A. H. Carrieri, and C. F. Chabalowski, Theoreti- cal Prediction of Vibrational Circular Dichroism Spectra...Jensen, A. H. Carrieri, G. R. Famini , and C. F. Chabalowski, Theoreti- cal Prediction of Vibrational Circular Dichroism Spectra of Sugars, Summer 1990 U.S...1983), Chapter 3. 15. J. M. Leonard and G. R. Famini , A User’s Guide to the Molecular Modelling, Analysis, Display System (MMADS)", 2" ed., CRDEC-TR

  12. Investigation of Human Albumin-Induced Circular Dichroism in Dansylglycine

    Science.gov (United States)

    Graciani, Fernanda S.; Ximenes, Valdecir F.

    2013-01-01

    Induced circular dichroism (ICD), or induced chirality, is a phenomenon caused by the fixation of an achiral substance inside a chiral microenvironment, such as the hydrophobic cavities in proteins. Dansylglycine belongs to a class of dansylated amino acids, which are largely used as fluorescent probes for the characterization of the binding sites in albumin. Here, we investigated the ICD in dansylglycine provoked by its binding to human serum albumin (HSA). We found that the complexation of HSA with dansylglycine resulted in the appearance of an ICD band centred at 346 nm. Using this ICD signal and site-specific ligands of HSA, we confirmed that dansylglycine is a site II ligand. The intensity of the ICD signal was dependent on the temperature and revealed that the complexation between the protein and the ligand was reversible. The induced chirality of dansylglycine was susceptive to the alteration caused by the oxidation of the protein. A comparison was made between hypochlorous acid (HOCl) and hypobromous acid (HOBr), and revealed that site II in the protein is more susceptible to alteration provoked by the latter oxidant. These findings suggest the relevance of the aromatic amino acids in the site II, since HOBr is a more efficient oxidant of these residues in proteins than HOCl. The three-dimensional structure of HSA is pH-dependent, and different conformations have been characterised. We found that HSA in its basic form at pH 9.0, which causes the protein to be less rigid, lost the capacity to bind dansylglycine. At pH 3.5, HSA retained almost all of its capacity for binding to dansylglycine. Since the structure of HSA at pH 3.5 is expanded, separating the domain IIIA from the rest of the molecule, we concluded that this separation did not alter its binding capacity to dansylglycine. PMID:24146932

  13. Investigation of human albumin-induced circular dichroism in dansylglycine.

    Directory of Open Access Journals (Sweden)

    Fernanda S Graciani

    Full Text Available Induced circular dichroism (ICD, or induced chirality, is a phenomenon caused by the fixation of an achiral substance inside a chiral microenvironment, such as the hydrophobic cavities in proteins. Dansylglycine belongs to a class of dansylated amino acids, which are largely used as fluorescent probes for the characterization of the binding sites in albumin. Here, we investigated the ICD in dansylglycine provoked by its binding to human serum albumin (HSA. We found that the complexation of HSA with dansylglycine resulted in the appearance of an ICD band centred at 346 nm. Using this ICD signal and site-specific ligands of HSA, we confirmed that dansylglycine is a site II ligand. The intensity of the ICD signal was dependent on the temperature and revealed that the complexation between the protein and the ligand was reversible. The induced chirality of dansylglycine was susceptive to the alteration caused by the oxidation of the protein. A comparison was made between hypochlorous acid (HOCl and hypobromous acid (HOBr, and revealed that site II in the protein is more susceptible to alteration provoked by the latter oxidant. These findings suggest the relevance of the aromatic amino acids in the site II, since HOBr is a more efficient oxidant of these residues in proteins than HOCl. The three-dimensional structure of HSA is pH-dependent, and different conformations have been characterised. We found that HSA in its basic form at pH 9.0, which causes the protein to be less rigid, lost the capacity to bind dansylglycine. At pH 3.5, HSA retained almost all of its capacity for binding to dansylglycine. Since the structure of HSA at pH 3.5 is expanded, separating the domain IIIA from the rest of the molecule, we concluded that this separation did not alter its binding capacity to dansylglycine.

  14. Circular dichroism tensor of a triarylmethyl propeller in sodium chlorate crystals.

    Science.gov (United States)

    Bing, Yonghong; Selassie, David; Paradise, Ruthanne H; Isborn, Christine; Kramer, Nicholas; Sadilek, Martin; Kaminsky, Werner; Kahr, Bart

    2010-06-02

    In 1919, Perucca reported anomalous optical rotatory dispersion from chiral NaClO(3) crystals that were colored by having been grown from a solution containing an equilibrium racemic mixture of a triarylmethane dye (Perucca, E. Nuovo Cimento 1919, 18, 112-154). Perucca's chiroptical observations are apparently consistent with a resolution of the propeller-shaped dye molecules by NaClO(3) crystals. This implies that Perucca achieved the first enantioselective adsorption of a racemic mixture on an inorganic crystal, providing evidence of the resolution of a triarylmethyl propeller compound lacking bulky ortho substituents. Following the earlier report, NaClO(3) crystals dyed with aniline blue are described herein. The rich linear optical properties of (001), (110), and (111) sections of these mixed crystals are described via their absorbance spectra in polarized light as well as images related to linear dichroism, linear birefringence, circular dichroism, and anomalous circular extinction. The linear dichroism fixes the transition electric dipole moments in the aromatic plane with respect to the growth faces of the NaClO(3) cubes. Likewise, circular dichroism measurements of four orientations of aniline blue in NaClO(3) fix a bisignate tensor with respect to the crystal growth faces. Electronic transition moments and circular dichroism tensors were computed ab initio for aniline blue. These calculations, in conjunction with the crystal-optical properties, establish a consistent mixed-crystal model. The nature of the circular extinction depends upon the crystallographic direction along which the crystals are examined. Along 100, the crystals evidence circular dichroism. Along 110, the crystals evidence mainly anomalous circular extinction. These two properties, while measured by the differential transmission of left and right circularly polarized light, are easily distinguished in their transformation properties with respect to reorientations of the sample plates

  15. Quantum interference spectroscopy in the vacuum ultraviolet

    NARCIS (Netherlands)

    Eikema, K. S E; Zinkstok, R. Th; Witte, S.; Hogervorst, W.; Ubachs, W.

    2006-01-01

    With two experiments on respectively krypton at 2 x 212 nm and xenon at 125 nm we have demonstrated the method of quantum interference spectroscopy in the deep- and vacuum-ultraviolet. Multiple pulses from a frequency comb laser are amplified and frequency converted and used in a Ramsey-like direct

  16. Extreme optical activity and circular dichroism of chiral metal hole arrays

    CERN Document Server

    Gorkunov, M V; Artemov, V V; Rogov, O Y; Yudin, S G

    2014-01-01

    We report extremely strong optical activity and circular dichroism exhibited by subwavelength arrays of four-start-screw holes fabricated with one-pass focused ion beam milling of freely suspended silver films. Having the fourth order rotational symmetry, the structures exhibit the polarization rotation up to 90 degrees and peaks of full circular dichroism and operate as circular polarizers within certain ranges of wavelengths in the visible. We discuss the observations on the basis of general principles (symmetry, reciprocity and reversibility) and conclude that the extreme optical chirality is determined by the chiral localized plasmonic resonances.

  17. Ligand Induced Circular Dichroism and Circularly Polarized Luminescence in CdSe Quantum Dots

    Science.gov (United States)

    Tohgha, Urice; Deol, Kirandeep K.; Porter, Ashlin G.; Bartko, Samuel G.; Choi, Jung Kyu; Leonard, Brian M.; Varga, Krisztina; Kubelka, Jan; Muller, Gilles; Balaz, Milan

    2014-01-01

    Chiral thiol capping ligands L- and D-cysteines induced modular chiroptical properties in achiral cadmium selenide quantum dots (CdSe QDs). Cys-CdSe prepared from achiral oleic acid capped CdSe by post-synthetic ligand exchange displayed size-dependent electronic circular dichroism (CD) and circularly polarized luminescence (CPL). Opposite CPL signals were measured for the CdSe QDs capped with D- and L-cysteine. The CD profile and CD anisotropy varied with size of CdSe nanocrystals with largest anisotropy observed for CdSe nanoparticles of 4.4 nm. Magic angle spinning solid state NMR (MAS ssNMR) experiments suggested bidentate interaction between cysteine and the surface of CdSe. Density functional theory (DFT) calculations verified that attachment of L- and D-cysteine to the surface of model (CdSe)13 nanoclusters induces measurable opposite CD signals for the exitonic band of the nanocluster. The chirality was induced by the hybridization of highest occupied CdSe molecular orbitals with those of the chiral ligand. PMID:24200288

  18. Structural characterization of chiral molecules using vibrational circular dichroism spectroscopy

    DEFF Research Database (Denmark)

    Lassen, Peter Rygaard

    2006-01-01

    . This is the cornerstone of biological specificity. Chiral molecules also interact differently with different polarization states of electromagnetic radiation, because the absorption coefficient depends on the state of polarization. This is called dichroism and gives rise to several spectroscopic techniques targeting...

  19. Anomalous circular dichroism in high harmonic generation of stereoisomers with two chiral centers.

    Science.gov (United States)

    Zhu, Xiaosong; Liu, Xi; Lan, Pengfei; Wang, Dian; Zhang, Qingbin; Li, Wei; Lu, Peixiang

    2016-10-31

    When a molecule has more than one chiral center, it can be either a chiral molecule or a meso isomer. High harmonic generation (HHG) of stereoisomers with two chiral centers driven by circularly polarized (CP) laser pulses is investigated. Counterintuitively, it is found that the HHG exhibits prominent circular dichroism for the meso isomer, while the harmonic spectra with left and right CP laser pulses are nearly the same for the chiral isomers. We show that the anomalous circular dichroism is attributed to the characteristic recollision dynamics of HHG. This feature makes the HHG a promising tool to discriminate the meso isomer and racemic mixture, where no optical activity can be found in both cases. Similar dichroism responses are also found by applying the counter-rotating bicircular laser pulses.

  20. Experimental determination of excitonic band structures of single-walled carbon nanotubes using circular dichroism spectra.

    Science.gov (United States)

    Wei, Xiaojun; Tanaka, Takeshi; Yomogida, Yohei; Sato, Naomichi; Saito, Riichiro; Kataura, Hiromichi

    2016-10-05

    Experimental band structure analyses of single-walled carbon nanotubes have not yet been reported, to the best of our knowledge, except for a limited number of reports using scanning tunnelling spectroscopy. Here we demonstrate the experimental determination of the excitonic band structures of single-chirality single-walled carbon nanotubes using their circular dichroism spectra. In this analysis, we use gel column chromatography combining overloading selective adsorption with stepwise elution to separate 12 different single-chirality enantiomers. Our samples show higher circular dichroism intensities than the highest values reported in previous works, indicating their high enantiomeric purity. Excitonic band structure analysis is performed by assigning all observed Eii and Eij optical transitions in the circular dichroism spectra. The results reproduce the asymmetric structures of the valence and conduction bands predicted by density functional theory. Finally, we demonstrate that an extended empirical formula can estimate Eij optical transition energies for any (n,m) species.

  1. DichroMatch at the protein circular dichroism data bank (DM@PCDDB): A web-based tool for identifying protein nearest neighbors using circular dichroism spectroscopy.

    Science.gov (United States)

    Whitmore, Lee; Mavridis, Lazaros; Wallace, B A; Janes, Robert W

    2017-06-05

    Circular dichroism spectroscopy is a well-used, but simple method in structural biology for providing information on the secondary structure and folds of proteins. DichroMatch (DM@PCDDB) is an online tool that is newly available in the Protein Circular Dichroism Data Bank (PCDDB), which takes advantage of the wealth of spectral and metadata deposited therein, to enable identification of spectral nearest neighbors of a query protein based on four different methods of spectral matching. DM@PCDDB can potentially provide novel information about structural relationships between proteins and can be used in comparison studies of protein homologs and orthologs. © 2017 The Authors Protein Science published by Wiley Periodicals, Inc. on behalf of The Protein Society.

  2. Note: Derivation of two-photon circular dichroism - Addendum to "two-photon circular dichroism" [J. Chem. Phys. 62, 1006 (1975)

    OpenAIRE

    Friese, Daniel Henrik

    2015-01-01

    Published version, also available at http://dx.doi.org/10.1063/1.4930017 This addendum shows the detailed derivation of the fundamental equations for two-photon circular dichroism which are given in a very condensed form in the original publication [I. Tinoco, J. Chem. Phys. 62, 1006 (1975)]. In addition, some minor errors are corrected and some of the derivations in the original publication are commented.

  3. Vibrational Circular Dichroism (VCD) Reveals Subtle Conformational Aspects and Intermolecular Interactions in the Carnitine Family.

    Science.gov (United States)

    Mazzeo, Giuseppe; Abbate, Sergio; Longhi, Giovanna; Castiglioni, Ettore; Villani, Claudio

    2015-12-01

    Vibrational circular dichroism spectra (VCD) in the mid-IR region and electronic circular dichroism (ECD) spectra for three carnitine derivatives in the form of hydrochloride salts were recorded in deuterated methanol solutions. Density Functional Theory calculations help one to understand the significance of the observed VCD bands. VCD and ECD spectra are informative about the absolute configuration of the molecule, but VCD data reveal also some conformational aspects in the N,N,N-trimethyl moiety and inform us about intermolecular interactions gained from the carbonyl stretching region for the acyl substituted carnitines. © 2015 Wiley Periodicals, Inc.

  4. Conformational analysis and circular dichroism of bilirubin, the yellow pigment of jaundice

    Science.gov (United States)

    Lightner, David A.; Person, Richard; Peterson, Blake; Puzicha, Gisbert; Pu, Yu-Ming; Bojadziev, Stefan

    1991-06-01

    Conformational analysis of (4Z, 15Z)-bilirubin-IX(alpha) by molecular mechanics computations reveals a global energy minimum folded conformation. Powerful added stabilization is achieved through intramolecular hydrogen bonding. Theoretical treatment of bilirubin as a molecular exciton predicts an intense bisignate circular dichroism spectrum for the folded conformation: (Delta) (epsilon) is congruent to 270 L (DOT) mole-1 (DOT) cm-1 for the $OM450 nm electronic transition(s). Synthesis of bilirubin analogs with propionic acid groups methylated at the (alpha) or (beta) position introduces an allosteric effect that allows for an optical resolution of the pigments, with enantiomers exhibiting the theoretically predicted circular dichroism.

  5. Large-Area Vacuum Ultraviolet Sensors

    Science.gov (United States)

    Aslam, Shahid; Franz, David

    2012-01-01

    Pt/(n-doped GaN) Schottky-barrier diodes having active areas as large as 1 cm square have been designed and fabricated as prototypes of photodetectors for the vacuum ultraviolet portion (wavelengths approximately equal 200 nm) of the solar spectrum. In addition to having adequate sensitivity to photons in this wavelength range, these photodetectors are required to be insensitive to visible and infrared components of sunlight and to have relatively low levels of dark current.

  6. A Simple Spreadsheet Program to Simulate and Analyze the Far-UV Circular Dichroism Spectra of Proteins

    Science.gov (United States)

    Abriata, Luciano A.

    2011-01-01

    A simple algorithm was implemented in a spreadsheet program to simulate the circular dichroism spectra of proteins from their secondary structure content and to fit [alpha]-helix, [beta]-sheet, and random coil contents from experimental far-UV circular dichroism spectra. The physical basis of the method is briefly reviewed within the context of…

  7. Fano-Induced Circular Dichroism in Three-Dimensional Plasmonic Chiral Metamolecules

    Science.gov (United States)

    Le, Khai Q.

    2017-10-01

    This paper introduces a three-dimensional (3-D) artificial chiral nanostructure, which has variant total optical loss spectroscopies under left- and right-handed circularly polarized (LCP and RCP) incident light. The resulting circular dichroism is induced by Fano resonance generated by the engineered chiral metamolecule, which consists of asymmetrically arranged gold (Au) nanoparticles in three dimensions. The Fano resonance generation is a consequence of modal interference between bright and dark plasmonic modes of asymmetric constituent dimers of the metamolecule.

  8. UV-CD12: synchrotron radiation circular dichroism beamline at ANKA.

    Science.gov (United States)

    Bürck, Jochen; Roth, Siegmar; Windisch, Dirk; Wadhwani, Parvesh; Moss, David; Ulrich, Anne S

    2015-05-01

    Synchrotron radiation circular dichroism (SRCD) is a rapidly growing technique for structure analysis of proteins and other chiral biomaterials. UV-CD12 is a high-flux SRCD beamline installed at the ANKA synchrotron, to which it had been transferred after the closure of the SRS Daresbury. The beamline covers an extended vacuum-UV to near-UV spectral range and has been open for users since October 2011. The current end-station allows for temperature-controlled steady-state SRCD spectroscopy, including routine automated thermal scans of microlitre volumes of water-soluble proteins down to 170 nm. It offers an excellent signal-to-noise ratio over the whole accessible spectral range. The technique of oriented circular dichroism (OCD) was recently implemented for determining the membrane alignment of α-helical peptides and proteins in macroscopically oriented lipid bilayers as mimics of cellular membranes. It offers improved spectral quality dichroism artifacts.

  9. Determination of Myoglobin Stability by Circular Dichroism Spectroscopy: Classic and Modern Data Analysis

    Science.gov (United States)

    Mehl, Andrew F.; Crawford, Mary A.; Zhang, Lei

    2009-01-01

    Few laboratory procedures describe the use of circular dichroism (CD) at the undergraduate level. To increase the number of laboratory exercises using CD, a thermal denaturation study of myoglobin using CD is described to assess protein stability. Values obtained from a more classic linear data analysis approach are consistent with data analyzed…

  10. Probing electronic coupling between adenine bases in RNA strands from synchrotron radiation circular dichroism experiments

    DEFF Research Database (Denmark)

    Nielsen, Lisbeth Munksgård; Hoffmann, Søren Vrønning; Nielsen, Steen Brøndsted

    2012-01-01

    Circular dichroism spectra (176–330 nm) of RNA adenine oligomers, (rA)n (n = 1–10, 12, 15, and 20), reveal electronic coupling between two bases in short strands. The number of interacting bases in long strands is more and larger than that reported previously for the corresponding DNA strands....

  11. Circular Dichroism Investigation of Dess-Martin Periodinane Oxidation in the Organic Chemistry Laboratory

    Science.gov (United States)

    Reed, Nicole A.; Rapp, Robert D.; Hamann, Christian S.; Artz, Pamela G.

    2005-01-01

    Dess-Martin periodinane oxidation is an experiment that provides an avenue to the introduction of Circular Dichroism (CD) spectroscopy in organic chemistry curriculum as a diagnostic tool for examination of the results of a familiar reaction, and absolute configuration. From the experiment, students increased their understanding of CD theory and…

  12. Application of circular dichroism spectroscopy in the study of mixed-valence asymmetric ruthenium polypyridyl complexes

    NARCIS (Netherlands)

    Ahmed, Hamid M. Y.; Coburn, Nadia; Dini, Danilo; de Jong, Jaap J. D.; Villani, Claudio; Browne, Wesley R.; Vos, Johannes G.

    2011-01-01

    Circular dichroism (CD) spectroelectrochemistry is used to determine the extent of singly occupied molecular orbital delocalization in mixed-valence multinuclear complexes, specifically the mixed-valence (RuRuIII)-Ru-II states of the four diastereoisomers of [(Ru(bpy)(2))(2)(bpt)](3+) [1; bpy =

  13. Unboiling an Egg: An Introduction to Circular Dichroism and Protein Refolding

    Science.gov (United States)

    Hoben, John P.; Wang, Jianing; Miller, Anne-Frances

    2017-01-01

    A signature of life is that biological molecules occur as a single stereoisomer with respect to each chiral center, and this is echoed in the structures of biological polymers. Thus, circular dichroism (CD) has emerged as a hallmark of biomolecular structures. The tangible and familiar phenomenon of raw egg white's conversion from transparent…

  14. Optical absorption and magnetic circular dichroism spectra of thiouracils: a quantum mechanical study in solution

    DEFF Research Database (Denmark)

    Martínez-Fernández, L.; Fahleson, Tobias; Norman, Patrick

    2017-01-01

    The excited electronic states of 2-thiouracil, 4-thiouracil and 2,4-dithiouracil, the analogues of uracil where the carbonyl oxygens are substituted by sulphur atoms, have been investigated by computing the magnetic circular dichroism (MCD) and one-photon absorption (OPA) spectra at the time-depe...

  15. Characterization of dry globular proteins and protein fibrils by synchrotron radiation vacuum UV circular dichroism

    DEFF Research Database (Denmark)

    Nesgaard, Lise; Hoffmann, Søren V.; Andersen, Christian Beyschau

    2008-01-01

    Circular dichroism using synchrotron radiation (SRCD) can extend the spectral range down to approximately 130 nm for dry proteins, potentially providing new structural information. Using a selection of dried model proteins, including alpha-helical, beta-sheet, and mixed-structure proteins, we obs...

  16. On the equivalence of conformational and enantiomeric changes of atomic configuration for vibrational circular dichroism

    NARCIS (Netherlands)

    Heshmat, M.; Nicu, V.P.; Baerends, E.J.

    2012-01-01

    We study systematically the vibrational circular dichroism (VCD) spectra of the conformers of a simple chiral molecule, with one chiral carbon and an "achiral" alkyl substituent of varying length. The vibrational modes can be divided into a group involving the chiral center and its direct neighbors

  17. Circular Dichroism in Laser-Assisted Ion-Atom Collisions

    Science.gov (United States)

    Feuerstein, Bernold; Thumm, Uwe

    2003-05-01

    We investigate theoretically the effects of a strong laser field on the dynamics of ion-atom collisions. The time-dependent Schrödinger equation is solved on a numerical grid for a reduced dimensionality model of the scattering system. The single active electron system is confined to the two dimensions of the scattering plane, which also includes the laser electric field vector. This allows the study of the influence of the laser intensity and polarization (linear, circular, elliptic) on the collision dynamics (capture and ionization probabilities) The projectile follows a classical trajectory with impact parameter b. We found a strong circular dirchroism in the capture probability P(b) for slow proton-hydrogen collisions. First results will be presented and discussed. Supported in part by NSF (grant PHY-0071035) and Division of Chemical Sciences, Office of Basic Energy Scienes, Office of Energy Research, US DOE.

  18. Circular dichroism in a three-dimensional semiconductor chiral photonic crystal

    CERN Document Server

    Takahashi, S; Ota, Y; Tatebayashi, J; Iwamoto, S; Arakawa, Y

    2014-01-01

    Circular dichroism covering the telecommunication band is experimentally demonstrated in a semiconductor-based three-dimensional chiral photonic crystal (PhC). We design a rotationally-stacked woodpile PhC structure where neighboring layers are rotated by 60 degrees and three layers construct a single helical unit. The mirror-asymmetric PhC made from GaAs with sub-micron periodicity is fabricated by a micro-manipulation technique. Due to the large contrast of refractive indices between GaAs and air, the experimentally obtained circular dichroism extends over a wide wavelength range, with the transmittance of right-handed circularly polarized incident light being 85% and that of left-handed light being 15% at a wavelength of 1300 nm. The obtained results show good agreement with numerical simulations.

  19. Nuclear-Spin-Induced Circular Dichroism in the Infrared Region for Liquids.

    Science.gov (United States)

    Chen, Fang; Yao, Guo-hua; Zhang, Zhen-lin; Liu, Fan-chen; Chen, Dong-ming

    2015-06-22

    Recently, the nuclear-spin-induced optical rotation (NSOR) and circular dichroism (NSCD) for liquids were discovered and extensively studied and developed. However, so far, nuclear-spin-induced magnetic circular dichroism in the IR region (IR-NSCD) has not been explored, even though all polyatomic molecules exhibit extensive IR spectra. Herein, IR-NSCD is proposed and discussed theoretically. The results indicate that in favorable conditions the IR-NSCD angle may be much larger than the NSOR angle in the UV/Vis region due to a vibrational resonance effect and can be measurable by using the NSOR experiment scheme. IR-NSCD can automatically combine and give NMR spectra and IRCD spectra of the nuclear spin prepolarized samples in liquids, which, in principle, could be developed to become a unique, novel analytical tool. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Circular dichroism of surface complexes based on quantum dots and azo dye.

    Science.gov (United States)

    Kundelev, Evgeny V; Orlova, Anna O; Maslov, Vladimir G; Baranov, Alexander V; Fedorov, Anatoly V

    2018-03-01

    Chiral properties of surface complexes based on CdSe/ZnS quantum dots (QDs) and 1-(2-pyridylazo)-2-naphthol (PAN) azo dye were investigated by circular dichroism spectroscopy. The use of L-, D-cysteine (Lcys, Dcys) capping ligands allowed us to obtain water-soluble chiral QD-PAN complexes. The characterization of the complexes was performed by UV-vis, FTIR, and CD spectroscopy. Quantum chemical TDDFT calculated CD spectra reproduced the experimentally observed sign patterns, which originate from binding Lcys or Dcys and PAN molecules to the same Zn atom on the QD surface. The resulting complex is characterized by a large circular dichroism in comparison with an ordinary QD chirality induced by cysteine molecules. The pattern of CD signal is the same for Lcys and Dcys ligands in chiral QD-PAN complex. © 2017 Wiley Periodicals, Inc.

  1. Circular dichroism, magnetic circular dichroism, and variable temperature variable field magnetic circular dichroism studies of biferrous and mixed-valent myo-inositol oxygenase: insights into substrate activation of O2 reactivity.

    Science.gov (United States)

    Snyder, Rae Ana; Bell, Caleb B; Diao, Yinghui; Krebs, Carsten; Bollinger, J Martin; Solomon, Edward I

    2013-10-23

    myo-Inositol oxygenase (MIOX) catalyzes the 4e(-) oxidation of myo-inositol (MI) to D-glucuronate using a substrate activated Fe(II)Fe(III) site. The biferrous and Fe(II)Fe(III) forms of MIOX were studied with circular dichroism (CD), magnetic circular dichroism (MCD), and variable temperature variable field (VTVH) MCD spectroscopies. The MCD spectrum of biferrous MIOX shows two ligand field (LF) transitions near 10000 cm(-1), split by ~2000 cm(-1), characteristic of six coordinate (6C) Fe(II) sites, indicating that the modest reactivity of the biferrous form toward O2 can be attributed to the saturated coordination of both irons. Upon oxidation to the Fe(II)Fe(III) state, MIOX shows two LF transitions in the ~10000 cm(-1) region, again implying a coordinatively saturated Fe(II) site. Upon MI binding, these split in energy to 5200 and 11200 cm(-1), showing that MI binding causes the Fe(II) to become coordinatively unsaturated. VTVH MCD magnetization curves of unbound and MI-bound Fe(II)Fe(III) forms show that upon substrate binding, the isotherms become more nested, requiring that the exchange coupling and ferrous zero-field splitting (ZFS) both decrease in magnitude. These results imply that MI binds to the ferric site, weakening the Fe(III)-μ-OH bond and strengthening the Fe(II)-μ-OH bond. This perturbation results in the release of a coordinated water from the Fe(II) that enables its O2 activation.

  2. Magnetic moments in a gadolinium iron garnet studied by soft-X-ray magnetic circular dichroism

    NARCIS (Netherlands)

    Rudolf, P.; Sette, F.; Tjeng, L.H.; Meigs, G.; Chen, C.T.

    1992-01-01

    The magnetic moments of Gd and Fe in gadolinium iron garnet (Gd3Fe5O12) were probed at 77 and 300 K by soft-X-ray magnetic circular dichroism (SXMCD) measurements at the GdMa4,5 and at the FeL2,3 absorption edges. The SXMCD signal at each edge allows one to independently determine the magnetic

  3. Ultracentrifuge and circular dichroism studies of folding equilibria in a retro GCN4-like leucine zipper.

    OpenAIRE

    Holtzer, Marilyn Emerson; Braswell, Emory; Angeletti, Ruth Hogue; Mints, Lisa; Zhu, Dan; Holtzer, Alfred

    2000-01-01

    Equilibrium ultracentrifuge and circular dichroism (CD) studies of a retropeptide of a GCN4-like leucine zipper in neutral saline buffer are reported as functions of temperature. Ultracentrifuge results indicate the presence of three oligomeric species: monomer, dimer, and tetramer, in quantifiable amounts, and the data provide values for the standard DeltaG, DeltaH, and DeltaS for interconversion. CD at 222 nm displays the strong concentration dependence characteristic of dissociative unfold...

  4. Resonant second-harmonic-generation circular-dichroism microscopy reveals molecular chirality in native biological tissues

    CERN Document Server

    Chen, Mei-Yu; Kan, Che-Wei; Lin, Yen-Yin; Ye, Cin-Wei; Wu, Meng-Jer; Liu, Hsiang-Lin; Chu, Shi-Wei

    2016-01-01

    Conventional linear optical activity effects are widely used for studying chiral materials. However, poor contrast and artifacts due to sample anisotropy limit the applicability of these methods. Here we demonstrate that nonlinear second-harmonic-generation circular dichroism spectral microscopy can overcome these limits. In intact collagenous tissues, clear spectral resonance is observed with sub-micrometer spatial resolution. By performing gradual protein denaturation studies, we show that the resonant responses are dominantly due to the molecular chirality.

  5. Circular dichroism in free-free transitions of high energy electron-atom scattering

    CERN Document Server

    Cionga, Aurelia; Zloh, Gabriela; 10.1103/PhysRevA.62.063406

    2013-01-01

    We consider high energy electron scattering by hydrogen atoms in the presence of a laser field of moderate power and higher frequencies. If the field is a superposition of a linearly and a circularly polarized laser beam in a particular configuration, then we can show that circular dichroism in two photon transitions can be observed not only for the differential but also for the integrated cross sections, provided the laser-dressing of the atomic target is treated in second order perturbation theory and the coupling between hydrogenic bound and continuum states is involved.

  6. Vacuum Ultraviolet Photoionization of Complex Chemical Systems.

    Science.gov (United States)

    Kostko, Oleg; Bandyopadhyay, Biswajit; Ahmed, Musahid

    2016-05-27

    Tunable vacuum ultraviolet (VUV) radiation coupled to mass spectrometry is applied to the study of complex chemical systems. The identification of novel reactive intermediates and radicals is revealed in flame, pulsed photolysis, and pyrolysis reactors, leading to the elucidation of spectroscopy, reaction mechanisms, and kinetics. Mass-resolved threshold photoelectron photoion coincidence measurements provide unprecedented access to vibrationally resolved spectra of free radicals present in high-temperature reactors. Photoionization measurements in water clusters, nucleic acid base dimers, and their complexes with water provide signatures of proton transfer in hydrogen-bonded and π-stacked systems. Experimental and theoretical methods to track ion-molecule reactions and fragmentation pathways in intermolecular and intramolecular hydrogen-bonded systems in sugars and alcohols are described. Photoionization of laser-ablated molecules, clusters, and their reaction products inform thermodynamics and spectroscopy that are relevant to astrochemistry and catalysis. New directions in coupling VUV radiation to interrogate complex chemical systems are discussed.

  7. Circular Dichroism of DNA G-Quadruplexes: Combining Modeling and Spectroscopy To Unravel Complex Structures.

    Science.gov (United States)

    Gattuso, Hugo; Spinello, Angelo; Terenzi, Alessio; Assfeld, Xavier; Barone, Giampaolo; Monari, Antonio

    2016-03-31

    We report on the comparison between the computational and experimental determination of electronic circular dichroism spectra of different guanine quadruplexes obtained from human telomeric sequences. In particular the difference between parallel, antiparallel, and hybrid structures is evidenced, as well as the induction of transitions between the polymorphs depending on the solution environment. Extensive molecular dynamics simulations (MD) are used to probe the conformational space of the different quadruplexes, and subsequently state-of-the-art hybrid quantum mechanics/molecular mechanics (QM/MM) techniques coupled with excitonic semiempirical Hamiltonian are used to simulate the macromolecular induced circular dichroism. The coupling of spectroscopy and molecular simulation allows an efficient one-to-one mapping between structures and optical properties, offering a way to disentangle the rich, yet complicated, quantity of information embedded in circular dichroism spectra. We show that our methodology is robust and efficient and allows us to take into account subtle conformational changes. As such, it could be used as an efficient tool to investigate structural modification upon DNA/drug interactions.

  8. Circular dichroism spectroscopy study of crystalline-to-amorphous transformation in chiral platinum(II) complexes.

    Science.gov (United States)

    Zhang, Xiao-Peng; Wu, Tao; Liu, Jian; Zhao, Jin-Cheng; Li, Cheng-Hui; You, Xiao-Zeng

    2013-07-01

    Two couples of enantiomeric platinum(II) complexes: Pt(L1a )Cl (1a), Pt(L1b )Cl (1b) and Pt(L1a )(C ≡ C - Ph) (2a), Pt(L1b )(C ≡ C - Ph) (2b) (L1a  = (+)-1,3-di-(2-(4,5-pinene)pyridyl)benzene, L1b  = (-)-1,3-di-(2-(4,5-pinene)pyridyl)benzene) were synthesized and characterized. Their absolute configurations were determined by single crystal X-ray diffraction and further verified by circular dichroism (CD) spectra (including electronic circular dichroism [ECD] and vibrational circular dichroism [VCD]). These complexes show interesting mechanoluminescence and/or vapoluminescence due to crystalline-to-amorphous transformation. The crystalline solids, grinding-induced amorphous powders, and vapor-induced amorphous powders of complexes 2a and 2b were comparatively investigated by solid-state ECD and VCD spectra. The transformation from crystalline solids to amorphous powders was accompanied by significant variances of the spectral feature in both ECD and VCD spectra. © 2013 Wiley Periodicals, Inc.

  9. Direct determination of absolute configuration: a vibrational circular dichroism study on dimethyl-substituted phenyloxiranes synthesized by Shi epoxidation

    DEFF Research Database (Denmark)

    Fristrup, Peter; Lassen, Peter Rygaard; Tanner, David Ackland

    2008-01-01

    The three possible dimethylsubstituted phenyloxiranes (cis, trans and geminal) were synthesized in both racemic (mCPBA) and enantiomerically enriched forms (Shi epoxidation) and subjected to a vibrational circular dichroism study. The experimental spectra were compared to theoretical spectra...

  10. Organic photodiodes from homochiral l-proline derived squaraine compounds with strong circular dichroism.

    Science.gov (United States)

    Schulz, Matthias; Mack, Majvor; Kolloge, Oliver; Lützen, Arne; Schiek, Manuela

    2017-03-08

    We suggest and explore a novel route towards organic photodetectors sensitive to the circular polarization state of light. For this, we insert fullerene-blended thin films of homochiral squaraine compounds acting as a highly circular dichroic active layer into conventional bulk hetero-junction photodiodes. Initially, we discuss steady-state characterization of photodiodes with unpolarized light. The homochiral, l-proline derived squaraine compounds are obtained via a chiral pool synthesis in sizable quantities. The aggregation behavior of the two compounds with varying side chain length is complex. They exhibit H-type spectral signatures only in colloidal solution, and both H- and J-type features with large splitting in neat and fullerene-blended thin films. We probe strong excitonic circular dichroism for both aggregate species, showing the most competitive dissymmetry factors up to -0.055 in fullerene-blended thin films. We vary the blend ratio and layer thickness of such active layers in the photodiodes. The device performance is in all cases limited by a low fill factor which is accompanied by a voltage-dependent photocurrent. Current-voltage measurements show light intensity dependent characteristics, which are S-shaped, contrary to our expectations, only for thin active layers independent of the blend ratio. The external quantum efficiency is in some cases extraordinarily high, exceeding 100 percent in the blue spectral range under modest reverse bias voltages for thin, fullerene-rich devices. However, the most promising are the devices with thick, donor-rich layers defined by a spectral overlap of the strongest photocurrent response and the maximum circular dichroism within the green spectral range. Thus, we demonstrate the feasibility of combining photodiode functionality and strong circular dichroism as intrinsic material properties.

  11. Circular Dichroism of Electric-Field-Oriented CdSe/CdS Quantum Dots-in-Rods.

    Science.gov (United States)

    Mukhina, Maria V; Baimuratov, Anvar S; Rukhlenko, Ivan D; Maslov, Vladimir G; Purcell Milton, Finn; Gun'ko, Yurii K; Baranov, Alexander V; Fedorov, Anatoly V

    2016-09-27

    Here we report anisotropy of intrinsic chiroptical response in CdSe/CdS quantum dot-in-rod systems. These nanostructures being oriented in an external electric field demonstrate dependence of circular dichroism signal on the orientation of the nanocrystals. The type of circular polarization in these nanostructures correlates with preferential direction of linear polarization, and the degree of circular polarization is the maximal for the first circular dichroism band corresponding to the absorption band edge. We also support our experimental data with a theoretical model. Using this model, we show a direct connection between theoretically derived morphological parameters of twisting in nanocrystals lattices and calculated from experimental data parameters of circular dichroism anisotropy.

  12. UV-CD12: synchrotron radiation circular dichroism beamline at ANKA

    Science.gov (United States)

    Bürck, Jochen; Roth, Siegmar; Windisch, Dirk; Wadhwani, Parvesh; Moss, David; Ulrich, Anne S.

    2015-01-01

    Synchrotron radiation circular dichroism (SRCD) is a rapidly growing technique for structure analysis of proteins and other chiral biomaterials. UV-CD12 is a high-flux SRCD beamline installed at the ANKA synchrotron, to which it had been transferred after the closure of the SRS Daresbury. The beamline covers an extended vacuum-UV to near-UV spectral range and has been open for users since October 2011. The current end-station allows for temperature-controlled steady-state SRCD spectroscopy, including routine automated thermal scans of microlitre volumes of water-soluble proteins down to 170 nm. It offers an excellent signal-to-noise ratio over the whole accessible spectral range. The technique of oriented circular dichroism (OCD) was recently implemented for determining the membrane alignment of α-helical peptides and proteins in macroscopically oriented lipid bilayers as mimics of cellular membranes. It offers improved spectral quality <200 nm compared with an OCD setup adapted to a bench-top instrument, and accelerated data collection by a factor of ∼3. In addition, it permits investigations of low hydrated protein films down to 130 nm using a rotatable sample cell that avoids linear dichroism artifacts. PMID:25931105

  13. Large circular dichroism and optical rotation in titanium doped chiral silver nanorods

    Energy Technology Data Exchange (ETDEWEB)

    Titus, Jitto; Perera, A.G. Unil [Department of Physics and Astronomy, Optoelectronics Laboratory, GSU, Atlanta, GA (United States); Larsen, George; Zhao, Yiping [Department of Physics and Astronomy, Nanolab, UGA, Athens, GA (United States)

    2016-10-15

    The circular dichroism of titanium-doped silver chiral nanorod arrays grown using the glancing angle deposition (GLAD) method is investigated in the visible and near infrared ranges using transmission ellipsometry and spectroscopy. These films are found to have significant circular polarization effects across broad ranges of the visible to NIR spectrum, including large values for optical rotation. The characteristics of these circular polarization effects are strongly influenced by the morphology of the deposited arrays. Thus, the morphological control of the optical activity in these nanostructures demonstrates significant optimization capability of the GLAD technique for fabricating chiral plasmonic materials. (copyright 2016 by WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  14. Angular momentum-induced circular dichroism in non-chiral nanostructures

    CERN Document Server

    Zambrana-Puyalto, Xavier; Molina-Terriza, Gabriel

    2014-01-01

    Circular dichroism (CD), i.e. the differential response of a system to left and right circularly polarized light, is one of the only techniques capable of providing morphological information of certain samples. In biology, for instance, CD spectroscopy is widely used to study the structure of proteins. More recently, it has also been used to characterize metamaterials and plasmonic structures. Typically, CD can only be observed in chiral objects. Here, we present experimental results showing that a non-chiral sample such as a sub-wavelength circular nano-aperture can produce giant CD when a vortex beam is used to excite it. These measurements can be understood by studying the symmetries of the sample and the total angular momentum that vortex beams carry. Our results show that CD can provide a wealth of information about the sample when combined with the control of the total angular momentum of the input field.

  15. Circular dichroism of twisted photons in non-chiral atomic matter

    Science.gov (United States)

    Afanasev, Andrei; Carlson, Carl E.; Solyanik, Maria

    2017-10-01

    We calculate the circular dichroism (CD) for the absorption of the twisted photons, or optical vortices, by atoms, caused by atomic excitation into discrete energy levels. The effects of photon spin on the rates and cross sections of atomic photo-excitation are considered. It is demonstrated that, although for electric dipole transitions the atomic excitation rates depend on the relative orientation of photon spin and orbital angular momentum (OAM), the resulting CD is zero. However, CD is nonzero for atomic transitions of higher multipolarity, and it is predicted to peak near the phase singularity in the optical vortex center. The effects remain large in a paraxial limit, where analytic expressions are provided. The predicted spin asymmetries are equivalent to OAM dichroism for the fixed photon spin.

  16. Apparent circular dichroism signature of stirring-oriented DNA and drug-DNA complexes.

    Science.gov (United States)

    Zsila, Ferenc

    2015-01-01

    It is shown that in water with no added salts calf-thymus DNA and its drug-loaded forms exhibit peculiar, completely reversible circular dichroism (CD) spectroscopic changes upon mechanical rotatory stirring. Due to the stirring-induced spatial alignment of the helices, the CD spectra are overwhelmed by the much more intense linear dichroism contribution. This apparent chiroptical response can be generated and detected without using any sophisticated attachment. It is a technically simple complement to existing methods suitable to obtain additional structural information which can not be derived from isotropic spectra. Drug-DNA interactions generating no or very weak CD spectroscopic changes under isotropic conditions become easily detectable upon stirring the sample solution. Stirring-induced changes of the CD profile also enable to clarify the DNA binding mode of various compounds (e.g., imatinib, thioflavin T) which would remain ambiguous considering isotropic spectral data only. Copyright © 2014 Elsevier B.V. All rights reserved.

  17. Imaging photoelectron circular dichroism of chiral molecules by femtosecond multiphoton coincidence detection.

    Science.gov (United States)

    Lehmann, C Stefan; Ram, N Bhargava; Powis, Ivan; Janssen, Maurice H M

    2013-12-21

    Here, we provide a detailed account of novel experiments employing electron-ion coincidence imaging to discriminate chiral molecules. The full three-dimensional angular scattering distribution of electrons is measured after photoexcitation with either left or right circular polarized light. The experiment is performed using a simplified photoelectron-photoion coincidence imaging setup employing only a single particle imaging detector. Results are reported applying this technique to enantiomers of the chiral molecule camphor after three-photon ionization by circularly polarized femtosecond laser pulses at 400 nm and 380 nm. The electron-ion coincidence imaging provides the photoelectron spectrum of mass-selected ions that are observed in the time-of-flight mass spectra. The coincident photoelectron spectra of the parent camphor ion and the various fragment ions are the same, so it can be concluded that fragmentation of camphor happens after ionization. We discuss the forward-backward asymmetry in the photoelectron angular distribution which is expressed in Legendre polynomials with moments up to order six. Furthermore, we present a method, similar to one-photon electron circular dichroism, to quantify the strength of the chiral electron asymmetry in a single parameter. The circular dichroism in the photoelectron angular distribution of camphor is measured to be 8% at 400 nm. The electron circular dichroism using femtosecond multiphoton excitation is of opposite sign and about 60% larger than the electron dichroism observed before in near-threshold one-photon ionization with synchrotron excitation. We interpret our multiphoton ionization as being resonant at the two-photon level with the 3s and 3p Rydberg states of camphor. Theoretical calculations are presented that model the photoelectron angular distribution from a prealigned camphor molecule using density functional theory and continuum multiple scattering X alpha photoelectron scattering calculations

  18. Circular dichroism measurements at an x-ray free-electron laser with polarization control.

    Science.gov (United States)

    Hartmann, G; Lindahl, A O; Knie, A; Hartmann, N; Lutman, A A; MacArthur, J P; Shevchuk, I; Buck, J; Galler, A; Glownia, J M; Helml, W; Huang, Z; Kabachnik, N M; Kazansky, A K; Liu, J; Marinelli, A; Mazza, T; Nuhn, H-D; Walter, P; Viefhaus, J; Meyer, M; Moeller, S; Coffee, R N; Ilchen, M

    2016-08-01

    A non-destructive diagnostic method for the characterization of circularly polarized, ultraintense, short wavelength free-electron laser (FEL) light is presented. The recently installed Delta undulator at the LCLS (Linac Coherent Light Source) at SLAC National Accelerator Laboratory (USA) was used as showcase for this diagnostic scheme. By applying a combined two-color, multi-photon experiment with polarization control, the degree of circular polarization of the Delta undulator has been determined. Towards this goal, an oriented electronic state in the continuum was created by non-resonant ionization of the O2 1s core shell with circularly polarized FEL pulses at hν ≃ 700 eV. An also circularly polarized, highly intense UV laser pulse with hν ≃ 3.1 eV was temporally and spatially overlapped, causing the photoelectrons to redistribute into so-called sidebands that are energetically separated by the photon energy of the UV laser. By determining the circular dichroism of these redistributed electrons using angle resolving electron spectroscopy and modeling the results with the strong-field approximation, this scheme allows to unambiguously determine the absolute degree of circular polarization of any pulsed, ultraintense XUV or X-ray laser source.

  19. Circular dichroism measurements at an x-ray free-electron laser with polarization control

    Energy Technology Data Exchange (ETDEWEB)

    Hartmann, G.; Shevchuk, I.; Walter, P.; Viefhaus, J. [Deutsches Elektronen-Synchrotron, Notkestraße 85, 22607 Hamburg (Germany); Lindahl, A. O. [PULSE at Stanford, 2575 Sand Hill Road, Menlo Park, California 94025 (United States); Knie, A. [Institut für Physik, University of Kassel, Heinrich-Plett-Str. 40, 34132 Kassel (Germany); Hartmann, N.; Lutman, A. A.; MacArthur, J. P.; Glownia, J. M.; Helml, W.; Huang, Z.; Marinelli, A.; Nuhn, H.-D.; Moeller, S.; Coffee, R. N.; Ilchen, M., E-mail: markus.ilchen@xfel.eu [SLAC National Accelerator Laboratory, 2575 Sand Hill Road, Menlo Park, California 94025 (United States); Buck, J.; Galler, A.; Liu, J. [European XFEL GmbH, Albert-Einstein-Ring 19, 22761 Hamburg (Germany); and others

    2016-08-15

    A non-destructive diagnostic method for the characterization of circularly polarized, ultraintense, short wavelength free-electron laser (FEL) light is presented. The recently installed Delta undulator at the LCLS (Linac Coherent Light Source) at SLAC National Accelerator Laboratory (USA) was used as showcase for this diagnostic scheme. By applying a combined two-color, multi-photon experiment with polarization control, the degree of circular polarization of the Delta undulator has been determined. Towards this goal, an oriented electronic state in the continuum was created by non-resonant ionization of the O{sub 2} 1s core shell with circularly polarized FEL pulses at hν ≃ 700 eV. An also circularly polarized, highly intense UV laser pulse with hν ≃ 3.1 eV was temporally and spatially overlapped, causing the photoelectrons to redistribute into so-called sidebands that are energetically separated by the photon energy of the UV laser. By determining the circular dichroism of these redistributed electrons using angle resolving electron spectroscopy and modeling the results with the strong-field approximation, this scheme allows to unambiguously determine the absolute degree of circular polarization of any pulsed, ultraintense XUV or X-ray laser source.

  20. Vacuum ultraviolet detector for gas chromatography.

    Science.gov (United States)

    Schug, Kevin A; Sawicki, Ian; Carlton, Doug D; Fan, Hui; McNair, Harold M; Nimmo, John P; Kroll, Peter; Smuts, Jonathan; Walsh, Phillip; Harrison, Dale

    2014-08-19

    Analytical performance characteristics of a new vacuum ultraviolet (VUV) detector for gas chromatography (GC) are reported. GC-VUV was applied to hydrocarbons, fixed gases, polyaromatic hydrocarbons, fatty acids, pesticides, drugs, and estrogens. Applications were chosen to feature the sensitivity and universal detection capabilities of the VUV detector, especially for cases where mass spectrometry performance has been limited. Virtually all chemical species absorb and have unique gas phase absorption cross sections in the approximately 120-240 nm wavelength range monitored. Spectra are presented, along with the ability to use software for deconvolution of overlapping signals. Some comparisons with experimental synchrotron data and computed theoretical spectra show good agreement, although more work is needed on appropriate computational methods to match the simultaneous broadband electronic and vibronic excitation initiated by the deuterium lamp. Quantitative analysis is governed by Beer-Lambert Law relationships. Mass on-column detection limits reported for representatives of different classes of analytes ranged from 15 (benzene) to 246 pg (water). Linear range measured at peak absorption for benzene was 3-4 orders of magnitude. Importantly, where absorption cross sections are known for analytes, the VUV detector is capable of absolute determination (without calibration) of the number of molecules present in the flow cell in the absence of chemical interferences. This study sets the stage for application of GC-VUV technology across a wide breadth of research areas.

  1. Circular Dichroism of RbHe and RbN$_2$ Molecules

    CERN Document Server

    Lancor, B; Wyllie, R; Walker, T G

    2010-01-01

    We present measurements of the circular dichroism of optically pumped Rb vapor near the D1 resonance line. Collisions with the buffer gases $^3$He and N$_2$ reduce the transparency of the vapor, even when fully polarized. We use two methods to measure this effect, show that the He results can be understood from RbHe potential curves, and show how this effect conspires with the spectral profile of the optical pumping light to increase the laser power demands for optical pumping of very optically thick samples.

  2. Enhancement of magnetic circular dichroism in bi-layered ZnO-Bi:YIG thin films

    Science.gov (United States)

    Mito, Shinichiro; Shiotsu, Yusaku; Sasano, Junji; Takagi, Hiroyuki; Inoue, Mitsuteru

    2017-05-01

    Bi-layered zinc oxide (ZnO) and bismuth substituted yttrium iron garnet (Bi:YIG) was fabricated and magneto-optically investigated. Enhancement of Faraday rotation and magnetic circular dichroism (MCD) was observed. The wavelength of MCD enhancement was in good agreement with exciton wavelength of ZnO. This enhancement was only observed in the bi-layer, and implies that the exciton generated in ZnO interacted with Bi:YIG. Because the exciton wavelength of ZnO can be controlled by electro-optic effect, this result has the potential for realizing voltage control of magneto-optic effect.

  3. Assignment of absolute stereostructures through quantum mechanics electronic and vibrational circular dichroism calculations.

    Science.gov (United States)

    Dai, Peng; Jiang, Nan; Tan, Ren-Xiang

    2016-01-01

    Elucidation of absolute configuration of chiral molecules including structurally complex natural products remains a challenging problem in organic chemistry. A reliable method for assigning the absolute stereostructure is to combine the experimental circular dichroism (CD) techniques such as electronic and vibrational CD (ECD and VCD), with quantum mechanics (QM) ECD and VCD calculations. The traditional QM methods as well as their continuing developments make them more applicable with accuracy. Taking some chiral natural products with diverse conformations as examples, this review describes the basic concepts and new developments of QM approaches for ECD and VCD calculations in solution and solid states.

  4. Ab initio calculations of anharmonic vibrational circular dichroism intensities of trans-2,3-dideuteriooxirane

    DEFF Research Database (Denmark)

    Bak, KL; Bludsky, O.; Jorgensen, P

    1995-01-01

    A priori theory is derived for anharmonic calculations of vibrational circular dichroism (VCD). The anharmonic VCD expression is gauge origin independent and reduce to the magnetic field perturbation theory expression in the double-harmonic approximation. The theory has been implemented using...... for the atomic axial tensors and using second-order Moller-Plesset theory for the atomic polar tensors and the force fields, The changes of the vibrational rotatory strengths from anharmonicities are small, and do not explain the previously observed large discrepancies between the double-harmonic results...

  5. Vacuum Ultraviolet Laser Probe of Chemical Dynamics of Aerospace Relevance

    Science.gov (United States)

    2012-09-12

    RESPONSIBLE PERSON 19b. TELEPHONE NUMBER (Include area code) 09/12/12 01/15/09-11/30/11 VACUUM ULTRAVIOLET LASER PROBES OF CHEMICAL DYNAMICS PF...is to be limited. Standard Form 298 Back (Rev. 8/98) FINAL AFOSR REPORT (Dec. 1, 2008-Nov. 30, 2011) I. Grant Title: Vacuum Ultraviolet ...goal of this research program is to provide pertinent information about the energetics, photochemistry , and chemical dynamics of spacecraft effluents

  6. Analysis of the kinetics of folding of proteins and peptides using circular dichroism

    Science.gov (United States)

    Greenfield, Norma J.

    2009-01-01

    Circular dichroism (CD) is a useful spectroscopic technique for studying the secondary structure, folding and binding properties of proteins. This protocol covers how to use the intrinsic circular dichroic properties of proteins to follow their folding and unfolding as a function of time. Included will be methods of obtaining data and how to analyze the folding and unfolding data to determine the rate constants and the order of the folding/unfolding reactions. The protocol focuses on the use of CD to follow folding when it is relatively slow, on the order of minutes to days. The methods for analyzing the data, however, can also be applied to data collected with a CD machine equipped with stopped-flow accessories in the millisecond to second range and folding analyzed by other spectroscopic methods including changes in absorption or fluorescence spectra as a function of time. PMID:17406548

  7. Enantiomeric Excess Sensitivity to Below One Percent by Using Femtosecond Photoelectron Circular Dichroism.

    Science.gov (United States)

    Kastner, Alexander; Lux, Christian; Ring, Tom; Züllighoven, Stefanie; Sarpe, Cristian; Senftleben, Arne; Baumert, Thomas

    2016-04-18

    Photoelectron circular dichroism (PECD) is experimentally investigated with chiral specimens with varying amounts of enantiomeric excess (ee). As a prototype, we measure and analyze the photoelectron angular distribution from randomly oriented fenchone molecules in the gas phase that result from ionization with circularly polarized femtosecond laser pulses. The quantification of these measurements shows a linear dependence with respect to the ee values. In addition, differences in the ee values (denoted as detection limit) of below one percent can be distinguished for nearly enantiopure samples, as well as for almost racemates. In combination with the use of a reference, the assignment of absolute ee values is possible. The present measurement time is a few minutes, but this could be reduced. This table-top laser-based approach should facilitate widespread implementation in chiral analysis. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Atomic Oscillator Strengths In The Vacuum Ultraviolet

    Science.gov (United States)

    Nave, Gillian; Sansonetti, C. J.; Szabo, C. I.

    2008-05-01

    Transitionsin singly-ionized and doubly-ionized iron-group elements give rise to prominent emission lines from a wide variety of astrophysical objects. Although the database of experimental oscillator strengths of Fe II has also been greatly extended by the FERRUM project, few experimental oscillator strengths are available in the region below 1600 Å, where many levels that give rise to emission lines at longer wavelengths have their dominant decays. The established way to measure accurate oscillator strengths for atomic lines combines the measurement of a lifetime of an upper energy level with a separate measurement of the branching fractions of all the lines emitted from that level. This technique relies on being able to observe all the spectral lines emitted by the upper level, which range down to Ly-α or below for many fluorescence lines. We have developed techniques to measure branching fractions in the vacuum ultraviolet using our 10.7-m normal incidence grating spectrograph. For this we use phosphor image plates as replacements for the photographic plates previously used on this instrument. Image plates are sensitive to wavelengths from the X-ray region to 2200 Å, and have a linear intensity response with a dynamic range of at least 10000. We have recorded spectra of iron-neon hollow cathode and Penning discharges, using a deuterium standard lamp for radiometric calibration. We will present the first measurements of oscillator strengths using this technique. We are also investigating methods of radiometric calibration below 1150 Å using hollow cathode standard lamps. This will enable us to measure branching ratios down to 800 Å or below. This work is partially funded by NASA under the inter-agency agreement W-10,255.

  9. A molecular dynamics and circular dichroism study of a novel synthetic antimicrobial peptide

    Science.gov (United States)

    Rodina, N. P.; Yudenko, A. N.; Terterov, I. N.; Eliseev, I. E.

    2013-08-01

    Antimicrobial peptides are a class of small, usually positively charged amphiphilic peptides that are used by the innate immune system to combat bacterial infection in multicellular eukaryotes. Antimicrobial peptides are known for their broad-spectrum antimicrobial activity and thus can be used as a basis for a development of new antibiotics against multidrug-resistant bacteria. The most challengeous task on the way to a therapeutic use of antimicrobial peptides is a rational design of new peptides with enhanced activity and reduced toxicity. Here we report a molecular dynamics and circular dichroism study of a novel synthetic antimicrobial peptide D51. This peptide was earlier designed by Loose et al. using a linguistic model of natural antimicrobial peptides. Molecular dynamics simulation of the peptide folding in explicit solvent shows fast formation of two antiparallel beta strands connected by a beta-turn that is confirmed by circular dichroism measurements. Obtained from simulation amphipatic conformation of the peptide is analysed and possible mechanism of it's interaction with bacterial membranes together with ways to enhance it's antibacterial activity are suggested.

  10. Sensing site-specific structural characteristics and chirality using vibrational circular dichroism of isotope labeled peptides.

    Science.gov (United States)

    Keiderling, Timothy A

    2017-10-04

    Isotope labeling has a long history in chemistry as a tool for probing structure, offering enhanced sensitivity, or enabling site selection with a wide range of spectroscopic tools. Chirality sensitive methods such as electronic circular dichroism are global structural tools and have intrinsically low resolution. Consequently, they are generally insensitive to modifications to enhance site selectivity. The use of isotope labeling to modify vibrational spectra with unique resolvable frequency shifts can provide useful site-specific sensitivity, and these methods have been recently more widely expanded in biopolymer studies. While the spectral shifts resulting from changes in isotopic mass can provide resolution of modes from specific parts of the molecule and can allow detection of local change in structure with perturbation, these shifts alone do not directly indicate structure or chirality. With vibrational circular dichroism (VCD), the shifted bands and their resultant sign patterns can be used to indicate local conformations in labeled biopolymers, particularly if multiple labels are used and if their coupling is theoretically modeled. This mini-review discusses selected examples of the use of labeling specific amides in peptides to develop local structural insight with VCD spectra. © 2017 Wiley Periodicals, Inc.

  11. Homonuclear 1H NMR and circular dichroism study of the HIV-1 Tat Eli variant

    Science.gov (United States)

    Watkins, Jennifer D; Campbell, Grant R; Halimi, Hubert; Loret, Erwann P

    2008-01-01

    Background The HIV-1 Tat protein is a promising target to develop AIDS therapies, particularly vaccines, due to its extracellular role that protects HIV-1-infected cells from the immune system. Tat exists in two different lengths, 86 or 87 residues and 99 or 101 residues, with the long form being predominant in clinical isolates. We report here a structural study of the 99 residue Tat Eli variant using 2D liquid-state NMR, molecular modeling and circular dichroism. Results Tat Eli was obtained from solid-phase peptide synthesis and the purified protein was proven biologically active in a trans-activation assay. Circular dichroism spectra at different temperatures up to 70°C showed that Tat Eli is not a random coil at 20°C. Homonuclear 1H NMR spectra allowed us to identify 1639 NMR distance constraints out of which 264 were interresidual. Molecular modeling satisfying at least 1474 NMR constraints revealed the same folding for different model structures. The Tat Eli model has a core region composed of a part of the N-terminus including the highly conserved Trp 11. The extra residues in the Tat Eli C-terminus protrude from a groove between the basic region and the cysteine-rich region and are well exposed to the solvent. Conclusion We show that active Tat variants share a similar folding pattern whatever their size, but mutations induce local structural changes. PMID:18808674

  12. Going deep into protein secondary structure with synchrotron radiation circular dichroism spectroscopy.

    Science.gov (United States)

    Kumagai, Patricia S; Araujo, Ana P U; Lopes, Jose L S

    2017-10-01

    Circular dichroism (CD) spectroscopy is a fast, powerful, well-established, and widely used analytical technique in the biophysical and structural biology community to study protein secondary structure and to track changes in protein conformation in different environments. The use of the intense light of a synchrotron beam as the light source for collecting CD measurements has emerged as an enhanced method, known as synchrotron radiation circular dichroism (SRCD) spectroscopy, that has several advantages over the conventional CD method, including a significant spectral range extension for data collection, deeper access to the lower limit (cut-off) of conventional CD spectroscopy, an improved signal-to-noise ratio to increase accuracy in the measurements, and the possibility to collect measurements in highly absorbing solutions. In this review, we discuss different applications of the SRCD technique by researchers from Latin America. In this context, we specifically look at the use of this method for examining the secondary structure and conformational behavior of proteins belonging to the four main classes of the hierarchical protein domain classification CATH (Class, Architecture, Topology, Homology) database, focusing on the advantages and improvements associated with SRCD spectroscopy in terms of characterizing proteins composed of different structural elements.

  13. Circular Dichroism is Sensitive to Monovalent Cation Binding in Monensin Complexes.

    Science.gov (United States)

    Nedzhib, Ahmed; Kessler, Jiří; Bouř, Petr; Gyurcsik, Béla; Pantcheva, Ivayla

    2016-05-01

    Monensin is a natural antibiotic that exhibits high affinity to certain metal ions. In order to explore its potential in coordination chemistry, circular dichroism (CD) spectra of monensic acid A (MonH) and its derivatives containing monovalent cations (Li(+) , Na(+) , K(+) , Rb(+) , Ag(+) , and Et4 N(+) ) in methanolic solutions were measured and compared to computational models. Whereas the conventional CD spectroscopy allowed recording of the transitions down to 192 nm, synchrotron radiation circular dichroism (SRCD) revealed other bands in the 178-192 nm wavelength range. CD signs and intensities significantly varied in the studied compounds, in spite of their similar crystal structure. Computational modeling based on the Density Functional Theory (DFT) and continuum solvent model suggests that the solid state monensin structure is largely conserved in the solutions as well. Time-dependent Density Functional Theory (TDDFT) simulations did not allow band-to-band comparison with experimental spectra due to their limited precision, but indicated that the spectral changes were caused by a combination of minor conformational changes upon the monovalent cation binding and a direct involvement of the metal electrons in monensin electronic transitions. Both the experiment and simulations thus show that the CD spectra of monensin complexes are very sensitive to the captured ions and can be used for their discrimination. Chirality 28:420-428, 2016. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

  14. Advantages of synchrotron radiation circular dichroism spectroscopy to study intrinsically disordered proteins.

    Science.gov (United States)

    Kumagai, Patricia S; DeMarco, Ricardo; Lopes, Jose L S

    2017-03-03

    The unordered secondary structural content of an intrinsically disordered protein (IDP) is susceptible to conformational changes induced by many different external factors, such as the presence of organic solvents, removal of water, changes in temperature, binding to partner molecules, and interaction with lipids and/or other ligands. In order to characterize the high-flexibility nature of an IDP, circular dichroism (CD) spectroscopy is a particularly useful method due to its capability of monitoring both subtle and remarkable changes in different environments, relative ease in obtaining measurements, the small amount of sample required, and the capability for sample recovery (sample not damaged) and others. Using synchrotron radiation as the light source for CD spectroscopy represents the state-of-the-art version of this technique with feasibility of accessing the lower wavelength UV region, and therefore presenting a series of advantages over conventional circular dichroism (cCD) to monitor a protein conformational behavior, check protein stability, detect ligand binding, and many others. In this paper, we have performed a comparative study using cCD and SRCD methods for investigating the secondary structure and the conformational behavior of natively unfolded proteins: MEG-14 and soybean trypsin inhibitor. We show that the SRCD technique greatly improves the analysis and accuracy of the studies on the conformations of IDPs.

  15. A Solid Phase Vibrational Circular Dichroism Study of Polypeptide-Surfactant Interaction.

    Science.gov (United States)

    Novotná, Pavlína; Urbanová, Marie

    2015-12-01

    We studied the interaction of poly-l-lysine (PLL) and poly-l-arginine (PLAG) with sodium dodecyl sulfate (SDS) surfactant and the interaction of poly-l-glutamic acid (PLGA) and poly-l-aspartic acid (PLAA) with tetradecyltrimethylammonium bromide (TTAB) surfactant using vibrational circular dichroism (VCD) spectroscopy in the region of C-H stretching vibration and in the Amide I region both in solution and in mulls. A chirality transfer from polypeptides to achiral surfactants was observed in the C-H stretching region, where measurements in solution were impossible. This observation was enabled by a special sample treatment technique using lyophilization and the preparation of mulls. This technique demonstrated itself as an interesting and beneficial tool for VCD measurements. In addition, we observed that SDS changed the secondary structure of PLL to the β-sheet and of PLAG to the α-helix. TTAB disrupted the PLGA and PLAA structure. These results were obtained in the mull but were confirmed by the VCD spectra measured in solution and by electronic circular dichroism. The chirality transfer from the polypeptides to SDS was caused by polypeptides ordered into a specific conformation during the interaction, while in the TTBA system it was induced primarily by the chirality of the amino acid residues. © 2015 Wiley Periodicals, Inc.

  16. Biophysical and structural characterisation of nucleic acid complexes with modified cyclodextrins using circular dichroism.

    Science.gov (United States)

    O'Mahony, Aoife M; Cronin, Michael F; McMahon, Anthony; Evans, James C; Daly, Kathleen; Darcy, Raphael; O'Driscoll, Caitriona M

    2014-05-01

    Modified cyclodextrins (CDs) have shown great promise as non-viral gene and siRNA delivery vectors in a range of in vitro and in vivo studies. In the current study, structural and biophysical characterisation of selected CDs was carried out to enhance our understanding of their interaction with nucleic acids. The methods used for such characterisation were dynamic light scattering, zeta potential measurements and circular dichroism. Variations in the chemistries of individual CDs and in the type of formulation were shown to affect key properties of complexes such as size, surface charge and nucleic acid conformation. Furthermore, the effects of temperature and pH on the conformation of nucleic acids were investigated. pH studies were intended to mimic the conditions encountered by cationic complexes during endocytosis. Circular dichroism studies revealed that changes occurred in DNA and siRNA conformation upon complexation with CDs and when exposed to increasing temperature and decreasing pH. Overall, siRNA appeared to be more susceptible to conformational changes although complexation of siRNA with CDs tended to have a stabilising effect. © 2014 Wiley Periodicals, Inc. and the American Pharmacists Association.

  17. Sum rule distortions in fluorescence-yield x-ray magnetic circular dichroism

    Science.gov (United States)

    Liu, Boyang; Piamonteze, Cinthia; Delgado-Jaime, Mario Ulises; Wang, Ru-Pan; Heidler, Jakoba; Dreiser, Jan; Chopdekar, Rajesh; Nolting, Frithjof; de Groot, Frank M. F.

    2017-08-01

    The quantitative analysis of 3 d transition metal L2 ,3 edge x-ray magnetic circular dichroism (XMCD) spectra and the related sum rules are compared for measurements with electron yield and fluorescence yield detection. Multiplet calculations on divalent ions show that fluorescence yield detected sum rule derived expectation values of Lz and Sz show noticeable deviations and detection angle dependence. We show that small deviations of the polarization dependent fluorescent decay values lead to significant deviations in the Lz and Sz sum rule values. Fe and Co experimental XMCD spectra of a supported 10 nm CoFe2O4 thin film are measured simultaneously by both electron and fluorescence yield. The deviations shown in the experimental data are well explained by the calculations and are shown to mainly depend on the polarization dependent total decay. We conclude that fluorescence yield detected x-ray magnetic circular dichroism is unsuitable for quantitative analysis of the Lz and Sz sum rule values.

  18. Ab initio electronic circular dichroism of fullerenes, single-walled carbon nanotubes, and ligand-protected metal nanoparticles.

    Science.gov (United States)

    Noguez, Cecilia; Hidalgo, Francisco

    2014-09-01

    The versatility and applicability of a time-perturbed density functional method implemented within the SIESTA program package to calculate electronic circular dichroism of diverse nanoparticles is discussed. Results for nanostructures, such as fullerenes, single-wall carbon nanotubes, as well as metallic nanoparticles composed of up to hundreds of atoms were examined by comparison with previously reported experimental and theoretical results. In all cases, the calculated electronic circular dichroism shows very good consistency with other calculations, and a remarkable agreement with experiments. It is concluded that such a high-level method provides theoretical support for the quantification, understanding, and prediction of chirality and its measurement in nanostructures. It is expected that this information would be useful to motivate further experimental studies and interpretation of optical activity in terms of electronic circular dichroism in novel nanostructures. © 2014 Wiley Periodicals, Inc.

  19. Femtosecond X-ray magnetic circular dichroism absorption spectroscopy at an X-ray free electron laser

    Science.gov (United States)

    Higley, Daniel J.; Hirsch, Konstantin; Dakovski, Georgi L.; Jal, Emmanuelle; Yuan, Edwin; Liu, Tianmin; Lutman, Alberto A.; MacArthur, James P.; Arenholz, Elke; Chen, Zhao; Coslovich, Giacomo; Denes, Peter; Granitzka, Patrick W.; Hart, Philip; Hoffmann, Matthias C.; Joseph, John; Le Guyader, Loïc; Mitra, Ankush; Moeller, Stefan; Ohldag, Hendrik; Seaberg, Matthew; Shafer, Padraic; Stöhr, Joachim; Tsukamoto, Arata; Nuhn, Heinz-Dieter; Reid, Alex H.; Dürr, Hermann A.; Schlotter, William F.

    2016-03-01

    X-ray magnetic circular dichroism spectroscopy using an X-ray free electron laser is demonstrated with spectra over the Fe L3,2-edges. The high brightness of the X-ray free electron laser combined with high accuracy detection of incident and transmitted X-rays enables ultrafast X-ray magnetic circular dichroism studies of unprecedented sensitivity. This new capability is applied to a study of all-optical magnetic switching dynamics of Fe and Gd magnetic sublattices in a GdFeCo thin film above its magnetization compensation temperature.

  20. Determination of the folding of proteins as a function of denaturants, osmolytes or ligands using circular dichroism

    Science.gov (United States)

    Greenfield, Norma J.

    2009-01-01

    Circular dichroism (CD) is an excellent tool for examining the interactions and stability of proteins. This protocol covers methods to obtain and analyze circular dichroism spectra to measure changes in the folding of proteins as a function of denaturants, osmolytes or ligands. Applications include determination of the free energy of folding of a protein, the effects of mutations on protein stability and the estimation of binding constants for the interactions of proteins with other proteins, DNA or ligands, such as substrates or inhibitors. The experiments take 2-5 h. PMID:17406529

  1. Enantioselective semi-preparative HPLC separation of PCB metabolites and their absolute structures determined by electronic and vibrational circular dichroism

    Energy Technology Data Exchange (ETDEWEB)

    Tuan, H.P.; Larsson, C.; Huehnerfuss, H. [Hamburg Univ. (Germany). Inst. fuer Organische Chemie; Hoffmann, F.; Froeba, M. [Giessen Univ. (Germany). Inst. fuer Anorganische und Analytische Chemie; Bergmann, Aa. [Stockholm Univ. (Sweden). Dept. of Environmental Chemistry

    2004-09-15

    The present paper represents a first result of an ongoing systematic study of atropisomeric methylsulfonyl, methylthionyl, hydroxy, and methoxy metabolites of environmentally most relevant PCBs. This involves semi-preparative enantioselective HPLC separation to obtain pure atropisomers from synthesized PCB metabolite standards, their configuration estimation using the electronic circular dichroism (UV-CD) method and the determination / confirmation of these absolute configurations applying the combined vibrational circular dichroism (VCD) / ab initio approach. The following substances have been investigated: 4-HO-, 4-MeO-, 4-MeS-, 4-MeSO2-, 3-MeS- and 3-MeSO{sub 2}-CB149.

  2. Femtosecond X-ray magnetic circular dichroism absorption spectroscopy at an X-ray free electron laser.

    Science.gov (United States)

    Higley, Daniel J; Hirsch, Konstantin; Dakovski, Georgi L; Jal, Emmanuelle; Yuan, Edwin; Liu, Tianmin; Lutman, Alberto A; MacArthur, James P; Arenholz, Elke; Chen, Zhao; Coslovich, Giacomo; Denes, Peter; Granitzka, Patrick W; Hart, Philip; Hoffmann, Matthias C; Joseph, John; Le Guyader, Loïc; Mitra, Ankush; Moeller, Stefan; Ohldag, Hendrik; Seaberg, Matthew; Shafer, Padraic; Stöhr, Joachim; Tsukamoto, Arata; Nuhn, Heinz-Dieter; Reid, Alex H; Dürr, Hermann A; Schlotter, William F

    2016-03-01

    X-ray magnetic circular dichroism spectroscopy using an X-ray free electron laser is demonstrated with spectra over the Fe L(3,2)-edges. The high brightness of the X-ray free electron laser combined with high accuracy detection of incident and transmitted X-rays enables ultrafast X-ray magnetic circular dichroism studies of unprecedented sensitivity. This new capability is applied to a study of all-optical magnetic switching dynamics of Fe and Gd magnetic sublattices in a GdFeCo thin film above its magnetization compensation temperature.

  3. Femtosecond X-ray magnetic circular dichroism absorption spectroscopy at an X-ray free electron laser

    Energy Technology Data Exchange (ETDEWEB)

    Higley, Daniel J., E-mail: dhigley@stanford.edu; Yuan, Edwin [SLAC National Accelerator Laboratory, 2575 Sand Hill Road, Menlo Park, California 94025 (United States); Department of Applied Physics, Stanford University, Stanford, California 94305 (United States); Hirsch, Konstantin; Dakovski, Georgi L.; Jal, Emmanuelle; Lutman, Alberto A.; Coslovich, Giacomo; Hart, Philip; Hoffmann, Matthias C.; Mitra, Ankush; Moeller, Stefan; Ohldag, Hendrik; Seaberg, Matthew; Stöhr, Joachim; Nuhn, Heinz-Dieter; Reid, Alex H.; Dürr, Hermann A.; Schlotter, William F. [SLAC National Accelerator Laboratory, 2575 Sand Hill Road, Menlo Park, California 94025 (United States); Liu, Tianmin; MacArthur, James P. [SLAC National Accelerator Laboratory, 2575 Sand Hill Road, Menlo Park, California 94025 (United States); Department of Physics, Stanford University, Stanford, California 94305 (United States); and others

    2016-03-15

    X-ray magnetic circular dichroism spectroscopy using an X-ray free electron laser is demonstrated with spectra over the Fe L{sub 3,2}-edges. The high brightness of the X-ray free electron laser combined with high accuracy detection of incident and transmitted X-rays enables ultrafast X-ray magnetic circular dichroism studies of unprecedented sensitivity. This new capability is applied to a study of all-optical magnetic switching dynamics of Fe and Gd magnetic sublattices in a GdFeCo thin film above its magnetization compensation temperature.

  4. Suppressed magnetic circular dichroism and valley-polarized magnetoabsorption due to the mass anisotopy in Bi

    Science.gov (United States)

    Kuzmenko, Alexey B.

    We measure broadband far-infrared magneto-optical conductivity spectra of pure bismuth separately for left- and right-handed circular polarizations in magnetic fields up to 7 T that allows us to obtain the magnetic circular dichroism (MCD). Thanks to a high spectral resolution we distinguish the Landau level (LL) transitions in the Dirac-like electron and the parabolic hole bands. The hole transitions exhibit a full (100%) MCD as is indeed expected for a circular cyclotron orbit. However, the MCD for electron-pocket transitions is reduced to only 13 +/-1%. This strong suppression can be attributed to the huge effective-mass anisotropy ( 200) in the electron pockets and can be generally interpreted as a signature of the mismatch between the spatial metric experienced by the photons and the electrons. An important consequence of this observation is that the magneto-absorption in bismuth is highly valley sensitive, which paves the way to future valleytronic applications in materials with a strong effective-mass anisotropy.

  5. Magnetocrystalline anisotropy in FePd alloys studied using transverse X-ray magnetic circular dichroism

    Energy Technology Data Exchange (ETDEWEB)

    Dhesi, S.S. E-mail: dhesi@esrf.fr; Laan, G. van der; Duerr, H.A.; Belakhovsky, M.; Marchesini, S.; Kamp, P.; Marty, A.; Gilles, B.; Rogalev, A

    2001-05-01

    The structural and magnetic properties of Fe{sub 0.5}Pd{sub 0.5} alloys have been correlated using X-ray diffraction (XD), vibrating sample magnetometry (VSM) and transverse X-ray magnetic circular dichroism (TXMCD) at the Pd L{sub 2,3} edges. XD indicates that codeposition of Fe and Pd, at elevated temperatures (350 deg. C), results in a well-ordered L1{sub 0} phase which exhibits perpendicular magnetic anisotropy (PMA). On the other hand, codeposition at room temperature results in a disordered phase with in-plane easy-axis of magnetization. By codepositing at intermediate temperatures, a series of alloys has been produced with varying degree of compositional order. The TXMCD results show that increased compositional ordering leads to an increased orbital moment anisotropy favouring PMA. The magnetocrystalline anisotropy energy resulting from the orbital anisotropy is compared to VSM results.

  6. Feasibility of non-invasive optical blood-glucose detection using overtone circular dichroism

    CERN Document Server

    Hokr, Brett H; Meng, Zhaokai; Petrov, Georgi I; Yakovlev, Vladislav V

    2016-01-01

    Diabetes is one of the most debilitating and costly diseases currently plaguing humanity. It is a leading cause of death and dismemberment in the world, and we know how to treat it. Accurate, continuous monitoring and control of blood glucose levels via insulin treatments are widely known to mitigate the majority of detrimental effects caused by the disease. The primary limitation of continuous glucose monitoring is patient non-compliance due to the unpleasant nature of "finger-stick" testing methods. This limitation can be largely, or even completely, removed by non-invasive testing methods. In this report, we demonstrate the vibrational overtone circular dichroism properties of glucose and analyze its use as a method of non-invasive glucose monitoring, capable of assuaging this trillion dollar scourge.

  7. Chirality detection of two enantiomorphic 3D lanthanide coordination polymers by vibrational circular dichroism spectra.

    Science.gov (United States)

    Zheng, Xiu-Ying; Zhang, Han; Cao, Ling-Yun; Kong, Xiang-Jian; Long, La-Sheng; Zheng, Lan-Sun

    2015-03-28

    Two enantiomorphic 3D lanthanide coordination polymers of {[Dy5(L)4(H2O)10][Dy(H2O)7][Na(H2O)5]}·(ClO4)7·(H2O)15 (1a for R and 1b for S) with chiral helical chains were synthesized based on an achiral ligand N-(2-hydroxyethyl)ethylenediamine-N,N',N'-triacetic acid (H3L) and Dy(ClO4)3. Crystal analysis revealed that 1a and 1b were crystallized in chiral space groups P4132 and P4332, respectively. The absolute configurations of the two structures were evidenced by vibrational circular dichroism (VCD) spectra with one single crystal sample.

  8. Beta sheets with a twist: the conformation of helical polyisocyanopeptides determined by using vibrational circular dichroism.

    Science.gov (United States)

    Schwartz, Erik; Liégeois, Vincent; Koepf, Matthieu; Bodis, Pavol; Cornelissen, Jeroen J L M; Brocorens, Patrick; Beljonne, David; Nolte, Roeland J M; Rowan, Alan E; Woutersen, Sander; Champagne, Benoît

    2013-09-23

    Detailed information on the architecture of polyisocyanopeptides based on vibrational circular dichroism (VCD) spectroscopy in combination with DFT calculations is presented. It is demonstrated that the screw sense of the helical polyisocyanides can be determined directly from the C=N-stretch vibrational region of the VCD spectrum. Analysis of the VCD signals associated with the amide I and amide II modes provides detailed information on the peptide side-chain arrangement in the polymer and indicates the presence of a helical β-sheet architecture, in which the dihedral angles are slightly different to those of natural β-sheet helices. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Switchable amplification of vibrational circular dichroism as a probe of local chiral structure.

    Science.gov (United States)

    Domingos, Sérgio R; Sanders, Hans J; Hartl, František; Buma, Wybren J; Woutersen, Sander

    2014-12-15

    A new method to detect the vibrational circular dichroism (VCD) of a localized part of a chiral molecular system is reported. A local VCD amplifier was implemented, and the distance dependence of the amplification was investigated in a series of peptides. The results indicate a characteristic distance of 2.0±0.3 bonds, which suggests that the amplification is a localized phenomenon. The amplifier can be covalently coupled to a specific part of a molecule, and can be switched ON and OFF electrochemically. By subtracting the VCD spectra obtained when the amplifier is in the ON and OFF states, the VCD of the local environment of the amplifier can be separated from the total VCD spectrum. Switchable local VCD amplification thus makes it possible to "zoom in" on a specific part of a chiral molecule. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Elucidating the backbone conformation of photoswitchable foldamers using vibrational circular dichroism.

    Science.gov (United States)

    Domingos, Sérgio R; Roeters, Steven J; Amirjalayer, Saeed; Yu, Zhilin; Hecht, Stefan; Woutersen, Sander

    2013-10-28

    The backbone conformation of amphiphilic oligo(azobenzene) foldamers is investigated using vibrational circular dichroism (VCD) spectroscopy on a mode involving the stretching of the N=N bonds in the backbone. From denaturation experiments, we find that the VCD response in the helical conformation arises mainly from through-space interaction between the N=N-stretch transition-dipole moments, so that the coupled-oscillator model can be used to predict the VCD spectrum associated with a particular conformation. Using this approach, we elucidate the origin of the VCD signals in the folded conformation, and can assign the observed partial loss of VCD signals upon photo-induced unfolding to specific conformational changes. Our results show that the N=N-stretch VCD response provides an excellent probe of the helical conformation of the N=N bonds in this type of switchable molecular system.

  11. Absolute configuration of podophyllotoxin related lignans from Bursera fagaroides using vibrational circular dichroism.

    Science.gov (United States)

    Velázquez-Jiménez, René; Torres-Valencia, J Martín; Cerda-García-Rojas, Carlos M; Hernández-Hernández, Juan D; Román-Marín, Luisa U; Manríquez-Torres, J Jesús; Gómez-Hurtado, Mario A; Valdez-Calderón, Alejandro; Motilva, Virginia; García-Mauriño, Sofía; Talero, Elena; Avila, Javier; Joseph-Nathan, Pedro

    2011-12-01

    The ethanol extract from the dried exudate of Bursera fagaroides (Burseraceae) showed significant cytotoxic activity in the HT-29 (human colon adenocarcinoma) test system. The extract provided four podophyllotoxin related lignans, identified as (7'R,8R,8'R)-(-)-deoxypodophyllotoxin (3), (7'R,8R,8'R)-(-)-morelensin (4), (8R,8'R)-(-)-yatein (5), and (8R,8'R)-(-)-5'-desmethoxyyatein (6), whose spectroscopic and chiroptical properties were compared with those of (7R,7'R,8R,8'R)-(-)-podophyllotoxin (1) and its acetyl derivative (2). Their absolute configurations were assigned by comparison of the vibrational circular dichroism spectra of 1 and 3 with those obtained by density functional theory calculations. Copyright © 2011 Elsevier Ltd. All rights reserved.

  12. A study of aliphatic amino acids using simulated vibrational circular dichroism and Raman optical activity spectra

    CERN Document Server

    Ganesan, Aravindhan; Wang, Feng

    2013-01-01

    Vibrational optical activity (VOA) spectra, such as vibrational circular dichroism (VCD) and Raman optical activity (ROA) spectra, of aliphatic amino acids are simulated using density functional theory (DFT) methods in both gas phase (neutral form) and solution (zwitterionic form), together with their respective infrared (IR) and Raman spectra of the amino acids. The DFT models, which are validated by excellent agreements with the available experimental Raman and ROA spectra of alanine in solution, are employed to study other aliphatic amino acids. The inferred (IR) intensive region (below 2000 cm-1) reveals the signature of alkyl side chains, whereas the Raman intensive region (above 3000 cm-1) contains the information of the functional groups in the amino acids. Furthermore, the chiral carbons of the amino acids (except for glycine) dominate the VCD and ROA spectra in the gas phase, but the methyl group vibrations produce stronger VCD and ROA signals in solution. The C-H related asymmetric vibrations domina...

  13. Dodine as a transparent protein denaturant for circular dichroism and infrared studies.

    Science.gov (United States)

    Guin, Drishti; Sye, Kori; Dave, Kapil; Gruebele, Martin

    2016-05-01

    The fungicide dodine combines the cooperative denaturation properties of guanidine with the mM denaturation activity of SDS. It was previously tested only on two small model proteins. Here we show that it can be used as a chemical denaturant for phosphoglycerate kinase (PGK), a much larger two-domain enzyme. In addition to its properties as a chemical denaturant, dodine facilitates thermal denaturation of PGK, and we show for the first time that it also facilitates pressure denaturation of a protein. Much higher quality circular dichroism and amide I' infrared spectra of PGK can be obtained in dodine than in guanidine, opening the possibility for use of dodine as a denaturant when UV or IR detection is desirable. One caution is that dodine denaturation, like other detergent-based denaturants, is less reversible than guanidine denaturation. © 2016 The Protein Society.

  14. Effects of Trehalose on Thermodynamic Properties of Alpha-synuclein Revealed through Synchrotron Radiation Circular Dichroism

    Science.gov (United States)

    Ruzza, Paolo; Hussain, Rohanah; Biondi, Barbara; Calderan, Andrea; Tessari, Isabella; Bubacco, Luigi; Siligardi, Giuliano

    2015-01-01

    Many neurodegenerative diseases, including Huntington’s, Alzheimer’s and Parkinson’s diseases, are characterized by protein misfolding and aggregation. The capability of trehalose to interfere with protein misfolding and aggregation has been recently evaluated by several research groups. In the present work, we studied, by means of synchrotron radiation circular dichroism (SRCD) spectroscopy, the dose-effect of trehalose on α-synuclein conformation and/or stability to probe the capability of this osmolyte to interfere with α-synuclein’s aggregation. Our study indicated that a low trehalose concentration stabilized α-synuclein folding much better than at high concentration by blocking in vitro α-synuclein’s polymerisation. These results suggested that trehalose could be associated with other drugs leading to a new approach for treating Parkinson’s and other brain-related diseases. PMID:25946077

  15. Chirality sensing of bioactive compounds with amino alcohol unit via circular dichroism.

    Science.gov (United States)

    Górecki, Marcin; Groszek, Grażyna; Frelek, Jadwiga

    2017-10-01

    The aim of the present work was to test various chiroptical techniques, including in particular the in situ dirhodium methodology, to assign the absolute configuration of 1,2- and 1,3-amino alcohols. As models, we selected mainly compounds that have both an additional strongly absorbing and interfering chromophoric system and application in medicinal chemistry. Determination of the absolute configuration (AC) of the tested molecules such as cinchona alkaloids, Tamiflu, and others was carried out using a combination of electronic and vibrational circular dichroism (ECD, VCD) spectroscopy. It has been demonstrated that both 1,2- and 1,3-aminol moieties are subject to the same sector rule correlating stereostructure of formed Rh2 -complex with chiroptical properties, and that the changes in the position of the stereogenic center do not affect its proper use. © 2017 Wiley Periodicals, Inc.

  16. Elucidation of the absolute configuration of rhizopine by chiral supercritical fluid chromatography and vibrational circular dichroism.

    Science.gov (United States)

    Krief, Alain; Dunkle, Melissa; Bahar, Masoud; Bultinck, Patrick; Herrebout, Wouter; Sandra, Pat

    2015-07-01

    The absolute configuration of rhizopine, an opine-like natural product present in nitrogen-fixing nodules of alfalfa infected by rhizobia, is elucidated using a combination of state-of-the-art analytical and semi-preparative supercritical fluid chromatography and vibrational circular dichroism spectroscopy. A synthetic peracetylated racemate was fractionated into its enantiomers and subjected to absolute configuration analysis revealing that natural rhizopine exists as a single enantiomer. The stereochemistry of non-derivatized natural rhizopine corresponds to (1R,2S,3R,4R,5S,6R)-4-amino-6-methoxycyclohexane-1,2,3,5-tetraol. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Sizeable magnetic circular dichroism of artificially precipitated Co clusters in amorphous carbon

    Directory of Open Access Journals (Sweden)

    H. S. Hsu

    2012-09-01

    Full Text Available This study examines sizeable magnetic circular dichroism (MCD in Co(20%-doped amorphous carbon (a-C films. While as-grown films exhibit a non-detectable MCD signal, films that undergo rapid thermal annealing (RTA at 600°C in a vacuum yield broad MCD spectra with a large amplitude of ∼3.9 × 104 deg/cm in saturation field 0.78 T at the σ-σ* gap transition (∼5.5 eV. In such films after RTA, the metastable Co-C bonding is decomposed and suitable Co nanoparticles/a-C interfaces are thus formed. Our results indicate that the large change in MCD is contributed from Co nanoparticles and associated with the spin-dependent electronic structure at the Co/a-C interfaces.

  18. Circular dichroism of stem bromelain: a third spectral class within the family of cysteine proteinases.

    Science.gov (United States)

    Arroyo-Reyna, A; Hernandez-Arana, A; Arreguin-Espinosa, R

    1994-01-01

    Two forms of stem bromelain (EC 3.4.22.4) were isolated from commercial, crude and chromatographically purified preparations of the enzyme by means of gel-filtration and cation-exchange liquid chromatography. These forms possess nearly identical secondary and tertiary structures, as judged from their circular dichroism (c.d.) spectra. The spectral characteristics of stem bromelain suggest that this enzyme belongs to the alpha + beta protein class, as other cysteine proteinases do. In agreement with these results, quantitative estimation of secondary structures yielded amounts similar to those for papain and proteinase omega. However, the bromelain c.d. curve is clearly distinguishable from those reported for papain and proteinase omega, on one hand, and that of chymopapain, on the other. Thus, it is apparent that there are at least three types of c.d. spectra associated with the family of cysteine proteinases. PMID:8198520

  19. Magnetic field dependence of the circular dichroism in EuTe

    Energy Technology Data Exchange (ETDEWEB)

    Henriques, A B [Instituto de Fisica, Universidade de Sao Paulo, Caixa Postal 66318, 05315-970 Sao Paulo (Brazil); Galgano, G D [Instituto de Fisica, Universidade de Sao Paulo, Caixa Postal 66318, 05315-970 Sao Paulo (Brazil); DIaz, B L [LAS-INPE, Avenida dos Astronautas, 1758-Jd. Granja, 12227-010, Sao Jose dos Campos (Brazil); Rappl, P H O [LAS-INPE, Avenida dos Astronautas, 1758-Jd. Granja, 12227-010, Sao Jose dos Campos (Brazil); Abramof, E [LAS-INPE, Avenida dos Astronautas, 1758-Jd. Granja, 12227-010, Sao Jose dos Campos (Brazil)

    2007-10-10

    The absorption magnetic circular dichroism in EuTe was investigated as a function of the magnetic field at T = 2 K. In order to describe the optical spectra theoretically, we developed a model that takes into account the magnetic order of the lattice as a function of the magnetic field. The model allows us to calculate the absorption spectrum as a continuous function of the magnetic field intensity. The theory accounts for the strongly dichroic absorption seen at high fields, and for its continuous evolution towards the B = 0 spectrum, which is described by a much weaker and much broader absorption line. The drastic changes observed in the experimental spectra as a function of magnetic field are fully explained by the dependence of the Eu{sup 2+} spin arrangement on the external magnetic field.

  20. Energetics, structures, vibrational frequencies, vibrational absorption, vibrational circular dichroism and Raman intensities of Leu-enkephalin

    DEFF Research Database (Denmark)

    Jalkanen, Karl J.

    2003-01-01

    Here we present several low energy conformers of Leu-enkephalin (LeuE) calculated with the density functional theory using the Becke 3LYP hybrid functional and the 6-31G* basis set. The structures, conformational energies, vibrational frequencies, vibrational absorption (VA) intensities......, vibrational circular dichroism (VCD) intensities and Raman scattering intensities are reported for the conformers of LeuE which are expected to be populated at room temperature. The species of LeuE-present in non-polar solvents is the neutral non-ionic species with the NH2 and CO2H groups, in contrast...... to the zwitterionic neutral species with the NH3+ and CO2- groups which predominates in aqueous solution and in the crystal. All of our attempts to find the zwitterionic species in the isolated state failed, with the result that a hydrogen atom from the positively charged N-terminus ammonium group transferred either...

  1. Vitamin E Circular Dichroism Studies: Insights into Conformational Changes Induced by the Solvent’s Polarity

    Directory of Open Access Journals (Sweden)

    Drew Marquardt

    2016-12-01

    Full Text Available We used circular dichroism (CD to study differences in CD spectra between α-, δ-, and methylated-α-tocopherol in solvents with different polarities. CD spectra of the different tocopherol structures differ from each other in intensity and peak locations, which can be attributed to chromanol substitution and the ability to form hydrogen bonds. In addition, each structure was examined in different polarity solvents using the Reichardt index—a measure of the solvent’s ionizing ability, and a direct measurement of solvent–solute interactions. Differences across solvents indicate that hydrogen bonding is a key contributor to CD spectra at 200 nm. These results are a first step in examining the hydrogen bonding abilities of vitamin E in a lipid bilayer.

  2. Relation between molecular electronic structure and nuclear spin-induced circular dichroism

    DEFF Research Database (Denmark)

    Štěpánek, Petr; Coriani, Sonia; Sundholm, Dage

    2017-01-01

    The recently theoretically described nuclear spin-induced circular dichroism (NSCD) is a promising method for the optical detection of nuclear magnetization. NSCD involves both optical excitations of the molecule and hyperfine interactions and, thus, it offers a means to realize a spectroscopy...... with the spatial distribution of the excited states and couplings between them, reflecting changes in molecular structure and conformation. This constitutes a marked difference to the nuclear magnetic resonance (NMR) chemical shift, which only reflects the local molecular structure in the ground electronic state...... are discussed. The results underline NSCD spectroscopy as a plausible tool with a power for the identification of not only different molecules, but their specific structures as well....

  3. Conformational effects on the circular dichroism of Human Carbonic Anhydrase II: a multilevel computational study.

    Directory of Open Access Journals (Sweden)

    Tatyana G Karabencheva-Christova

    Full Text Available Circular Dichroism (CD spectroscopy is a powerful method for investigating conformational changes in proteins and therefore has numerous applications in structural and molecular biology. Here a computational investigation of the CD spectrum of the Human Carbonic Anhydrase II (HCAII, with main focus on the near-UV CD spectra of the wild-type enzyme and it seven tryptophan mutant forms, is presented and compared to experimental studies. Multilevel computational methods (Molecular Dynamics, Semiempirical Quantum Mechanics, Time-Dependent Density Functional Theory were applied in order to gain insight into the mechanisms of interaction between the aromatic chromophores within the protein environment and understand how the conformational flexibility of the protein influences these mechanisms. The analysis suggests that combining CD semi empirical calculations, crystal structures and molecular dynamics (MD could help in achieving a better agreement between the computed and experimental protein spectra and provide some unique insight into the dynamic nature of the mechanisms of chromophore interactions.

  4. Circular dichroism spectroscopy: An efficient approach for the quantitation of ampicillin in presence of cloxacillin

    Science.gov (United States)

    Rahman, Nafisur; Khan, Sumaiya

    2016-05-01

    Ampicillin exhibited a negative and a positive cotton effects on the circular dichroism (CD) spectra in the wavelength range of 200-280 nm. Cloxacillin showed a positive cotton band peaking at 228 nm. Three sensitive, precise and accurate CD spectroscopic methods have been developed for the determination of ampicillin and cloxacillin. Method A was used for the determination of ampicillin in presence of cloxacillin by measuring ellipticity at 206 nm. Method B and C were employed to determine ampicillin and cloxacillin based on evaluation of ellipticity at 233 nm and 228 nm, respectively. Methods A, B and C showed linearity in the concentration range of 10-40 μg mL- 1, 5-40 μg mL- 1 ampicillin and 10-80 μg mL- 1 cloxacillin, respectively. The method A was successfully applied to the determination of ampicillin in commercial dosage forms containing equivalent amount of cloxacillin.

  5. Advances of Vibrational Circular Dichroism (VCD) in bioanalytical chemistry. A review.

    Science.gov (United States)

    Kurouski, Dmitry

    2017-10-16

    Vibrational Circular Dichroism (VCD) is a unique and relatively new spectroscopic technique that is capable of determining an absolute configuration of chiral molecules. VCD can be also used to determine structure of large macromolecules. This review highlights the most recent advances of VCD in bioanalytical chemistry. It shows that VCD is capable of unraveling supramolecular organization of peptides, proteins, saccharides, glycerophospholipids, polypeptide microcrystals, as well as amyloid fibrils and DNA. This review also demonstrates how VCD can be utilized to explore molecule-molecule interactions that determine mechanisms of chiral separations in chromatography. It aims to attract attention of scientists from all different research areas demonstrating the strength and capability of this very powerful spectroscopic technique. Copyright © 2017 Elsevier B.V. All rights reserved.

  6. Effects of Trehalose on Thermodynamic Properties of Alpha-synuclein Revealed through Synchrotron Radiation Circular Dichroism

    Directory of Open Access Journals (Sweden)

    Paolo Ruzza

    2015-05-01

    Full Text Available Many neurodegenerative diseases, including Huntington’s, Alzheimer’s and Parkinson’s diseases, are characterized by protein misfolding and aggregation. The capability of trehalose to interfere with protein misfolding and aggregation has been recently evaluated by several research groups. In the present work, we studied, by means of synchrotron radiation circular dichroism (SRCD spectroscopy, the dose-effect of trehalose on α-synuclein conformation and/or stability to probe the capability of this osmolyte to interfere with α-synuclein’s aggregation. Our study indicated that a low trehalose concentration stabilized α-synuclein folding much better than at high concentration by blocking in vitro α-synuclein’s polymerisation. These results suggested that trehalose could be associated with other drugs leading to a new approach for treating Parkinson’s and other brain-related diseases.

  7. Enhanced circular dichroism based on the dual-chiral metamaterial in terahertz regime

    Science.gov (United States)

    Jian, Shao; Jie, Li; Ying-Hua, Wang; Jia-Qi, Li; Zheng-Gao, Dong; Lin, Zhou

    2016-05-01

    The obvious circular dichroism (CD) and optical activity can be obtained based on the chiral metamaterial due to the plasmon-enhanced effect, which is very attractive for future compact devices with enhanced capabilities of light manipulation. In this paper, we propose a dual-chiral metamaterial composed of bilayer asymmetric split ring resonators (ASRR) that are in mirror-symmetry shape. It is demonstrated that the CD can get enhancement in the terahertz regime. Moreover, the CD can be further improved by modulating the asymmetry of ASRR. The enhanced CD effect in the terahertz regime has great potential applications in sensing, biomedical imaging, and molecular recognition. Project supported by the National Natural Science Foundation of China (Grant Nos. 11174051, 11374049, and 11204139), the Natural Science Foundation of Jiangsu Province of China (Grant No. BK20131283), and the Fundamental Research Funds for the Central Universities, China.

  8. X-ray absorption and magnetic circular dichroism studies of annealed magnetic tunnel junctions

    Science.gov (United States)

    Schmalhorst, J.; Sacher, M.; Thomas, A.; Brückl, H.; Reiss, G.; Starke, K.

    2005-06-01

    The magnetic and chemical interface properties of Mn -Ir/Co-Fe/Al+oxidation/Ni-Fe magnetic tunnel junctions are investigated for different barrier thickness, oxidation times, and annealing conditions by x-ray absorption spectroscopy and x-ray magnetic circular dichroism. For underoxidized samples the formation of Co-Fe-Al alloy at the lower barrier interface during optimal annealing is observed. For optimally oxidized and overoxidized samples FeOx is formed during oxidation, which is reduced by Mn diffusing to the barrier during annealing. The reduction of FeOx is accompanied by an increase of the interfacial magnetic Fe moment, whereas the Co moments hardly change with the postannealing. Comparison of these results with transport properties of the junctions shows that their polycrystalline structure has to be taken into account to understand the annealing temperature and oxidation state dependence of the tunneling magnetoresistance effect.

  9. Species-dependent binding of tocainide analogues to albumin: affinity chromatography and circular dichroism study.

    Science.gov (United States)

    Pistolozzi, Marco; Fortugno, Cecilia; Franchini, Carlo; Corbo, Filomena; Muraglia, Marilena; Roy, Myriam; Félix, Guy; Bertucci, Carlo

    2014-10-01

    A series of novel tocainide analogues were characterized for their HSA and RSA binding, by using high-performance liquid affinity chromatography (HPLAC) and circular dichroism (CD). In this HPLAC study, HSA and RSA were covalently immobilized to the silica matrix of HPLC columns, with a procedure that maintained unaltered the binding properties of the proteins. The tocainide analogues were ranked for their affinity to HSA and RSA on the basis of their bound fractions measured by the two albumin-based columns. This technique was also applied to characterize the high affinity binding sites of these tocainide analogues to the protein. For this purpose displacement experiments were carried out by means of increasing concentrations in the mobile phase of competitors known to bind selectively to the main binding sites of HSA. The results obtained with the immobilized proteins were confirmed by investigating the same drug-protein systems in solution by circular dichroism. The comparison of the data collected with both methodologies highlighted the dramatic effect of small differences in the amino acidic sequences of the two proteins. In fact, despite their similar primary and secondary structures, a small difference in the amino acidic sequence leads to significant differences in their three-dimensional structure reflecting their different binding capacity and their stereoselectivity. Therefore, this study confirms how it is crucial to consider the significant differences among the animal models when performing pharmacokinetic studies. It is also clear that the knowledge of serum carrier binding parameters at an early stage of drug discovery represents a great advantage that may help to save time and efforts. Copyright © 2014 Elsevier B.V. All rights reserved.

  10. Mid-infrared Plasmonic Circular Dichroism Generated by Graphene Nanodisk Assemblies

    Science.gov (United States)

    Kong, Xiang-Tian; Zhao, Runbo; Wang, Zhiming; Govorov, Alexander O.

    2017-08-01

    It is very interesting to bring plasmonic circular dichroism spectroscopy to the mid-infrared spectral interval, and there are two reasons for this. This spectral interval is very important for thermal bio-imaging and, simultaneously, this spectral range includes vibrational lines of many chiral biomolecules. Here we demonstrate that graphene plasmons indeed offer such opportunity. In particular, we show that chiral graphene assemblies consisting of a few graphene nanodisks can generate strong circular dichroism (CD) in the mid-infrared interval. The CD signal is generated due to the plasmon-plasmon coupling between adjacent nanodisks in the specially designed chiral graphene assemblies. Because of the large dimension mismatch between the thickness of a graphene layer and the incoming light's wavelength, three-dimensional configurations with a total height of a few hundred nanometers are necessary to obtain a strong CD signal in the mid-infrared range. The mid-infrared CD strength is mainly governed by the total dimensions (total height and helix scaffold radius) of the graphene nanodisk assembly, and by the plasmon-plasmon interaction strength between its constitutive nanodisks. Both positive and negative CD bands can be observed in the graphene assembly array. The frequency interval of the plasmonic CD spectra overlaps with the vibrational modes of some important biomolecules, such as DNA and many different peptides, giving rise to the possibility of enhancing the vibrational optical activity of these molecular species by attaching them to the graphene assemblies. Simultaneously the spectral range of chiral mid-infrared plasmons in our structures appears near the typical wavelength of the human-body thermal radiation and, therefore, our chiral metastructures can be potentially utilized as optical components in thermal imaging devices.

  11. Mutual structural effect of bilirubin and model membranes by vibrational circular dichroism.

    Science.gov (United States)

    Novotná, Pavlína; Goncharova, Iryna; Urbanová, Marie

    2014-03-01

    In this study, vibrational circular dichroism (VCD) spectroscopy was employed for the first time to study the bilirubin (BR) interaction with model membranes and models for membrane proteins. An enantioselective interaction of BR with zwitterionic 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) and sphingomyelin (SPM) liposomes was observed by VCD and electronic circular dichroism (ECD) complemented by absorption and fluorescence spectroscopy. The M-form of BR was preferentially recognized in the BR/DMPC system at concentration above 1×10(-4)M, for lower concentrations the P-form of BR was recognized by the DMPC liposomes. The VCD spectra also showed that the SPM liposomes, which represent the main component of nerve cell membrane, were significantly more disturbed by the presence of BR than the DMPC liposomes-a stable association with a strong VCD signal was observed providing the explanations for the supposed BR neurotoxicity. The effect of time and pH on the BR/DMPC or SPM liposome systems was shown to be essential while the effect of temperature in the range of 15-70°C was negligible demonstrating the surprisingly high temperature stability of BR when interacting with the studied membranes. The influence of a membrane protein was tested on a model consisting of poly-l-arginine (PLAG) bound in the α-helical form to the surface of 1,2-dimyristoyl-sn-glycero-3-phospho-(1'-rac-glycerol) liposomes and sodium dodecyl sulfate micelles. VCD and also ECD spectra showed that a variety of BR diastereoisomers interacted with PLAG in such systems. In a system of PLAG with micelles composed of sodium dodecyl sulfate, the M-form of bound BR was observed. Copyright © 2013 Elsevier B.V. All rights reserved.

  12. Characterisation of Conformational and Ligand Binding Properties of Membrane Proteins Using Synchrotron Radiation Circular Dichroism (SRCD).

    Science.gov (United States)

    Hussain, Rohanah; Siligardi, Giuliano

    Membrane proteins are notoriously difficult to crystallise for use in X-ray crystallographic structural determination, or too complex for NMR structural studies. Circular dichroism (CD) is a fast and relatively easy spectroscopic technique to study protein conformational behaviour in solution. The advantage of synchrotron radiation circular dichroism (SRCD) measured with synchrotron beamlines compared to the CD from benchtop instruments is the extended spectral far-UV region that increases the accuracy of secondary structure estimations, in particular under high ionic strength conditions. Membrane proteins are often available in small quantities, and for this SRCD measured at the Diamond B23 beamline has successfully facilitated molecular recognition studies. This was done by probing the local tertiary structure of aromatic amino acid residues upon addition of chiral or non-chiral ligands using long pathlength cells (1-5 cm) of small volume capacity (70 μl-350 μl). In this chapter we describe the use of SRCD to qualitatively and quantitatively screen ligand binding interactions (exemplified by Sbma, Ace1 and FsrC proteins); to distinguish between functionally similar drugs that exhibit different mechanisms of action towards membrane proteins (exemplified by FsrC); and to identify suitable detergent conditions to observe membrane protein-ligand interactions using stabilised proteins (exemplified by inositol transporters) as well as the stability of membrane proteins (exemplified by GalP, Ace1). The importance of the in solution characterisation of the conformational behaviour and ligand binding properties of proteins in both far- andnear-UV regions and the use of high-throughput CD (HT-CD) using 96- and 384-well multiplates to study the folding effects in various protein crystallisation buffers are also discussed.

  13. Vibrational and electronic circular dichroism study of bile pigments: complexes of bilirubin and biliverdin with metals.

    Science.gov (United States)

    Goncharova, Iryna; Urbanová, Marie

    2009-09-01

    Complexation of bilirubin (BR) and biliverdin (BV) with biogenic and toxic metals (Mn, Cu, Cd, Co, Fe, Ni, Zn, and Ag) has been studied by means of electronic circular dichroism (ECD) and vibrational circular dichroism (VCD). Poly-L-lysine and beta-cyclodextrin in water were chosen as matrices capable of recognizing the single stereoconformer of the pigments with defined M-helicity. Such systems allow structural changes caused by complexation of pigments with metals in aqueous solution at pH 10-11 to be followed using chiroptical methods, which are intrinsically sensitive to spatial structure. These and other spectroscopic techniques have revealed that BV and BR form monomeric complexes with Cd, Cu, and Zn and dimeric complexes with Mn. The stabilities of the complexes with Fe, Ni, Co, and Ag are remarkably lower. The sign of the ECD and VCD patterns of the complexed BV does not change for the chelates of any of the studied metals other than Zn, this exception being interpreted in terms of manifestation of the opposite helicity of BV in its chelate with Zn. In the case of BR, the observed inversion of ECD signal after complexation, together with the analysis of VCD spectra, reveals that a flattening of the molecule takes place, i.e., an increase in the angle between the pyrrinone chromophores without an inversion of helicity. This chiral stereoselectivity, which is very specific in the case of the Zn chelates, is discussed in connection with the specific inhibition of Zn-required enzymes by bile pigments.

  14. Irreversible denaturation of maltodextrin glucosidase studied by differential scanning calorimetry, circular dichroism, and turbidity measurements.

    Science.gov (United States)

    Goyal, Megha; Chaudhuri, Tapan K; Kuwajima, Kunihiro

    2014-01-01

    Thermal denaturation of Escherichia coli maltodextrin glucosidase was studied by differential scanning calorimetry, circular dichroism (230 nm), and UV-absorption measurements (340 nm), which were respectively used to monitor heat absorption, conformational unfolding, and the production of solution turbidity. The denaturation was irreversible, and the thermal transition recorded at scan rates of 0.5-1.5 K/min was significantly scan-rate dependent, indicating that the thermal denaturation was kinetically controlled. The absence of a protein-concentration effect on the thermal transition indicated that the denaturation was rate-limited by a mono-molecular process. From the analysis of the calorimetric thermograms, a one-step irreversible model well represented the thermal denaturation of the protein. The calorimetrically observed thermal transitions showed excellent coincidence with the turbidity transitions monitored by UV-absorption as well as with the unfolding transitions monitored by circular dichroism. The thermal denaturation of the protein was thus rate-limited by conformational unfolding, which was followed by a rapid irreversible formation of aggregates that produced the solution turbidity. It is thus important to note that the absence of the protein-concentration effect on the irreversible thermal denaturation does not necessarily means the absence of protein aggregation itself. The turbidity measurements together with differential scanning calorimetry in the irreversible thermal denaturation of the protein provided a very effective approach for understanding the mechanisms of the irreversible denaturation. The Arrhenius-equation parameters obtained from analysis of the thermal denaturation were compared with those of other proteins that have been reported to show the one-step irreversible thermal denaturation. Maltodextrin glucosidase had sufficiently high kinetic stability with a half-life of 68 days at a physiological temperature (37°C).

  15. Mid-infrared Plasmonic Circular Dichroism Generated by Graphene Nanodisk Assemblies.

    Science.gov (United States)

    Kong, Xiang-Tian; Zhao, Runbo; Wang, Zhiming; Govorov, Alexander O

    2017-08-09

    It is very interesting to bring plasmonic circular dichroism spectroscopy to the mid-infrared spectral interval, and there are two reasons for this. This spectral interval is very important for thermal bioimaging, and simultaneously, this spectral range includes vibrational lines of many chiral biomolecules. Here we demonstrate that graphene plasmons indeed offer such opportunity. In particular, we show that chiral graphene assemblies consisting of a few graphene nanodisks can generate strong circular dichroism (CD) in the mid-infrared interval. The CD signal is generated due to the plasmon-plasmon coupling between adjacent nanodisks in the specially designed chiral graphene assemblies. Because of the large dimension mismatch between the thickness of a graphene layer and the incoming light's wavelength, three-dimensional configurations with a total height of a few hundred nanometers are necessary to obtain a strong CD signal in the mid-infrared range. The mid-infrared CD strength is mainly governed by the total dimensions (total height and helix scaffold radius) of the graphene nanodisk assembly and by the plasmon-plasmon interaction strength between its constitutive nanodisks. Both positive and negative CD bands can be observed in the graphene assembly array. The frequency interval of the plasmonic CD spectra overlaps with the vibrational modes of some important biomolecules, such as DNA and many different peptides, giving rise to the possibility of enhancing the vibrational optical activity of these molecular species by attaching them to the graphene assemblies. Simultaneously the spectral range of chiral mid-infrared plasmons in our structures appears near the typical wavelength of the human-body thermal radiation, and therefore, our chiral metastructures can be potentially utilized as optical components in thermal imaging devices.

  16. Theory of Anisotropic Circular Dichroism of Excitonically Coupled Systems: Application to the Baseplate of Green Sulfur Bacteria.

    Science.gov (United States)

    Lindorfer, Dominik; Renger, Thomas

    2018-03-02

    A simple exciton theory for the description of anisotropic circular dichroism (ACD) spectra of multichromophoric systems is presented that is expected to be of general use for the analysis of structure-function relationships of molecular aggregates such as photosynthetic light-harvesting antennae. The theory is applied to the baseplate of green sulfur bacteria. It is demonstrated that only the combined analysis of ACD and circular dichroism (CD) spectra for the present baseplate bacteriochlorophyll (BChl) a dimer allows for an unambiguous determination of the parameters of the exciton Hamiltonian from experimental data. The analysis of experimental absorption and linear dichroism spectra suggests that either the NMR structure has to be refined or in addition to the dimers seen in the NMR structure and in the CD and ACD spectra, BChl a monomers are present in the baseplate carotenosome sample. A refined dimer structure is presented, explaining all four optical spectra.

  17. Soft-X-ray magnetic circular dichroism : a new technique for probing magnetic properties of magnetic surfaces and ultrathin films

    NARCIS (Netherlands)

    Tjeng, L.H.; Idzerda, Y.U.; Rudolf, P.; Sette, F.; Chen, C.T.

    1992-01-01

    We demonstrate the feasibility of applying the novel soft-X-ray magnetic circular dichroism (SXMCD) technique to investigate the magnetic properties of magnetic surfaces and uitrathin films. Measurements have been carried out on Ni films of various thickness on a Cu(100) substrate at the Ni L2,3

  18. Circular Dichroism of G-Quadruplex: A Laboratory Experiment for the Study of Topology and Ligand Binding

    Science.gov (United States)

    Carvalho, Josue´; Queiroz, João A.; Cruz, Carla

    2017-01-01

    Circular dichroism (CD) has emerged as one of the standard biophysical techniques for the study of guaninequadruplex (G4) folding, cation effect, and ligand binding. The utility of this technique is based on its robustness, ease of use, and requirement of only small quantities of nucleic acid. This experiment is also extendable to the classroom…

  19. X-ray magnetic circular dichroism spectra and distortions at Fe2+ L(2,3) edges

    NARCIS (Netherlands)

    Wang, X.; de Groot, F.M.F.; Cramer, S.P.

    We have shown from ligand field multiplet calculations that the shape of X-ray magnetic circular dichroism (XMCD) spectra changes drastically with the distortion parameter Ds. The temperature dependence study of XMCD makes it possible to determine both Ds and spin-orbit coupling.

  20. Interplay of exciton coupling and large-amplitude motions in the vibrational circular dichroism spectrum of dehydroquinidine

    NARCIS (Netherlands)

    Nicu, V.P.; Domingos, S.R.; Strudwick, B.H.; Brouwer, A.M.; Buma, W.J.

    2015-01-01

    A detailed analysis of the computed structure, energies, vibrational absorption (VA) and circular dichroism (VCD) spectra of 30 low-energy conformers of dehydroquinidine reveals the existence of families of pseudo-conformers, the structures of which differ mostly in the orientation of a single

  1. X-ray magnetic circular dichroism at IrL 2, 3 edges in Fe 100- Ir ...

    Indian Academy of Sciences (India)

    3, 10 and 17) and Co100-Ir (=5, 17, 25 and 32) alloys has been investigated by X-ray magnetic circular dichroism (XMCD) at Ir L2,3 absorption edges. Sum rule analysis of the XMCD data show that the orbital moment of Ir is in the range of ...

  2. Optimized Spiral Metal-Gallium-Nitride Nanowire Cavity for Ultra-High Circular Dichroism Ultraviolet Lasing at Room Temperature.

    Science.gov (United States)

    Liao, Wei-Chun; Liao, Shu-Wei; Chen, Kuo-Ju; Hsiao, Yu-Hao; Chang, Shu-Wei; Kuo, Hao-Chung; Shih, Min-Hsiung

    2016-05-25

    Circularly polarized laser sources with small footprints and high efficiencies can possess advanced functionalities in optical communication and biophotonic integrated systems. However, the conventional lasers with additional circular-polarization converters are bulky and hardly compatible with nanophotonic circuits, and most active chiral plasmonic nanostructures nowadays exhibit broadband emission and low circular dichroism. In this work, with spirals of gallium nitride (GaN) nanowires (NWRs) covered by a metal layer, we demonstrated an ultrasmall semiconductor laser capable of emitting circularly-polarized photons. The left- and right-hand spiral metal nanowire cavities with varied periods were designed at ultraviolet wavelengths to achieve the high quality factor circular dichroism metastructures. The dissymmetry factors characterizing the degrees of circular polarizations of the left- and right-hand chiral lasers were 1.4 and -1.6 (±2 if perfectly circular polarized), respectively. The results show that the chiral cavities with only 5 spiral periods can achieve lasing signals with the high degrees of circular polarizations.

  3. Stokes-Mueller matrix polarimetry technique for circular dichroism/birefringence sensing with scattering effects.

    Science.gov (United States)

    Phan, Quoc-Hung; Lo, Yu-Lung

    2017-04-01

    A surface plasmon resonance (SPR)-enhanced method is proposed for measuring the circular dichroism (CD), circular birefringence (CB), and degree of polarization (DOP) of turbid media using a Stokes–Mueller matrix polarimetry technique. The validity of the analytical model is confirmed by means of numerical simulations. The simulation results show that the proposed detection method enables the CD and CB properties to be measured with a resolution of 10 ? 4 refractive index unit (RIU) and 10 ? 5 ?? RIU , respectively, for refractive indices in the range of 1.3 to 1.4. The practical feasibility of the proposed method is demonstrated by detecting the CB/CD/DOP properties of glucose–chlorophyllin compound samples containing polystyrene microspheres. It is shown that the extracted CB value decreases linearly with the glucose concentration, while the extracted CD value increases linearly with the chlorophyllin concentration. However, the DOP is insensitive to both the glucose concentration and the chlorophyllin concentration. Consequently, the potential of the proposed SPR-enhanced Stokes–Mueller matrix polarimetry method for high-resolution CB/CD/DOP detection is confirmed. Notably, in contrast to conventional SPR techniques designed to detect relative refractive index changes, the SPR technique proposed in the present study allows absolute measurements of the optical properties (CB/CD/DOP) to be obtained.

  4. Extrinsic 2D chirality: giant circular conversion dichroism from a metal-dielectric-metal square array

    Science.gov (United States)

    Cao, Tun; Wei, Chenwei; Mao, Libang; Li, Yang

    2014-01-01

    Giant chiroptical responses routinely occur in three dimensional chiral metamaterials (MMs), but their resonance elements with complex subwavelength chiral shapes are challenging to fabricate in the optical region. Here, we propose a new paradigm for obtaining strong circular conversion dichroism (CCD) based on extrinsic 2D chirality in multilayer achiral MMs, showing that giant chiroptical response can be alternatively attained without complex structures. Our structure consists of an array of thin Au squares separated from a continuous Au film by a GaAs dielectric layer, where the Au squares occupy the sites of a rectangular lattice. This structure gives rise to a pronounced extrinsically 2D-chiral effect (CCD) in the mid-infrared (M-IR) region under an oblique incidence, where the 2D-chiral effect is due to the mutual orientation of the Au squares array and the incident light propagation direction; the large magnitude of CCD due to the large difference between left-to-left and right-to-right circularly polarized reflectance conversion efficiencies. PMID:25501766

  5. Circular dichroism measured on single chlorosomal light-harvesting complexes of green photosynthetic bacteria

    KAUST Repository

    Furumaki, Shu

    2012-12-06

    We report results on circular dichroism (CD) measured on single immobilized chlorosomes of a triple mutant of green sulfur bacterium Chlorobaculum tepidum. The CD signal is measured by monitoring chlorosomal bacteriochlorphyll c fluorescence excited by alternate left and right circularly polarized laser light with a fixed wavelength of 733 nm. The excitation wavelength is close to a maximum of the negative CD signal of a bulk solution of the same chlorosomes. The average CD dissymmetry parameter obtained from an ensemble of individual chlorosomes was gs = -0.025, with an intrinsic standard deviation (due to variations between individual chlorosomes) of 0.006. The dissymmetry value is about 2.5 times larger than that obtained at the same wavelength in the bulk solution. The difference can be satisfactorily explained by taking into account the orientation factor in the single-chlorosome experiments. The observed distribution of the dissymmetry parameter reflects the well-ordered nature of the mutant chlorosomes. © 2012 American Chemical Society.

  6. Suppressed Magnetic Circular Dichroism and Valley-Selective Magnetoabsorption due to the Effective Mass Anisotropy in Bismuth

    Science.gov (United States)

    de Visser, Pieter J.; Levallois, Julien; Tran, Michaël K.; Poumirol, Jean-Marie; Nedoliuk, Ievgeniia O.; Teyssier, Jérémie; Uher, Ctirad; van der Marel, Dirk; Kuzmenko, Alexey B.

    2016-07-01

    We measure the far-infrared reflectivity and Kerr angle spectra on a high-quality crystal of pure semimetallic bismuth as a function of magnetic field, from which we extract the conductivity for left- and right-handed circular polarizations. The high spectral resolution allows us to separate the intraband Landau level transitions for electrons and holes. The hole transition exhibits 100% magnetic circular dichroism; it appears only for one polarization as expected for a circular cyclotron orbit. However, the dichroism for electron transitions is reduced to only 13 ±1 %, which is quantitatively explained by the large effective mass anisotropy of the electron pockets of the Fermi surface. This observation is a signature of the mismatch between the metric experienced by the photons and the electrons. It allows for a contactless measurement of the effective mass anisotropy and provides a direction towards valley polarized magnetooptical pumping with elliptically polarized light.

  7. Frequency comb laser spectroscopy in the vacuum-ultraviolet region

    NARCIS (Netherlands)

    Zinkstok, R.T.; Witte, S.; Ubachs, W.M.G.; Hogervorst, W.; Eikema, K.S.E.

    2006-01-01

    We demonstrate that the output of a frequency comb laser can be amplified and upconverted to the vacuum ultraviolet (vuv) in a gaseous medium while its phase coherence is maintained to a high degree (< 1 30 of a vuv cycle). The produced vuv pulses are well suited to perform frequency comb

  8. Vacuum ultraviolet photoabsorption spectroscopy of crystalline and amorphous benzene

    DEFF Research Database (Denmark)

    Dawes, Anita; Pascual, Natalia; Hoffmann, Soren V.

    2017-01-01

    We present the first high resolution vacuum ultraviolet photoabsorption study of amorphous benzene with com parisons to annealed crystalline benzene and the gas phase. Vapour deposited benzene layers w ere grow n at 25 K and annealed to 90 K under conditions pertinent to interstellaricy dust grains...

  9. Vacuum ultraviolet radiometry of xenon positive column discharges

    Science.gov (United States)

    Doughty, D. A.; Fobare, D. F.

    1995-10-01

    In order to judge the potential fluorescent lamp applications of various low-pressure positive column discharges it is necessary to measure the absolute power emitted in the ultraviolet region of the spectrum. For rare-gas discharges the principle emission occurs in the vacuum ultraviolet so that it is difficult to measure the radiant emittance (power per unit area) of the resonance radiation by standard methods. Two independent techniques are discussed for measuring the radiant emittance of positive column discharges in the vacuum ultraviolet. These techniques are used to study xenon positive column discharges at the resonance wavelength of 147 nm. The first method relies on the measurement of the resonance level density by absorption techniques. The effective decay rate of the resonance level is then determined by the simulation of resonance radiation transport. These two quantities are combined to yield the radiant emittance at 147 nm without implementing vacuum ultraviolet techniques. The second method uses a measurement of the resonance radiation normal to the positive column axis made with a calibrated vacuum ultraviolet detector. The angular distribution of the resonance radiation leaving the tube is determined by the simulation of resonance radiation transport. The detector measurement places the angular distribution of the radiance on an absolute scale, which can then be integrated to yield the radiant emittance. These two techniques are compared for pure xenon discharges at various pressures and currents.

  10. Investigation of X-ray natural circular dichroism in a CsCuCl{sub 3} single crystal: Theory and experiment

    Energy Technology Data Exchange (ETDEWEB)

    Rogalev, A., E-mail: rogalev@esrf.fr; Goulon, J.; Wilhelm, F. [European Synchrotron Radiation Facility (France); Kozlovskaya, K. A.; Ovchinnikova, E. N. [Moscow State University (Russian Federation); Soboleva, L. V.; Konstantinova, A. F.; Dmitrienko, V. E., E-mail: dmitrien@ns.crys.ras.ru [Russian Academy of Sciences, Shubnikov Institute of Crystallography (Russian Federation)

    2008-05-15

    X-ray natural circular dichroism in the near-Cu K edge in a CsCuCl{sub 3} single crystal, caused by dipole-quadrupole (E1E2) transitions between electronic states of different parity, has been experimentally and theoretically investigated. Numerical simulation of the experimental X-ray absorption spectrum and circular dichroism has been performed. It is established that a circular dichroism signal is observed in the pre-edge spectral region; therefore, it is mainly due to the localized electronic p-d states.

  11. DNA binding of sunitinib: Spectroscopic evidence via circular dichroism and nuclear magnetic resonance.

    Science.gov (United States)

    Kiss, Eszter; Mirzahosseini, Arash; Hubert, Ágnes; Ambrus, Attila; Őrfi, László; Horváth, Péter

    2018-02-20

    Sunitinib is a non-selective tyrosine kinase inhibitor, but in its chemical structure there can be discovered certain features, which suggest the ability to bind to DNA. These elements are the planar aromatic system and the tertiary amine function, which is protonated at the pH of the organism. In this study, the binding of the drug sunitinib to DNA was investigated using circular dichroism (CD), 1 H NMR and UV spectroscopies, along with CD melting. For these studies DNA was isolated from calf thymus (CT), salmon fish sperm (SS), and chicken erythrocyte (CE), however for our purposes an artificially constructed and highly purified plasmid DNA (pUC18) preparation proved to be the most suitable. DNA binding of the drug was confirmed by shifts in the characteristic CD bands of the DNA, the appearance of an induced CD (ICD) signal in the upper absorption region of sunitinib (300 nm-500 nm), and the evidence from CD melting studies and the NMR. Based on the CD and NMR measurements, it can be assumed that sunitinib has a multiple-step binding mechanism. Copyright © 2017 Elsevier B.V. All rights reserved.

  12. Probing tertiary structure of proteins using single Trp mutations with circular dichroism at low temperature.

    Science.gov (United States)

    Gasymov, Oktay K; Abduragimov, Adil R; Glasgow, Ben J

    2014-01-30

    Trp is the most spectroscopically informative aromatic amino acid of proteins. However, the near-UV circular dichroism (CD) spectrum of Trp is complicated because the intensity and sign of (1)La and (1)Lb bands vary independently. To resolve vibronic structure and gain site-specific information from complex spectra, deconvolution was combined with cooling and site-directed tryptophan substitution. Low temperature near-UV CD was used to probe the local tertiary structure of a loop and α-helix in tear lipocalin. Upon cooling, the enhancement of the intensities of the near-UV CD was not uniform, but depends on the position of Trp in the protein structure. The most enhanced (1)Lb band was observed for Trp at position 124 in the α-helix segment matching the known increased conformational mobility during ligand binding. Some aspects of the CD spectra of W28 and W130 were successfully linked to specific rotamers of Trp previously obtained from fluorescence lifetime measurements. The discussion was based on a framework that the magnitude of the energy differences in local conformations governs the changes in the CD intensities at low temperature. The Trp CD spectral classification of Strickland was modified to facilitate the recognition of pseudo peaks. Near-UV CD spectra harbor abundant information about the conformation of proteins that site directed Trp CD can report.

  13. Simultaneous Analysis of Secondary Structure and Light Scattering from Circular Dichroism Titrations: Application to Vectofusin-1

    Science.gov (United States)

    Vermeer, Louic S.; Marquette, Arnaud; Schoup, Michel; Fenard, David; Galy, Anne; Bechinger, Burkhard

    2016-01-01

    Circular Dichroism data are often decomposed into their constituent spectra to quantify the secondary structure of peptides or proteins but the estimation of the secondary structure content fails when light scattering leads to spectral distortion. If peptide-induced liposome self-association occurs, subtracting control curves cannot correct for this. We show that if the cause of the light scattering is independent from the peptide structural changes, the CD spectra can be corrected using principal component analysis (PCA). The light scattering itself is analysed and found to be in good agreement with backscattering experiments. This method therefore allows to simultaneously follow structural changes related to peptide-liposome binding as well as peptide induced liposome self-association. We apply this method to study the structural changes and liposome binding of vectofusin-1, a transduction enhancing peptide used in lentivirus based gene therapy. Vectofusin-1 binds to POPC/POPS liposomes, causing a reversal of the negative liposome charge at high peptide concentrations. When the peptide charges exactly neutralise the lipid charges on both leaflets reversible liposome self-association occurs. These results are in good agreement with biological observations and provide further insight into the conditions required for efficent transduction enhancement. PMID:28004740

  14. Transmission vs. Diffuse Transmission in Circular Dichroism: What to Choose for Probing Solid-State Samples?

    Science.gov (United States)

    Górecki, Marcin

    2015-07-01

    Recent advances in equipment enabled the collection of solid-state electronic circular dichroism (ECD) spectra using the commercially available integrating sphere attachment for a regular ECD spectrometer. This accessory was designed to reduce negative factors occurring in solid-state ECD measurements, and is, thereby, very useful for recording diffuse transmittance CD (DTCD) spectra using the pellet technique. In the present article, the operating principle of the integrating sphere and utility of the DTCD method in recording solid-state ECD spectra is demonstrated. Based on illustrative examples, i.e., 10-camphorsulfonic acid ammonium, cholest-4-en-3-one, (3R,4R,5S)-oseltamivir, and (S)-linezolid, ECD solid-state measurements were performed by means of both transmission and diffusion methods and later compared. Selection of these compounds as models for comparative studies was made in view of their different chromophoric systems and the profound importance in the pharmaceutical industry. During the course of this work the benefits and limitations of the use of integrating sphere are presented. The final conclusion is that more relevant solid-state spectra can be obtained by means of the DTCD method. © 2015 Wiley Periodicals, Inc.

  15. Circular dichroism spectroscopy: An efficient approach for the quantitation of ampicillin in presence of cloxacillin.

    Science.gov (United States)

    Rahman, Nafisur; Khan, Sumaiya

    2016-05-05

    Ampicillin exhibited a negative and a positive cotton effects on the circular dichroism (CD) spectra in the wavelength range of 200-280nm. Cloxacillin showed a positive cotton band peaking at 228nm. Three sensitive, precise and accurate CD spectroscopic methods have been developed for the determination of ampicillin and cloxacillin. Method A was used for the determination of ampicillin in presence of cloxacillin by measuring ellipticity at 206nm. Method B and C were employed to determine ampicillin and cloxacillin based on evaluation of ellipticity at 233nm and 228nm, respectively. Methods A, B and C showed linearity in the concentration range of 10-40μgmL(-1), 5-40μgmL(-1) ampicillin and 10-80μgmL(-1) cloxacillin, respectively. The method A was successfully applied to the determination of ampicillin in commercial dosage forms containing equivalent amount of cloxacillin. Copyright © 2016 Elsevier B.V. All rights reserved.

  16. Probing Tertiary Structure of Proteins Using Single Trp Mutations with Circular Dichroism at Low Temperature

    Science.gov (United States)

    2015-01-01

    Trp is the most spectroscopically informative aromatic amino acid of proteins. However, the near-UV circular dichroism (CD) spectrum of Trp is complicated because the intensity and sign of 1La and 1Lb bands vary independently. To resolve vibronic structure and gain site-specific information from complex spectra, deconvolution was combined with cooling and site-directed tryptophan substitution. Low temperature near-UV CD was used to probe the local tertiary structure of a loop and α-helix in tear lipocalin. Upon cooling, the enhancement of the intensities of the near-UV CD was not uniform, but depends on the position of Trp in the protein structure. The most enhanced 1Lb band was observed for Trp at position 124 in the α-helix segment matching the known increased conformational mobility during ligand binding. Some aspects of the CD spectra of W28 and W130 were successfully linked to specific rotamers of Trp previously obtained from fluorescence lifetime measurements. The discussion was based on a framework that the magnitude of the energy differences in local conformations governs the changes in the CD intensities at low temperature. The Trp CD spectral classification of Strickland was modified to facilitate the recognition of pseudo peaks. Near-UV CD spectra harbor abundant information about the conformation of proteins that site directed Trp CD can report. PMID:24404774

  17. Circular dichroism sensor based on cadmium sulfide quantum dots for chiral identification and detection of penicillamine.

    Science.gov (United States)

    Ngamdee, Kessarin; Puangmali, Theerapong; Tuntulani, Thawatchai; Ngeontae, Wittaya

    2015-10-22

    A new chemical sensor based on the measuring of circular dichroism signal (CD) was fabricated from cysteamine capped cadmium sulfide quantum dots (Cys-CdS QDs). The chiral-thiol molecules, d-penicillamine (DPA) and l-penicillamine (LPA), were used to evaluate potentials of this sensor. Basically, DPA and LPA provide very low CD signals. However, the CD signals of DPA and LPA can be enhanced in the presence of Cys-CdS QDs. The CD spectra of DPA and LPA exhibited a mirror image profile. Parameters affecting the determination of DPA and LPA were thoroughly investigated in details. Under the optimized condition, the CD signals of DPA and LPA displayed a linear relationship with the concentrations of both enantiomers, ranging from 1 to 35 μM. Detection limits of this sensor were 0.49 and 0.74 μM for DPA and LPA, respectively. To demonstrate a potential application of this sensor, the proposed sensor was used to determine DPA and LPA in real urine samples. It was confirmed that the proposed detection technique was reliable and could be utilized in a broad range of applications. Copyright © 2015 Elsevier B.V. All rights reserved.

  18. First-principles analysis of X-ray magnetic circular dichroism for transition metal complex oxides

    Energy Technology Data Exchange (ETDEWEB)

    Ikeno, Hidekazu, E-mail: h-ikeno@21c.osakafu-u.ac.jp [Nanoscience and Nanotechnology Research Center, Research Organization for the 21st Century, Osaka Prefecture University, 1-2 Gakuen-cho, Naka-ku, Sakai, Osaka 599-8570 (Japan)

    2016-10-14

    X-ray magnetic circular dichroism (XMCD) is widely used for the characterization of magnetism of materials. However, information from XMCD related to the atomic, electronic, and magnetic structures is not fully utilized due to the lack of reliable theoretical tools for spectral analysis. In this work, the first-principles configuration interaction (CI) calculations for X-ray absorption spectra developed by the author were extended for the calculation of XMCD, where the Zeeman energy was taken into the Hamiltonian of the CI to mimic magnetic polarization in the solid state. This technique was applied to interpret the L{sub 2,3} XMCD from 3d transition metal complex oxides, such as NiFe{sub 2}O{sub 4} and FeTiO{sub 3}. The experimental XMCD spectra were quantitatively reproduced using this method. The oxidation states as well as the magnetic ordering between transition metal ions on crystallographically different sites in NiFe{sub 2}O{sub 4} can be unambiguously determined. A first-principles analysis of XMCD in FeTiO{sub 3} revealed the presence of Fe{sup 3+} and Ti{sup 3+} ions, which indicates that the charge transfer from Fe to Ti ions occurs. The origin of magnetic polarization of Ti ions in FeTiO{sub 3} was also discussed.

  19. Utilization of circular dichroism experiment to distinguish acanthoside D and eleutheroside E.

    Science.gov (United States)

    Kil, Yun-Seo; Park, Ji-Yeon; Kim, Youngmee; Nam, Sang-Jip; Kim, Sung-Jin; Kim, Yeong Shik; Seo, Eun Kyoung

    2015-11-01

    Two lignan glycosides, acanthoside D (1) (=liriodendrin, (+)-syringaresinol di-O-β-D-glucopyranoside) and eleutheroside E (2) have been confused each other for so long time, and hard to be distinguished each other. Now, this two compounds need to be defined properly so that all the commercial mistakes and confusions should not be made. They have identical planar structures except for the configurations at C-7 and C-8 in each structure according to the chemistry database, SciFinder(®). The systematic name of acanthoside D is [(1S,3aR,4S,6aR)-tetrahydro-1H,3H-furo[3,4-c]furan-1,4-diyl]bis(2,6-dimethoxy-4,1-phenylene) bis-β-D-glucopyranoside (1), and the name of eleutheroside E is [(1R,3aR,4S,6aS)-tetrahydro-1H,3H-furo[3,4-c]furan-1,4-diyl]bis(2,6-dimethoxy-4,1-phenylene) bis-β-D-glucopyranoside (2). The differences at two chiral centers do not make any differences in the NMR spectra. Thus, the circular dichroism were utilized to dissolve this difficult problem. Acanthoside D (1) showed a positive Cotton effect at 200 nm, whereas eleutheroside E (2) exhibited a negative cotton effect at 200 nm. The absolute structure of acanthoside D was also confirmed by X-ray crystallography.

  20. Reliable HPLC separation, vibrational circular dichroism spectra, and absolute configurations of isoborneol enantiomers.

    Science.gov (United States)

    Gao, Rui-Qi; Fan, Jun; Tan, Qi; Guo, Dong; Chen, Tao; He, Ru-Jian; Li, Dan; Zhang, Hui; Zhang, Wei-Guang

    2017-09-01

    Resolution of chiral compounds has played an important role in the pharmaceutical field, involving detailed studies of pharmacokinetics, physiological, toxicological, and metabolic activities of enantiomers. Herein, a reliable method by high-performance liquid chromatography (HPLC) coupled with an optical rotation detector was developed to separate isoborneol enantiomers. A cellulose tris(3, 5-dimethylphenylcarbamate)-coated chiral stationary phase showed the best separation performance for isoborneol enantiomers in the normal phase among four polysaccharide chiral packings. The effects of alcoholic modifiers and column temperature were studied in detail. Resolution of the isoborneol racemate displayed a downward trend along with an increase in the content of ethanol and column temperature, indicating that less ethanol in the mobile phase and lower temperature were favorable to this process. Moreover, two isoborneol enantiomers were obtained via a semipreparative chiral HPLC technique under optimum conditions, and further characterized by analytical HPLC, and experimental and calculated vibrational circular dichroism (VCD) spectroscopy, respectively. The solution VCD spectrum of the first-eluted component was consistent with the Density Functional Theory (DFT) calculated pattern based on the SSS configuration, indicating that this enantiomer should be (1S, 2S, 4S)-(+)-isoborneol. Briefly, these results have provided reliable information to establish a method for analysis, preparative separation, and absolute configuration of chiral compounds without typical chromophoric groups. © 2017 Wiley Periodicals, Inc.

  1. Assessing the Utility of Circular Dichroism and FTIR Spectroscopy in Monoclonal-Antibody Comparability Studies.

    Science.gov (United States)

    Lin, Jasper C; Glover, Zephania Kwong; Sreedhara, Alavattam

    2015-12-01

    Protein characterization is a necessary activity during development, technical transfers, and licensure. One important aspect of protein characterization is higher order structure assessment, which can be accomplished in a variety of ways. Circular dichroism (CD) and Fourier transform infrared (FTIR) spectroscopies provide global higher order structure and are routinely used to measure the overall structure for product characterization; however, their use as comparability tools is uncertain because of their insensitivity to local or small structure changes. We use a monoclonal antibody (mAb) to explore the usefulness of CD and FTIR compared with other indirect methods of structure characterization such as size-exclusion and ion-exchange chromatographies (SEC and IEC). A panel of degraded samples of a mAb was generated; their higher order structure evaluated using CD and FTIR and was found to be largely unchanged. However, the SEC and IEC chromatograms of certain degraded samples were found to have measurable changes. Based on these studies, we conclude that the application of CD and FTIR should be reserved for global higher order structure identification or product characterization only. The use of CD or FTIR comparability of mAbs should be carefully evaluated, as comparability can be sensitively determined using indirect methods based on chromatography. © 2015 Wiley Periodicals, Inc. and the American Pharmacists Association.

  2. Absolute Configuration of 3-METHYLCYCLOHEXANONE by Chiral Tag Rotational Spectroscopy and Vibrational Circular Dichroism

    Science.gov (United States)

    Evangelisti, Luca; Holdren, Martin S.; Mayer, Kevin J.; Smart, Taylor; West, Channing; Pate, Brooks

    2017-06-01

    The absolute configuration of 3-methylcyclohexanone was established by chiral tag rotational spectroscopy measurements using 3-butyn-2-ol as the tag partner. This molecule was chosen because it is a benchmark measurement for vibrational circular dichroism (VCD). A comparison of the analysis approaches of chiral tag rotational spectroscopy and VCD will be presented. One important issue in chiral analysis by both methods is the conformational flexibility of the molecule being analyzed. The analysis of conformational composition of samples will be illustrated. In this case, the high spectral resolution of molecular rotational spectroscopy and potential for spectral simplification by conformational cooling in the pulsed jet expansion are advantages for chiral tag spectroscopy. The computational chemistry requirements for the two methods will also be discussed. In this case, the need to perform conformer searches for weakly bound complexes and to perform reasonably high level quantum chemistry geometry optimizations on these complexes makes the computational time requirements less favorable for chiral tag rotational spectroscopy. Finally, the issue of reliability of the determination of the absolute configuration will be considered. In this case, rotational spectroscopy offers a "gold standard" analysis method through the determination of the ^{13}C-subsitution structure of the complex between 3-methylcyclohexanone and an enantiopure sample of the 3-butyn-2-ol tag.

  3. [Study of collagen mimetic peptide's triple-helix structure and its thermostability by circular dichroism].

    Science.gov (United States)

    Zhang, Zhi-Bao; Wang, Jing-Jie; Chen, Hui-Juan; Xiong, Qing-Qing; Liu, Ling-Rong; Zhang, Qi-Qing

    2014-04-01

    In the present study, the authors explore the triple-helix conformation and thermal stability of collagen mimetic peptides (CMPs) as a function of peptide sequence and/or chain length by circular dichroism(CD). Five CMPs were designed and synthetized varying the number of POG triplets or incorporating an integrin alpha2beta1 binding motif Gly-Phe-Hyp-Gly-Glu-Arg (GFOGER). CD spectroscopy from 260 to 190 nm was recorded to confirm the existence of triple-helix conformation at room temperature, while thermal melting and thermal annealing of triple-helix (thermal unfolding and refolding of triple-helix, respectively) was characterized by monitoring ellipticity at 225 nm as a function of temperature. The results demonstrated that all the CMPs adopted triple-helix conformation, and the thermal stability of the CMPs was enhanced with increasing the number of POG triplets. In contrast to natural collagen, the thermal denaturation processes of CMPs were reversible, i. e. the triple-helix unfolded upon heating while refolded upon cooling. Meanwhile, the phenomenon of "hysteresis" was observed by comparing melting and thermal curves. These findings add new insights to the mechanisms of collagen and CMPs assembly, as well as provide an alternative approach to the fabrication of artificial collagen-likes biomaterials.

  4. Introducing DInaMo: A Package for Calculating Protein Circular Dichroism Using Classical Electromagnetic Theory.

    Science.gov (United States)

    Uporov, Igor V; Forlemu, Neville Y; Nori, Rahul; Aleksandrov, Tsvetan; Sango, Boris A; Mbote, Yvonne E Bongfen; Pothuganti, Sandeep; Thomasson, Kathryn A

    2015-09-07

    The dipole interaction model is a classical electromagnetic theory for calculating circular dichroism (CD) resulting from the π-π* transitions of amides. The theoretical model, pioneered by J. Applequist, is assembled into a package, DInaMo, written in Fortran allowing for treatment of proteins. DInaMo reads Protein Data Bank formatted files of structures generated by molecular mechanics or reconstructed secondary structures. Crystal structures cannot be used directly with DInaMo; they either need to be rebuilt with idealized bond angles and lengths, or they need to be energy minimized to adjust bond lengths and bond angles because it is common for crystal structure geometries to have slightly short bond lengths, and DInaMo is sensitive to this. DInaMo reduces all the amide chromophores to points with anisotropic polarizability and all nonchromophoric aliphatic atoms including hydrogens to points with isotropic polarizability; all other atoms are ignored. By determining the interactions among the chromophoric and nonchromophoric parts of the molecule using empirically derived polarizabilities, the rotational and dipole strengths are determined leading to the calculation of CD. Furthermore, ignoring hydrogens bound to methyl groups is initially explored and proves to be a good approximation. Theoretical calculations on 24 proteins agree with experiment showing bands with similar morphology and maxima.

  5. On the magnetic circular dichroism of benzene. A density-functional study

    Science.gov (United States)

    Kaminský, Jakub; Kříž, Jan; Bouř, Petr

    2017-04-01

    Spectroscopy of magnetic circular dichroism (MCD) provides enhanced information on molecular structure and a more reliable assignment of spectral bands than absorption alone. Theoretical modeling can significantly enhance the information obtained from experimental spectra. In the present study, the time dependent density functional theory is employed to model the lowest-energy benzene transitions, in particular to investigate the role of the Rydberg states and vibrational interference in spectral intensities. The effect of solvent is explored on model benzene-methane clusters. For the lowest-energy excitation, the vibrational sub-structure of absorption and MCD spectra is modeled within the harmonic approximation, providing a very good agreement with the experiment. The simulations demonstrate that the Rydberg states have a much stronger effect on the MCD intensities than on the absorption, and a very diffuse basis set must be used to obtain reliable results. The modeling also indicates that the Rydberg-like states and associated transitions may persist in solutions. Continuum-like solvent models are thus not suitable for their modeling; solvent-solute clusters appear to be more appropriate, providing they are large enough.

  6. X-ray magnetic circular dichroism used to image magnetic domains

    CERN Document Server

    Fischer, P; Kalchgruber, R; Schütz, G M; Schmahl, G; Guttmann, P; Bayreuther, G

    1999-01-01

    A new technique to image magnetic domain structures has been established by the combination of the high resolution transmission X- ray microscope (TXM) at BESSY I based on the zone plate technique with the X-ray magnetic circular $9 dichroism (X-MCD) providing a huge magnetic contrast. A lateral spatial resolution down to 30 nm could be achieved. Basic features of X-MCD are the inherent element- specificity and the potential to gain information on the local spin $9 and orbital moments of the absorbing species applying magneto-optical sum rules. Key results at the Fe L/sub 3,2/ edges of Fe in a layered GdFe system and at the Co L/sub 3/ edge of a PtCo layered system demonstrate the potential of $9 this microscopy. The images can be recorded in varying magnetic fields which allows to study the evolution of magnetic domains within a complete hysteresis loop. (8 refs).

  7. Advanced Applications of Vibrational Circular Dichroism: from Small Chiral Molecules to Fibrils

    Science.gov (United States)

    Dukor, Rina K.

    2017-06-01

    Vibrational Circular Dichroism (VCD), first discovered in the early 1970s, and commercialized in the late 1990's, is finally coming of age! No longer a curiosity of the few selected academic groups, it is now used by all major pharmaceutical companies, regulatory agencies, government labs and academic institutions. The main application for the technology has been determination of absolute configuration of small pharmaceutical molecules. In more recent years, this has extended to more complicated molecules such as natural products with many chiral centers and conformational flexibility. Other applications include determination of enantiomeric purity, chiral polymers, and characterization of other biological molecules such as proteins, carohydrates and nucleic acids. One of the most fascinating discoveries in the VCD field has been been unusual enhancement in intensity for proteins that form fibrils. We have demonstrated sensitivity of VCD to in situ solution-phase probe of the process of fibrillogenesis and subsequent development that currently can only be studied in detail with dried samples by such techniques as scanning electron microscopy or atomic force microscopy. We have further shown that several different proteins, that in their native state have different secondary structures, have a very similar unique signature of mature fibrils. In this presentation, we will discuss fundamentals of VCD, demonstrate a few examples of different applications and showcase the sensitivity to structure of fibrils, including new results on micro-sampling.

  8. pH titration monitored by quantum cascade laser-based vibrational circular dichroism.

    Science.gov (United States)

    Rüther, Anja; Pfeifer, Marcel; Lórenz-Fonfría, Víctor A; Lüdeke, Steffen

    2014-04-10

    Vibrational circular dichroism (VCD) spectra of aqueous solutions of proline were recorded in the course of titrations from basic to acidic pH using a spectrometer equipped with a quantum cascade laser (QCL) as an infrared light source in the spectral range from 1320 to 1220 cm(-1). The pH-dependent spectra were analyzed by singular value decomposition and global fitting of a two-pK Henderson-Hasselbalch model. The analysis delivered relative fractions of the three different protonation species. Their agreement with the relative fractions obtained from performing the same analysis on pH-dependent Fourier transform infrared (FT-IR) and QCL-IR spectra validates the quantitative results from QCL-VCD. Global fitting of the pH-dependent VCD spectra of L-proline allowed for extraction of pure spectra corresponding to anionic, zwitterionic, and cationic L-proline. From a static experiment, only pure spectra of the zwitterion would be accessible in a straightforward way. A comparison to VCD spectra calculated for all three species led to assignment of vibrational modes that are characteristic for the respective protonation states. The study demonstrates the applicability of QCL-VCD both for quantitative evaluation and for qualitative interpretation of dynamic processes in aqueous solutions.

  9. Linear and circular dichroism characterization of thionine binding mode with DNA polynucleotides

    Science.gov (United States)

    Tuite, Eimer Mary; Nordén, Bengt

    2018-01-01

    The binding mode of thionine (3,7-diamino-5-phenothiazinium) with alternating and non-alternating DNA polynucleotides at low binding ratios was conclusively determined using linear and circular dichroism spectroscopies. The binding to [poly(dG-dC)]2 and poly(dG)·poly(dC) was purely intercalative and was insensitive to ionic strength. Intercalative binding to [poly(dA-dT)]2 is observed at low ionic strength, but a shift of some dye to an non-intercalative mode is observed as the background salt concentration increases. With poly(dA)·poly(dT), intercalative binding is unfavourable, although some dye molecules may intercalate at low ionic strength, and groove binding is strongly promoted with increasing concentration of background salt. However, stacking with bases is observed with single-stranded poly(dA) and with triplex poly(dT)*poly(dA)·poly(dT) which suggests that the unusual structure of poly(dA)·poly(dT) precludes intercalation. Thionine behaves similarly to the related dye methylene blue, and small differences may be attributed either to the ability of thionine to form H-bonds that stabilize intercalation or to its improved stacking interactions in the basepair pocket on steric grounds.

  10. Vertical-type chiroptical spectrophotometer (I): instrumentation and application to diffuse reflectance circular dichroism measurement.

    Science.gov (United States)

    Harada, Takunori; Hayakawa, Hiroshi; Kuroda, Reiko

    2008-07-01

    We have designed and built a novel universal chiroptical spectrophotometer (UCS-2: J-800KCMF), which can carry out in situ chirality measurement of solid samples without any pretreatment, in the UV-vis region and with high relative efficiency. The instrument was designed to carry out transmittance and diffuse reflectance (DR) circular dichroism (CD) measurements simultaneously, thus housing two photomultipliers. It has a unique feature that light impinges on samples vertically so that loose powders can be measured by placing them on a flat sample holder in an integrating sphere. As is our first universal chiroptical spectrophotometer, UCS-1, two lock-in amplifiers are installed to remove artifact signals arising from macroscopic anisotropies which are unique to solid samples. High performance was achieved by theoretically analyzing and experimentally proven the effect of the photoelastic modulator position on the CD base line shifts, and by selecting high-quality optical and electric components. Measurement of microcrystallines of both enantiomers of ammonium camphorsulfonate by the DRCD mode gave reasonable results.

  11. Circular Dichroism of Chiral Nematic Films of Cellulose Nanocrystals Loaded with Plasmonic Nanoparticles.

    Science.gov (United States)

    Querejeta-Fernández, Ana; Kopera, Bernd; Prado, Karen S; Klinkova, Anna; Methot, Myriam; Chauve, Grégory; Bouchard, Jean; Helmy, Amr S; Kumacheva, Eugenia

    2015-10-27

    In the search for induced chiral plasmonic activity, cholesteric films formed by cellulose nanocrystals have attracted great interest as potential hosts for plasmonic nanoparticles. Circular dichroism (CD) spectra of the composite films exhibit two peaks, one of which is ascribed to the cholesteric host and the other one to plasmonic chiroptical activity of the plasmonic nanoparticles. Here we report the results of comprehensive studies of extinction and CD properties of composite films formed by different types of cellulose nanocrystals and different types of plasmonic nanoparticles. We show that the second peak in the CD spectra acquired using CD spectrometers appears as the result of the local reduction of the CD signal of the host material, due to excessive absorption by the nanoparticles, and thus it cannot be interpreted as induced plasmonic chiroptical activity. Instead, we propose an alternative way to measure CD spectra of plasmonic cholesteric films by using Mueller matrix transmission ellipsometry. The results of this study are important for ongoing research in the field of chiral plasmonics and for the optical characterization of a broad range of chiral nematic nanostructured materials.

  12. Ultrafast carbonyl motion of the photoactive yellow protein chromophore probed by femtosecond circular dichroism.

    Science.gov (United States)

    Mendonça, Lucille; Hache, François; Changenet-Barret, Pascale; Plaza, Pascal; Chosrowjan, Haik; Taniguchi, Seiji; Imamoto, Yasushi

    2013-10-02

    Motions of the trans-p-coumaric acid carbonyl group following the photoexcitation of the R52Q mutant of photoactive yellow protein (PYP) are investigated, for the first time, by ultrafast time-resolved circular dichroism (TRCD) spectroscopy. TRCD is monitored in the near-ultraviolet, over a time scale of 10 ps. Immediately after excitation, TRCD is found to exhibit a large negative peak, which decays within a few picoseconds. A quantitative analysis of the signals shows that, upon excitation, the carbonyl group undergoes a fast (≪0.8 ps) and unidirectional flipping motion in the excited state with an angle of ca. 17-53°. For the subset of proteins that do not enter the signaling photocycle, TRCD provides strong evidence that the carbonyl group moves back to its initial position, leading to the formation of a nonreactive ground-state intermediate of trans conformation. The initial ground state is then restored within ca. 3 ps. Comparative study of R52Q and wild-type PYP provides direct evidence that the absence of Arg52 has no effect on the conformational changes of the chromophore during those steps.

  13. Interaction of fisetin with human serum albumin by fluorescence, circular dichroism spectroscopy and DFT calculations: binding parameters and conformational changes

    Energy Technology Data Exchange (ETDEWEB)

    Matei, Iulia; Ionescu, Sorana [Department of Physical Chemistry, Faculty of Chemistry, University of Bucharest, Bd. Regina Elisabeta 4-12, 030018 Bucharest (Romania); Hillebrand, Mihaela, E-mail: mihh@gw-chimie.math.unibuc.ro [Department of Physical Chemistry, Faculty of Chemistry, University of Bucharest, Bd. Regina Elisabeta 4-12, 030018 Bucharest (Romania)

    2011-08-15

    The interaction between fisetin, an antioxidant and neuroprotective flavonoid, and human serum albumin (HSA) is investigated by means of fluorescence (steady-state, synchronous, time-resolved) and circular dichroism (CD) spectroscopy. The formation of a 1:1 complex with a constant of about 10{sup 5} M{sup -1} was evidenced. Foerster's resonance energy transfer and competitive binding with site markers warfarin and ibuprofen were considered and discussed. Changes in the CD band of HSA indicate a decrease in the {alpha}-helix content upon binding. An induced CD signal for bound fisetin was observed and rationalized in terms of density functional theory calculations. - Highlights: > Fisetin-BSA system was studied by fluorescence spectroscopy. > Binding parameters, association constant and number of sites were estimated. > Binding site of fisetin was identified by competitive experiments. > Conformational changes in HSA and fisetin were evidenced by circular dichroism. > TDDFT calculated CD spectra supported the experimental data.

  14. Elucidating the Structure of Chiral Molecules by using Amplified Vibrational Circular Dichroism: From Theory to Experimental Realization.

    Science.gov (United States)

    Domingos, Sérgio R; Hartl, František; Buma, Wybren Jan; Woutersen, Sander

    2015-11-16

    Recent experimental observations of enhanced vibrational circular dichroism (VCD) in molecular systems with low-lying electronically excited states suggest interesting new applications of VCD spectroscopy. The theory describing VCD enhancement through vibronic coupling schemes was derived by Nafie in 1983, but only recently experimental evidence of VCD amplification has demonstrated the extent to which this effect can be exploited as a structure elucidation tool to probe local structure. In this Concept paper, we give an overview of the physics behind vibrational circular dichroism, in particular the equations governing the VCD amplification effect, and review the latest experimental developments with a prospective view on the application of amplified VCD to locally probe biomolecular structure. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Co-occurrence of linear and circular dichroism in chiral sculptured ZrO2 thin films

    Science.gov (United States)

    Muhammad, Zahir; Wali, Faiz; Song, Li

    2018-01-01

    Three dimensional chiral metamaterials, have unique helical shaped morphologies and periodically varying permittivity, possess inherent fascinatingly chiroptical activity in developing potential photonic applications. Herein, we demonstrate a systemic simulations of optical activity in chiral sculptured thin films (CSTFs) made of ZrO2 . In particular, a circular dichroism (CD) and linear dichroism (LD) are scrutinized for the proposed ZrO2 CSTFs. From the calculated differential absorption, LD and CD spectrum is computed using linear and circular polarized light beams respectively. The signated mode of different peaks for LD and CD is observed at different sweep angles with a large LD effect. Moreover, the CD diminishes at large sweep angle. This finding strongly indicates high potential of our proposed helical ZrO2 nanostructures as a perfect polarization converter. Simultaneously, optical remittance of different helical nanostructures are also compared.

  16. Measuring circular dichroism in a capillary cell using the b23 synchrotron radiation CD beamline at diamond light source.

    Science.gov (United States)

    Jávorfi, Tamás; Hussain, Rohanah; Myatt, Daniel; Siligardi, Giuliano

    2010-01-01

    Synchrotron radiation circular dichroism (SRCD) is a well-established method in structural biology. The first UV-VIS beamline dedicated to circular dichroism at Diamond Light Source, a third generation synchrotron facility in South Oxfordshire, has recently become operational and it is now available for the user community. Herein we present an important application of SRCD: the CD measurement of protein solutions in fused silica rectangular capillary cells. This was achieved without the use of any lens between the photoelastic modulator and the photomultiplier tube detectors by exploiting the high photon flux of the collimated beam that can be as little as half a millimeter squared. Measures to minimize or eliminate vacuum-UV protein denaturation effects are discussed. The CD spectra measured in capillaries is a proof of principle to address CD measurements in microdevice systems using the new B23 SRCD beamline. © 2010 Wiley-Liss, Inc.

  17. X-ray absorption and magnetic circular dichroism studies of ion-bombarded ferromagnet-antiferromagnet bilayers

    Science.gov (United States)

    Schmalhorst, J.; Sacher, M.; Höink, V.; Reiss, G.; Engel, D.; Ehresmann, A.

    2004-11-01

    The influence of He ion bombardment on the structural and magnetic interface properties of a polycrystalline Mn83Ir17/Co antiferromagnet-ferromagnet bilayer system is investigated. For annealed as well as for not annealed samples an exchange bias field of up to 200Oe is induced by the ion bombardment for doses up to 5×1014ions/cm2 . The x-ray absorption and the x-ray magnetic circular dichroism of Co and Mn is not significantly altered by this ion dose. For higher doses the exchange bias field is strongly reduced and accompanied by an increase of the ratio of the Mn to Co x-ray absorption intensities and a reduction of the Co x-ray magnetic circular dichroism signal. A model with a Gaussian-like intermixing zone at the AF/FM interface is developed to account for the observed changes of the x-ray absorption spectra.

  18. Intrinsic and Extrinsic Ferromagnetism in Co-Doped Indium Tin Oxide Revealed Using X-Ray Magnetic Circular Dichroism

    OpenAIRE

    Hakimi, A. M. H. R.; Schoofs, F.; Blamire, M. G.; S. Langridge; Dhesi, S. S.

    2017-01-01

    The effects of high-temperature annealing on ferromagnetic Co-doped Indium Tin Oxide (ITO) thin films have been investigated using X-ray diffraction (XRD), magnetometry, and X-Ray Magnetic Circular Dichroism (XMCD). Following annealing, the magnetometry results indicate the formation of Co clusters with a significant increase in the saturation magnetization of the thin films arising from defects introduced during cluster formation. However, sum rule analysis of the element-specific XMCD resul...

  19. Measurement of the polarization for soft x-ray magnetic circular dichroism at the BSRF beamline 4B7B

    CERN Document Server

    Zhi-Ying, Guo; Jing-Tao, Zhu; YI-Dong, Zhao; Lei, Zheng; Cai-Hao, Hong; Kun, Tang; Dong-Liang, Yang; Ming-Qi, Cui

    2012-01-01

    Three ultra-short-period W/B4C multilayers (1.244nm, 1.235nm and 1.034nm) have been fabricated and used for polarization measurement at the 4B7B Beamline of Beijing Synchrotron Radiation Facility (BSRF). By rotating analyzer ellipsometry method, the linear polarization degree of light emerging from this beamline has been measured and the circular polarization evaluated for 700eV-860eV. The first soft x-ray magnetic circular dichroism measurements are carried out at BSRF by positioning the beamline aperture out of the plane of the electron storage ring.

  20. Influence of hybridization in the magnetic circular X-ray dichroism at the Ce-M(4,5) absorption edges of Ce-Fe systems

    NARCIS (Netherlands)

    Finazzi, M; deGroot, FMF; Dias, AM; Kappler, JP; Schulte, O; Felsch, W; Krill, G

    We have performed a Magnetic Circular X-ray Dichroism (XMCD) study at the Ce-M(4,5) absorption edges on some Ce-Fe systems. We find that the dichroism signal in these systems is very sensitive to the degree of hybridization of the 4f electrons with the valence band. XMCD is able to demonstrate that

  1. Influence of hybridization in the Magnetic Circular X-ray Dichroism at the Ce-M4,5 absorption edges of Ce-Fe systems

    NARCIS (Netherlands)

    Finazzi, M.; de Groot, F.M.F.; Dias, A.-M.; Kappler, J.-P.; Schulte, O.; Felsch, W.; Krill, G.

    2013-01-01

    We have performed a Magnetic Circular X-ray Dichroism (XMCD) study at the Ce-M*,s absorption edges on some Ce-Fe systems. We find that the dichroism signal in these systems is very sensitive to the degree of hybridization of the 4f electrons with the valence band. XMCD is able to demonstrate that

  2. Recent advances and applications of gas chromatography vacuum ultraviolet spectroscopy.

    Science.gov (United States)

    Santos, Inês C; Schug, Kevin A

    2017-01-01

    The vacuum ultraviolet spectrophotometer was developed recently as an alternative to existing gas chromatography detectors. This detector measures the absorption of gas-phase chemical species in the range of 120-240 nm, where all chemical compounds present unique absorption spectra. Therefore, qualitative analysis can be performed and quantification follows standard Beer-Lambert law principles. Different fields of application, such as petrochemical, food, and environmental analysis have been explored. Commonly demonstrated is the capability for facile deconvolution of co-eluting analytes. The concept of additive absorption for co-eluting analytes has also been advanced for classification and speciation of complex mixtures using a data treatment procedure termed time interval deconvolution. Furthermore, pseudo-absolute quantitation can be performed for system diagnosis, as well as potentially calibrationless quantitation. In this manuscript an overview of these features, the vacuum ultraviolet spectrophotometer instrumentation, and performance capabilities are given. A discussion of the applications of the vacuum ultraviolet detector is provided by describing and discussing the papers published thus far since 2014. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Vibrational circular dichroism spectroscopy of a spin-triplet bis-(biuretato) cobaltate(III) coordination compound with low-lying electronic transitions

    DEFF Research Database (Denmark)

    Johannessen, Christian; Thulstrup, Peter W.

    2007-01-01

    Vibrational absorption (VA) and vibrational circular dichroism (VCD) spectroscopy was applied in the analysis of vibrational and low lying electronic transitions of a triplet ground state cobalt(III) coordination compound. The spectroscopic measurements were performed on the tetrabutylammonium salt...

  4. DNA Electronic Circular Dichroism on the Inter-Base Pair Scale: An Experimental-Theoretical Case Study of the AT Homo-Oligonucleotide.

    Science.gov (United States)

    Di Meo, Florent; Pedersen, Morten N; Rubio-Magnieto, Jenifer; Surin, Mathieu; Linares, Mathieu; Norman, Patrick

    2015-02-05

    A successful elucidation of the near-ultraviolet electronic circular dichroism spectrum of a short double-stranded DNA is reported. Time-dependent density functional theory methods are shown to accurately predict spectra and assign bands on the microscopic base-pair scale, a finding that opens the field for using circular dichroism spectroscopy as a sensitive nanoscale probe of DNA to reveal its complex interactions with the environment.

  5. Accurate secondary structure prediction and fold recognition for circular dichroism spectroscopy.

    Science.gov (United States)

    Micsonai, András; Wien, Frank; Kernya, Linda; Lee, Young-Ho; Goto, Yuji; Réfrégiers, Matthieu; Kardos, József

    2015-06-16

    Circular dichroism (CD) spectroscopy is a widely used technique for the study of protein structure. Numerous algorithms have been developed for the estimation of the secondary structure composition from the CD spectra. These methods often fail to provide acceptable results on α/β-mixed or β-structure-rich proteins. The problem arises from the spectral diversity of β-structures, which has hitherto been considered as an intrinsic limitation of the technique. The predictions are less reliable for proteins of unusual β-structures such as membrane proteins, protein aggregates, and amyloid fibrils. Here, we show that the parallel/antiparallel orientation and the twisting of the β-sheets account for the observed spectral diversity. We have developed a method called β-structure selection (BeStSel) for the secondary structure estimation that takes into account the twist of β-structures. This method can reliably distinguish parallel and antiparallel β-sheets and accurately estimates the secondary structure for a broad range of proteins. Moreover, the secondary structure components applied by the method are characteristic to the protein fold, and thus the fold can be predicted to the level of topology in the CATH classification from a single CD spectrum. By constructing a web server, we offer a general tool for a quick and reliable structure analysis using conventional CD or synchrotron radiation CD (SRCD) spectroscopy for the protein science research community. The method is especially useful when X-ray or NMR techniques fail. Using BeStSel on data collected by SRCD spectroscopy, we investigated the structure of amyloid fibrils of various disease-related proteins and peptides.

  6. A novel calibration strategy based on background correction for quantitative circular dichroism spectroscopy.

    Science.gov (United States)

    Zuo, Qi; Xiong, Shun; Chen, Zeng-Ping; Chen, Yao; Yu, Ru-Qin

    2017-11-01

    When using circular dichroism (CD) spectroscopy for quantitative analysis, the samples to be analyzed must be free of light-absorbing interferences. However, in real-world samples, the presence of background absorbers is practically unavoidable. The difference in the matrices between the real-world samples to be analyzed and the standard samples (on which either univariate or multivariate calibration model was built) would result in systematic errors in the quantification results of CD spectroscopy. In this contribution, a novel calibration strategy for quantitative CD spectroscopic analysis was proposed. The main idea of the proposed calibration strategy is to project the CD spectra of both the standard samples and the real-world sample to be analyzed onto a projection space orthogonal to the space spanned by the background CD spectrum of the real-world sample and then build a multivariate calibration model on the transformed CD spectra of the standard samples. The performance of the proposed calibration strategy was tested and compared with conventional univariate and multivariate calibration methods in the quantification of Pb(2+) in cosmetic samples using CD spectroscopy in combination with a G-quadruplex DNAzyme (e.g. PS2.M). Experiments results revealed that the proposed calibration strategy could mitigate the influence of the difference in the matrices between the standard samples and cosmetic samples and realized quantitative analysis of Pb(2+) in cosmetic samples, with precision and accuracy comparable to atomic absorption spectroscopy. The proposed calibration strategy has the features of simplicity and effectiveness, its combination with CD spectroscopic probes can realize accurate and precise quantification of analytes in complex samples using CD spectroscopy. Copyright © 2017 Elsevier B.V. All rights reserved.

  7. Ligand- and drug-binding studies of membrane proteins revealed through circular dichroism spectroscopy.

    Science.gov (United States)

    Siligardi, Giuliano; Hussain, Rohanah; Patching, Simon G; Phillips-Jones, Mary K

    2014-01-01

    A great number of membrane proteins have proven difficult to crystallise for use in X-ray crystallographic structural determination or too complex for NMR structural studies. Circular dichroism (CD) is a fast and relatively easy spectroscopic technique to study protein conformational behaviour. In this review examples of the applications of CD and synchrotron radiation CD (SRCD) to membrane protein ligand binding interaction studies are discussed. The availability of SRCD has been an important advancement in recent progress, most particularly because it can be used to extend the spectral region in the far-UV region (important for increasing the accuracy of secondary structure estimations) and for working with membrane proteins available in only small quantities for which SRCD has facilitated molecular recognition studies. Such studies have been accomplished by probing in the near-UV region the local tertiary structure of aromatic amino acid residues upon addition of chiral or non-chiral ligands using long pathlength cells of small volume capacity. In particular, this review describes the most recent use of the technique in the following areas: to obtain quantitative data on ligand binding (exemplified by the FsrC membrane sensor kinase receptor); to distinguish between functionally similar drugs that exhibit different mechanisms of action towards membrane proteins (exemplified by secretory phospholipase A2); and to identify suitable detergent conditions to observe membrane protein-ligand interactions using stabilised proteins (exemplified by the antiseptic transporter SugE). Finally, the importance of characterising in solution the conformational behaviour and ligand binding properties of proteins in both far- and near-UV regions is discussed. This article is part of a Special Issue entitled: Structural and biophysical characterisation of membrane protein-ligand binding. © 2013.

  8. Interaction of gelatin with promethazine hydrochloride: Conductimetry, tensiometry and circular dichroism studies

    Science.gov (United States)

    Rub, Malik Abdul; Asiri, Abdullah M.; Khan, Javed Masood; Khan, Rizwan Hasan; Kabir-ud Din

    2013-10-01

    The interaction of amphiphilic phenothiazine drug promethazine hydrochloride (PMT) with gelatin in aqueous as well as aqueous-electrolyte (50 mM NaCl) solutions has been studied by using conductimetry, tensiometry and circular dichroism (CD) techniques. The drug interacts with gelatin similar to the interaction of surfactants and polymers. Hence, we have considered the gelatin-amphiphile interaction approach using conductimetry and tensiometry. The plots of specific conductivity versus concentration of drug were nonlinear with three different linear regions with two clear breaks. The critical aggregation concentration (cac), i.e., first break point, appeared well below the usual critical micelle concentration (cmc). Second break is regarded as polymer saturation point (psp) which is similar to cmc. The interaction starts with the formation of a highly surface-active complex as revealed by the lowering of surface tension on the addition of drug to the macromolecule (gelatin). The results further show that the cac decreases on increasing the gelatin concentration, while psp increases for all concentrations of gelatin which is a clear indication of the interaction between the drug and gelatin. By the use of degree of ionization, free energies of aggregation (ΔGagg) and micellization (ΔGmic) were also evaluated. As inorganic salts increase the ionic strength, the solubility of amphiphile (drug) is lowered by ionic screening effects, resulting in a greater tendency to aggregate at lower concentration. Therefore, both the cac and psp/cmc values decrease. Effect of PMT on the secondary structure of gelatin in aqueous solutions was also investigated using CD measurements. The measurements demonstrated that the random coil content of gelatin increases with increasing the drug concentration.

  9. What can we Learn on Gas Phase Chiral Compounds by Photoelectron Circular Dichroism ?

    Science.gov (United States)

    Nahon, Laurent

    2017-06-01

    Since 15 years, a new type of chiroptical effect has been the subject of a large array of both theoretical and experimental studies: Photoelectron Circular Dichroism (PECD) in the angular distribution of photoelectrons produced by CPL-ionization of pure enantiomers in the gas phase observed as a very intense (up to 35 %) forward/backward asymmetry with respect to the photon axis and which reveals the chirality of the molecule (configuration). PECD happens to be an orbital-specific, photon energy dependent effect and is a very subtle probe of the molecular potential being very sensitive to static molecular structures such as conformers, chemical substitution, clusters, as well as to vibrational motion, much more so than other observables in photoionization such as the cross section or the β asymmetry parameter (for a recent review see L. Nahon, G. A. Garcia, and I. Powis, J. Elec. Spec. Rel. Phen. 204, 322 (2015)). Therefore PECD studies have both a fundamental interest as well and analytical interest, especially since chiral species are ubiquitous in the biosphere, food and medical industry. This last aspect is probably the driving force for the recent extension of PECD studies by the laser community using UV REMPI schemes. After a large introduction to the PECD process itself, and a description of our double imaging electron/ion coincidence set-up, several recent results on one-photon VUV PECD will be presented, including: - Sensitivity to chemical substitutions, isomerism and conformation - Case of floppy biomolecules such as amino acids alanine and proline with a conformer analysis and possible consequences for the origin of life's homochirality - Analytical capabilities in terms of enantiomeric excess determination on a pure molecule as well as on a mixture of compounds. Future trends for PECD studies will be given regarding the case of more complex/structured chiral systems as well as opportunities for time-resolved PECD opened by the recent first performance

  10. On the wavelength dependence of UV induced thymine photolesions: a synchrotron radiation circular dichroism study.

    Science.gov (United States)

    Madsen, Marlene Møller; Jones, Nykola C; Nielsen, Steen Brøndsted; Hoffmann, Søren Vrønning

    2016-11-09

    Solar mutagenesis via the formation of thymine dimer photoproducts is a primary cause of skin cancer. The aim of this study is to provide a direct method for following the development of photolesions in thymine single strands and to determine how the formation of these photoproducts depends on the excitation wavelength in the ultraviolet (UV) between 210 nm and 325 nm. Experiments were performed both with a 20 Hz pulsed, intense, tunable laser as well as UV lamps (at 254 nm and 302 nm), but we find that only the dose matters at these wavelengths for the yield of photoproducts. Hence in both cases the lesion process is due to one-photon absorption. The formation and yields of the photoproducts as the irradiation dose is increased is followed through measurement of synchrotron radiation circular dichroism (SRCD) spectra. A principal component analysis (PCA) of the SRCD data yields CD signatures for each of the resulting photoproducts and reveals a strong irradiation wavelength dependence upon which products are formed; cyclobutane pyrimidine dimers (CPDs) are formed primarily at higher irradiation wavelengths (from 250 to 300 nm); the 6,4 pyrimidine-pyrimidone photoadduct (64PP) is formed in the range 210 to 285 nm, with a higher rate of formation in the lower part of that range, while in the very lowest irradiation wavelength range (210 to 240 nm) we find thymidine monophosphate (dTMP), which indicates cleavage of the DNA backbone. Our work demonstrates the strength of SRCD spectroscopy compared to ordinary absorption spectroscopy, as the latter is not sufficient to obtain fingerprints of the thymine photoproducts.

  11. X-ray magnetic and natural circular dichroism from first principles: Calculation of K - and L1-edge spectra

    Science.gov (United States)

    Bouldi, N.; Vollmers, N. J.; Delpy-Laplanche, C. G.; Joly, Y.; Juhin, A.; Sainctavit, Ph.; Brouder, Ch.; Calandra, M.; Paulatto, L.; Mauri, F.; Gerstmann, U.

    2017-08-01

    An efficient first-principles approach to calculate x-ray magnetic circular dichroism (XMCD) and x-ray natural circular dichroism (XNCD) is developed and applied in the near-edge region at the K and L1 edges in solids. Computation of circular dichroism requires precise calculations of x-ray absorption spectra (XAS) for circularly polarized light. For the derivation of the XAS cross section, we used a relativistic description of the photon-electron interaction that results in an additional term in the cross section that couples the electric dipole operator with an operator σ .(ɛ ×r ) that we call the spin position operator. The numerical method relies on pseudopotentials, on the gauge including projected augmented-wave method, and on a collinear spin relativistic description of the electronic structure. We apply the method to calculations of K -edge XMCD spectra of ferromagnetic iron, cobalt, and nickel and of I L1-edge XNCD spectra of α -LiIO3 , a compound with broken inversion symmetry. For XMCD spectra we find that, even if the electric dipole term is the dominant one, the electric quadrupole term is not negligible (8% in amplitude in the case of iron). The term coupling the electric dipole operator with the spin-position operator is significant (28% in amplitude in the case of iron). We obtain a sum rule relating this term to the spin magnetic moment of the p states. In α -LiIO3 we recover the expected angular dependence of the XNCD spectra.

  12. Enantioselective recognition of radezolid by cyclodextrin modified capillary electrokinetic chromatography and electronic circular dichroism.

    Science.gov (United States)

    Michalska, Katarzyna; Gruba, Ewa; Bocian, Wojciech; Cielecka-Piontek, Judyta

    2017-05-30

    A method for the enantioseparation of radezolid (RAD), an analogue of a truly new class of antibacterial agents, oxazolidinones, was developed based on capillary electrokinetic chromatography using a cyclodextrin as a chiral pseudophase (CD-cEKC). The mechanism of RAD separation, together with its precursor, were investigated to directly define the relationship between the oxazolidinone structure and the complexation process. During the development of the method, anionic single isomer cyclodextrins were tested. They were ranked in order from hydrophilic to hydrophobic as follows: heptakis-(2,3-dihydroxy-6-sulfo)-β-cyclodextrin (HS-β-CD), heptakis-(2,3-diacetyl-6-sulfo)-β-cyclodextrin (HDAS-β-CD) and heptakis-(2,3-dimethyl-6-sulfo)-β-cyclodextrin (HDMS-β-CD). Experiments were performed at pH values of 2.5, 6.6, 8.2 and 9.6. The cyclodextrins that had an acetyl or methyl group at the C2 and C3 positions, referred to as HDAS-β-CD and HDMS-β-CD, respectively, exhibited partial and baseline separation of enantiomers in a low pH buffer. However, higher temperatures were required for HDAS-β-CD and acetonitrile addition was required for HDMS-β-CD. During the experiments, different organic solvents, varying in their amphiprotic or aprotic nature, were tested. The best results for the separation of enantiomers using the CD-cEKC method were obtained with 40mM HDMS-β-CD dissolved in a 50mM phosphate buffer (pH 2.5) with the addition of acetonitrile (65:35, v/v) at 27°C, reversed polarity and a voltage equal to 28kV. The apparent binding constants for each enantiomer to HDAS-β-CD or HDMS-β-CD were calculated. Finally, the stereochemistry of (S) and (R)-RAD and the behaviour of selected complex formations were established using electronic circular dichroism. Copyright © 2017 Elsevier B.V. All rights reserved.

  13. Calcium Binding Ability of Recombinant Buffalo Regucalcin: A Study Using Circular Dichroism Spectroscopy.

    Science.gov (United States)

    Harikrishna, P; Thomas, Jobin; Shende, A M; Bhure, S K

    2017-04-01

    Regucalcin is a calcium regulating multifunctional protein reported to have many important functions like calcium homeostasis, anti-oxidative, anti-apoptotic and anti-cancerous functions. Although it is demonstrated as a calcium regulating protein, the calcium binding ability of regucalcin is still a controversy. The main reason for the controversy is that it lacks a typical EF hand motif which is common to most of the calcium binding proteins. Even though many studies reported regucalcin as a calcium binding protein, there are some studies reporting regucalcin as non-calcium binding also. In the present study, we investigated the calcium binding ability of recombinant buffalo regucalcin by assessing the secondary structural changes of the protein using circular dichroism spectroscopy after adding Ca(2+) to the protein solution. Two types of calcium binding studies were done, one with different concentration of calcium chloride (0.5 mM CaCl2, 1 mM CaCl2, 2 mM CaCl2) and other at different time interval (no incubation and 10 min incubation) after addition of calcium chloride. Significant structural changes were observed in both studies which prove the calcium binding ability of recombinant regucalcin. A constant increase in the α-helix (1.1% with 0.5 mM CaCl2, 1.4% with 1 mM CaCl2, 3.5% with 2 mM CaCl2) and a decrease in β-sheets (78.5% with 0.5 mM CaCl2, 77.4% with 1 mM CaCl2, 75.7% with 2 mM CaCl2) were observed with the increase in calcium chloride concentration. There was a rapid increase in α-helix and decrease in β-sheets immediately after addition of calcium chloride, which subsides after 10 min incubation.

  14. Large area, surface discharge pumped, vacuum ultraviolet light source

    Science.gov (United States)

    Sze, Robert C.; Quigley, Gerard P.

    1996-01-01

    Large area, surface discharge pumped, vacuum ultraviolet (VUV) light source. A contamination-free VUV light source having a 225 cm.sup.2 emission area in the 240-340 nm region of the electromagnetic spectrum with an average output power in this band of about 2 J/cm.sup.2 at a wall-plug efficiency of approximately 5% is described. Only ceramics and metal parts are employed in this surface discharge source. Because of the contamination-free, high photon energy and flux, and short pulse characteristics of the source, it is suitable for semiconductor and flat panel display material processing.

  15. Vacuum ultraviolet electronic properties of liquids. Progress report

    Energy Technology Data Exchange (ETDEWEB)

    Painter, L.R.

    1980-06-01

    A program to study the electronic structure of liquids over the energy range from 2 to 25 eV was carried out from November, 1968 to October 1980. These studies basically consisted of measuring the reflectance, transmittance, photoionization, and photoemission of liquids in the vacuum ultraviolet spectral region as a function of angle of incidence and photon energy. Such measurements are analyzed to yield the optical and dielectric functions of the liquid as functions of photon energy. A summary of the progress in the program is presented. (GHT)

  16. CIV Polarization Measurements Using a Vacuum Ultraviolet Fabry Perot

    Science.gov (United States)

    West, Edward A.

    2009-01-01

    Marshall Space Flight Center's (MSFC) is developing a Vacuum Ultraviolet (VUV) Fabry Perot that will be launched on a sounding rocket for high throughput, high-cadence, extended field of view CIV (155nm) measurements. These measurements will provide (i) Dopplergrams for studies of waves, oscillations, explosive events, and mass motions through the transition region, and, (ii), polarization measurements to study the magnetic field in the transition region. This paper will describe the scientific goals of the instrument, a brief description of the optics and the polarization characteristics of the VUV Fabry Perot.

  17. Absolute photon-flux measurements in the vacuum ultraviolet

    Science.gov (United States)

    Samson, J. A. R.; Haddad, G. N.

    1974-01-01

    Absolute photon-flux measurements in the vacuum ultraviolet have extended to short wavelengths by use of rare-gas ionization chambers. The technique involves the measurement of the ion current as a function of the gas pressure in the ion chamber. The true value of the ion current, and hence the absolute photon flux, is obtained by extrapolating the ion current to zero gas pressure. Examples are given at 162 and 266 A. The short-wavelength limit is determined only by the sensitivity of the current-measuring apparatus and by present knowledge of the photoionization processes that occur in the rate gases.

  18. Circular dichroism spectroscopy and DFT calculations in determining absolute configuration and E/Z isomers of conjugated oximes.

    Science.gov (United States)

    Rode, Joanna E; Frelek, Jadwiga

    2017-11-01

    The primary purpose of this work was to demonstrate the suitability of circular dichroism (CD) spectroscopy in stereochemical studies of α,β-unsaturated oximes, with particular emphasis on determination of E and Z geometry of the oxime double bond. As models for this study, O-phenyl and O-triphenylmethyl (trityl) oximes of 4-hydroxy-2-methylcyclopent-2-en-1-one were selected. These model compounds differ in both absolute configuration at C4 carbon atom and E-Z configuration of the oxime double bond. The basic dichroic technique applied was electronic circular dichroism (ECD) assisted by quantum-chemical calculations and vibrational circular dichroism (VCD) for selected cases. Such an approach enabled effective implementation of both goals. Thus, we were able to associate the signs of Cotton effects in the range of 190-240 nm with the absolute configuration at C4 and within 240-300 nm with the E- or Z-geometry of the oxime double bond. Within this work, optical activity of the protecting trityl group was also studied towards formation of the propeller-shaped conformations by using the same combined CD/DFT methodology. As shown, the helical structure of the trityl group has a considerable influence on the ECD spectra. However, the MPM and PMP conformers of the trityl group are in fact almost equally populated in the conformational equilibrium, making it impossible to distinguish them. On the other hand, rotamers of the hydroxyl group at C4 show a decisive impact on the VCD spectra in both phenoxy and trityl oximes. © 2017 Wiley Periodicals, Inc.

  19. Circular dichroism spectroscopic investigation of double-decker phthalocyanine with G-Quadruplex as promising telomerase inhibitor

    Science.gov (United States)

    Baǧda, Efkan; Baǧda, Esra; Yabaş, Ebru

    2017-01-01

    In the present study, interaction of a double-decker phthalocyanine with two G-quadruplex DNA, Tel 21 and cMYC, was investigated. To the best of our knowledge, this is the first study about G-quadruplex-double decker phthalocyanine interaction. The spectrophotometric titration method was used for binding constant calculations. From the binding constants, it can be said that double-decker phthalocyanine more likely to bind Tel 21 rather than cMYC. The conformational changes upon binding were monitored via circular dichroism spectroscopy. The ethidium bromide replacement assay was investigated spectrofluorometrically.

  20. Elucidating the Structure of Chiral Molecules by using Amplified Vibrational Circular Dichroism: From Theory to Experimental Realization.

    Science.gov (United States)

    Domingos, Sérgio R; Hartl, František; Buma, Wybren Jan; Woutersen, Sander

    2015-10-22

    The front cover artwork is provided by Dr. Sérgio Rosa Domingos, Prof. Wybren Jan Buma, and Prof. Sander Woutersen (University of Amsterdam, The Netherlands) as well as Prof. František Hartl (University of Reading, UK). The image shows a researcher/explorer highlighting a moiety within a large molecular system by using a flashlight, and in that way detecting the vibrational circular dichroism of that specific moiety. Read the full text of the article at 10.1002/cphc.201500551. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. TD-DFT Investigation of the Magnetic Circular Dichroism Spectra of Some Purine and Pyrimidine Bases of Nucleic Acids

    DEFF Research Database (Denmark)

    Fahleson, Tobias; Kauczor, Joanna; Norman, Patrick

    2015-01-01

    We present a computational study of the magnetic circular dichroism (MCD) spectra in the 200–300 nm wavelength region of purine and its derivative hypoxanthine, as well as of the pyrimidine bases of nucleic acids uracil, thymine, and cytosine, using the B3LYP and CAM–B3LYP functionals. Solvent...... and the B term shape of the spectra of pyrimidine bases are reproduced. Our calculations also correctly reproduce the reversed phase of the MCD bands in purine compared to that of its derivatives present in nucleic acids. Solvent effects are sizable and system specific, but they do not in general alter...

  2. Induced Circular Dichroism in Phosphine Gold(I) Aryl Acetylide Urea Complexes through Hydrogen-Bonded Chiral Co-Assemblies.

    Science.gov (United States)

    Dubarle-Offner, Julien; Moussa, Jamal; Amouri, Hani; Jouvelet, Benjamin; Bouteiller, Laurent; Raynal, Matthieu

    2016-03-14

    Phosphine gold(I) aryl acetylide complexes equipped with a central bis(urea) moiety form 1D hydrogen-bonded polymeric assemblies in solution that do not display any optical activity. Chiral co-assemblies are formed by simple addition of an enantiopure (metal-free) complementary monomer. Although exhibiting an intrinsically achiral linear geometry, the gold(I) aryl acetylide fragment is located in the chiral environment displayed by the hydrogen-bonded co-assemblies, as demonstrated by induced circular dichroism (ICD). © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Relaxation Dynamics in Photoexcited Chiral Molecules Studied by Time-Resolved Photoelectron Circular Dichroism: Toward Chiral Femtochemistry

    CERN Document Server

    Comby, Antoine; Boggio-Pasqua, Martial; Descamps, Dominique; Légaré, Francois; Nahon, Laurent; Petit, Stéphane; Pons, Bernard; Fabre, Baptiste; Mairesse, Yann; Blanchet, Valérie

    2016-01-01

    Unravelling the main initial dynamics responsible for chiral recognition is a key stepin the understanding of many biological processes. However this challenging task requires a sensitive enantiospecic probe to investigate molecular dynamics on their natural femtosecond timescale. Here we show that, in the gas phase, the ultrafast relaxationdynamics of photoexcited chiral molecules can be tracked by recording Time-ResolvedPhotoElectron Circular Dichroism (TR-PECD) resulting from the photoionisation bya circularly polarized probe pulse. A large forward/backward asymmetry along theprobe propagation axis is observed in the photoelectron angular distribution. Its evolution with pump-probe delay reveals ultrafast dynamics that are inaccessible in theangle-integrated photoelectron spectrum nor via the usual electron emission anisotropyparameter ($\\beta$). PECD, which originates from the electron scattering in the chiral molecular potential, appears as a new sensitive observable for ultrafast molecular dynamicsin ch...

  4. Luminescence, circular dichroism and in silico studies of binding interaction of synthesized naphthylchalcone derivatives with bovine serum albumin.

    Science.gov (United States)

    Pasricha, Sharda; Sharma, Deepti; Ojha, Himanshu; Gahlot, Pragya; Pathak, Mallika; Basu, Mitra; Chawla, Raman; Singhal, Sugandha; Singh, Anju; Goel, Rajeev; Kukreti, Shrikant; Shukla, Shefali

    2017-11-01

    Chalcones possess various biological properties, for example, antimicrobial, anti-inflammatory, analgesic, antimalarial, anticancer, antiprotozoal and antitubercular activity. In this study, naphthylchalcone derivatives were synthesized and characterized using (1) H NMR (13) C NMR, Fourier transform infrared and mass techniques. Yields for all derivatives were found to be >90%. Protein-drug interactions influence the absorption, distribution, metabolism and excretion (ADME) properties of a drug. Therefore, to establish whether the synthesized naphthylchalcone derivatives can be used as drugs, their binding interaction toward a serum protein (bovine serum albumin) was investigated using fluorescence, circular dichroism and molecular docking techniques under physiological conditions. Fluorescence quenching of the protein in the presence of naphthylchalcone derivatives, and other derived parameters such as association constants, number of binding sites and static quenching involving confirmed non-covalent binding interactions in the protein-ligand complex were observed. Circular dichroism clearly showed changes in the secondary structure of the protein in the presence of naphthylchalcones, indicating binding between the derivatives and the serum protein. Molecular modelling further confirmed the binding mode of naphthylchalcone derivatives in bovine serum albumin. A site-specific molecular docking study of naphthylchalcone derivatives with serum albumin showed that binding took place primarily in the aromatic low helix and then in subdomain II. The dominance of hydrophobic, hydrophilic and hydrogen bonding was clearly visible and was responsible for stabilization of the complex. Copyright © 2017 John Wiley & Sons, Ltd.

  5. Enantioseparation of racemic trans-δ-viniferin using high speed counter-current chromatography based on induced circular dichroism technology.

    Science.gov (United States)

    Han, Chao; Xu, Jinfang; Wang, Xiaobing; Xu, Xiaoming; Luo, Jianguang; Kong, Lingyi

    2014-01-10

    A preparative chiral high speed counter-current chromatography (HSCCC) method based on induced circular dichroism (ICD) spectrum was developed to separate trans-δ-viniferin (TVN) enantiomers successfully. The important parameters for the chiral HSCCC separation process, including the type of chiral selector (CS), the concentration of chiral selector and the equilibrium temperature, were optimized using induced circular dichroism spectrum. The final separation procedure was established with a biphasic solvent system composed of n-hexane-ethyl acetate-25 mmol L(-1) hydroxypropyl-β-cyclodextrin aqueous solution (5:5:10, v/v/v) in the head-to-tail elution mode at 5 °C. Under optimum chiral HSCCC separation conditions, 8.2mg of (7S, 8S)-TVN (1) and 9.4 mg of (7R, 8R)-TVN (2) were successfully separated from 20mg TVN enantiomers with the purity of 99.51% and 99.36%, respectively. Copyright © 2013 Elsevier B.V. All rights reserved.

  6. Simulation of Vacuum UV Absorption and Electronic Circular Dichroism Spectra of Methyl Oxirane: the Role of Vibrational Effects

    Science.gov (United States)

    Hodecker, Manuel; Biczysko, Malgorzata; Dreuw, Andreas; Barone, Vincenzo

    2017-01-01

    Vibrationally resolved one-photon absorption and electronic circular dichroism spectra of (R)-methyl oxirane were calculated with different electronic and vibronic models selecting, through an analysis of the convergence of the results, the best compromise between reliability and computational cost. Linear-response TD-DFT/CAM-B3LYP/SNST electronic computations in conjunction with the simple vertical gradient vibronic model were chosen and employed for systematic comparison with the available experimental data. Remarkable agreement between simulated and experimental spectra was achieved for both one photon absorption and circular dichroism concerning peak positions, relative intensities, and general spectral shapes considering the computational efficiency of the chosen theoretical approach. The significant improvement of the results with respect to smearing of vertical electronic transitions by phenomenological Gaussian functions and the possible inclusion of solvent effects by polarizable continuum models at a negligible additional cost paves the route toward the simulation and analysis of spectral shapes of complex molecular systems in their natural environment. PMID:27159495

  7. Combining sequence-based prediction methods and circular dichroism and infrared spectroscopic data to improve protein secondary structure determinations

    Directory of Open Access Journals (Sweden)

    Lees Jonathan G

    2008-01-01

    Full Text Available Abstract Background A number of sequence-based methods exist for protein secondary structure prediction. Protein secondary structures can also be determined experimentally from circular dichroism, and infrared spectroscopic data using empirical analysis methods. It has been proposed that comparable accuracy can be obtained from sequence-based predictions as from these biophysical measurements. Here we have examined the secondary structure determination accuracies of sequence prediction methods with the empirically determined values from the spectroscopic data on datasets of proteins for which both crystal structures and spectroscopic data are available. Results In this study we show that the sequence prediction methods have accuracies nearly comparable to those of spectroscopic methods. However, we also demonstrate that combining the spectroscopic and sequences techniques produces significant overall improvements in secondary structure determinations. In addition, combining the extra information content available from synchrotron radiation circular dichroism data with sequence methods also shows improvements. Conclusion Combining sequence prediction with experimentally determined spectroscopic methods for protein secondary structure content significantly enhances the accuracy of the overall results obtained.

  8. A circular dichroism sensor for Ni(2+) and Co(2+) based on L-cysteine capped cadmium sulfide quantum dots.

    Science.gov (United States)

    Tedsana, Wimonsiri; Tuntulani, Thawatchai; Ngeontae, Wittaya

    2015-03-31

    A new circular dichroism sensor for detecting Ni(2+) and Co(2+) was proposed for the first time using chiral chelating quantum dots. The detection principle was based on changing of circular dichroism signals of the chiral quantum dots when forming a chiral complex with Ni(2+) or Co(2+). L-Cysteine capped cadmium sulfide quantum dots (L-Cyst-CdS QDs) were proposed as a chiral probe. The CD spectrum of L-Cyst-CdS QDs was significantly changed in the presence of Ni(2+) and Co(2+). On the other hand, other studied cations did not alter the original CD spectrum. Moreover, when increasing the concentration of Ni(2+) or Co(2+), the intensity of the CD spectrum linearly increased as a function of concentration and could be useful for the quantitative analysis. The proposed CD sensor showed linear working concentration ranges of 10-60 μM and 4-80 μM with low detection limits of 7.33 μМ and 1.13 μM for the detection of Ni(2+) and Co(2+), respectively. Parameters possibly affected the detection sensitivity such as solution pH and incubation time were studied and optimized. The proposed sensor was applied to detect Ni(2+) and Co(2+) in real water samples, and the results agreed well with the analysis using the standard ICP-OES. Copyright © 2014 Elsevier B.V. All rights reserved.

  9. The extra-terrestrial vacuum-ultraviolet wavelength range

    Science.gov (United States)

    Timothy, J. Gethyn; Wilhelm, Klaus; Xia, Lidong

    Electromagnetic radiation in the vacuum-ultraviolet (VUV) and extra-terrestrial range at wavelengths from 10 nm to 300 nm is absorbed in the upper atmosphere by ozone, molecular and atomic oxygen, and molecular nitrogen. Observations at wavelengths down to ≈ 200 nm can be carried out from stratospheric balloons, and observations below 200 nm require space platforms operating at altitudes above 250 km. The VUV spectral region contains emission lines and continua arising from plasma at formation temperatures ranging from about 104 K to more than 107 K. This chapter describes the wide range of plasma diagnostic techniques available at VUV wavelengths, and the development of instrumentation for studies of the high-temperature solar outer atmosphere and astrophysical plasmas. Finally, the prospects for future studies are briefly discussed.

  10. 3m vacuum ultraviolet spectrometer with optical multichanel detector

    Energy Technology Data Exchange (ETDEWEB)

    Marin, P.; Peraza, C. [Instituto Investigacion Basica. CIEMAT (Spain); Blanco, F.; Campos, J. [Universidad Complutense de Madrid (Spain). Facultad de Ciencias Fisicas

    1993-08-01

    This paper, describes the design and the performance of a normal incidence vacuum ultraviolet spectrometer, for the 300-2400 A spectral range. It is provided with a multichannel detection system. The monochromator is original design and it has been built at CIEMAT: It is equipped with a 3 m concave holographic grating with 2400 grooves/mm. The multichannel detector consists of a windowless double microchannel plate/phosphor screen image intensifier, coupled by fiber optic to a 1024 elements self-scanning linear photodiode array. The output from the arrays is digitized by a 12-bit analog to digital converter and stored in a computer for its later analysis. The necessary software to store and display data has been developed. (Author)

  11. 3m vacuum ultraviolet spectrometer with optical multichanel detector

    Energy Technology Data Exchange (ETDEWEB)

    Marin, P.; Peraza, C. (Instituto Investigacion Basica. CIEMAT (Spain)); Blanco, F.; Campos, J. (Universidad Complutense de Madrid (Spain). Facultad de Ciencias Fisicas)

    1993-01-01

    This paper, describes the design and the performance of a normal incidence vacuum ultraviolet spectrometer, for the 300-2400 A spectral range. It is provided with a multichannel detection system. The monochromator is original design and it has been built at CIEMAT: It is equipped with a 3 m concave holographic grating with 2400 grooves/mm. The multichannel detector consists of a windowless double microchannel plate/phosphor screen image intensifier, coupled by fiber optic to a 1024 elements self-scanning linear photodiode array. The output from the arrays is digitized by a 12-bit analog to digital converter and stored in a computer for its later analysis. The necessary software to store and display data has been developed. (Author)

  12. Vibrational circular dichroism (VCD), VCD exciton coupling, and X-ray determination of the absolute configuration of an α,β-unsaturated germacranolide.

    Science.gov (United States)

    Sánchez-Castellanos, Mariano; Bucio, María A; Hernández-Barragán, Angelina; Joseph-Nathan, Pedro; Cuevas, Gabriel; Quijano, Leovigildo

    2015-03-01

    The absolute configuration of was deduced by vibrational circular dichroism together with the evaluation of the Flack and Hooft X-ray parameters. Vibrational circular dichroism exciton coupling, using the carbonyl group signals, confirmed the absolute configuration of . In addition, sodium borohydride reduction of the 11,13-double bond of 6-epi-desacetyllaurenobiolide () yields an almost equimolecular mixture of C11 epimers, while reduction of the same double bond of 6-epi-laurenobiolide () provided almost exclusively the (11S) diastereoisomer . © 2015 Wiley Periodicals, Inc.

  13. A QM/MM-MD study on protein electronic properties: Circular dichroism spectra of oxytocin and insulin

    Science.gov (United States)

    Kitagawa, Yuya; Akinaga, Yoshinobu; Kawashima, Yukio; Jung, Jaewoon; Ten-no, Seiichiro

    2012-06-01

    A QM/MM (quantum-mechanical/molecular-mechanical) molecular-dynamics approach based on the generalized hybrid-orbital (GHO) method, in conjunction with the second-order perturbation (MP2) theory and the second-order approximate coupled-cluster (CC2) model, is employed to calculate electronic property accounting for a protein environment. Circular dichroism (CD) spectra originating from chiral disulfide bridges of oxytocin and insulin at room temperature are computed. It is shown that the sampling of thermal fluctuation of molecular geometries facilitated by the GHO-MD method plays an important role in the obtained spectra. It is demonstrated that, while the protein environments in an oxytocin molecule have significant electrostatic influence on its chiral center, it is compensated by solvent induced charges. This gives a reasonable explanation to experimental observations. GHO-MD simulations starting from different experimental structures of insulin indicate that existence of the disulfide bridges with negative dihedral angles is crucial.

  14. A QM/MM-MD study on protein electronic properties: Circular dichroism spectra of oxytocin and insulin

    Energy Technology Data Exchange (ETDEWEB)

    Kitagawa, Yuya [Graduate School of System Informatics, Kobe University, Kobe 657-8501 (Japan); CREST, Japan Science and Technology Agency (JST), 4-1-8 Honcho Kawaguchi, Saitama 332-0012 (Japan); Akinaga, Yoshinobu [RIKEN Advanced Institute for Computational Science, Kobe 650-0047 (Japan); Kawashima, Yukio [Department of Chemistry, Graduate School of Sciences, Kyushu University, Fukuoka 812-8581 (Japan); Institute of Advanced Research, Kyushu University, Fukuoka 812-8581 (Japan); Jung, Jaewoon [RIKEN Advanced Institute for Computational Science, Kobe 650-0047 (Japan); Ten-no, Seiichiro, E-mail: tenno@cs.kobe-u.ac.jp [Graduate School of System Informatics, Kobe University, Kobe 657-8501 (Japan); CREST, Japan Science and Technology Agency (JST), 4-1-8 Honcho Kawaguchi, Saitama 332-0012 (Japan)

    2012-06-05

    A QM/MM (quantum-mechanical/molecular-mechanical) molecular-dynamics approach based on the generalized hybrid-orbital (GHO) method, in conjunction with the second-order perturbation (MP2) theory and the second-order approximate coupled-cluster (CC2) model, is employed to calculate electronic property accounting for a protein environment. Circular dichroism (CD) spectra originating from chiral disulfide bridges of oxytocin and insulin at room temperature are computed. It is shown that the sampling of thermal fluctuation of molecular geometries facilitated by the GHO-MD method plays an important role in the obtained spectra. It is demonstrated that, while the protein environments in an oxytocin molecule have significant electrostatic influence on its chiral center, it is compensated by solvent induced charges. This gives a reasonable explanation to experimental observations. GHO-MD simulations starting from different experimental structures of insulin indicate that existence of the disulfide bridges with negative dihedral angles is crucial.

  15. Domain wall velocity measurement in permalloy nanowires with X-ray magnetic circular dichroism imaging and single shot Kerr microscopy

    Energy Technology Data Exchange (ETDEWEB)

    Moore, T.A., E-mail: t.a.moore@physics.or [Fachbereich Physik, Universitaet Konstanz, Universitaetsstrasse 10, 78457 Konstanz (Germany); Klaeui, M.; Heyne, L.; Moehrke, P. [Fachbereich Physik, Universitaet Konstanz, Universitaetsstrasse 10, 78457 Konstanz (Germany); Backes, D.; Rhensius, J. [Fachbereich Physik, Universitaet Konstanz, Universitaetsstrasse 10, 78457 Konstanz (Germany); Laboratory for Micro- and Nanotechnology, Paul Scherrer Institut, 5232 Villigen PSI (Switzerland); Ruediger, U. [Fachbereich Physik, Universitaet Konstanz, Universitaetsstrasse 10, 78457 Konstanz (Germany); Heyderman, L.J. [Laboratory for Micro- and Nanotechnology, Paul Scherrer Institut, 5232 Villigen PSI (Switzerland); Mentes, T.O.; Nino, M.A.; Locatelli, A. [Sincrotrone Trieste, 34012 Basovizza-Trieste (Italy); Potenza, A.; Marchetto, H.; Cavill, S.; Dhesi, S.S. [Diamond Light Source Ltd., Harwell Science and Innovation Campus, Didcot, Oxfordshire, OX11 0DE (United Kingdom)

    2010-05-15

    Domain walls (DWs) propagated along nanoscale magnetic wires by current or field pulses could potentially be used for data storage or logic applications, but the understanding of the DW dynamics, particularly under the influence of spin-polarized current, is incomplete. Measuring the velocity can give insights into the physics of the DW motion. Here we demonstrate DW velocity measurements in permalloy (Ni{sub 80}Fe{sub 20}) nanowires (1500 nm width and 20 nm thickness) using the techniques of X-ray magnetic circular dichroism photoemission electron microscopy (XMCD-PEEM) to image the magnetic contrast in the nanowires, and single shot Kerr microscopy, which allows for dynamic measurements. The magnetic imaging yields the average velocity as well as information on the DW spin structure, whereas the single shot method highlights the stochastic nature of the DW motion.

  16. Domain wall velocity measurement in permalloy nanowires with X-ray magnetic circular dichroism imaging and single shot Kerr microscopy

    Science.gov (United States)

    Moore, T. A.; Kläui, M.; Heyne, L.; Möhrke, P.; Backes, D.; Rhensius, J.; Rüdiger, U.; Heyderman, L. J.; Mentes, T. O.; Niño, M. Á.; Locatelli, A.; Potenza, A.; Marchetto, H.; Cavill, S.; Dhesi, S. S.

    2010-05-01

    Domain walls (DWs) propagated along nanoscale magnetic wires by current or field pulses could potentially be used for data storage or logic applications, but the understanding of the DW dynamics, particularly under the influence of spin-polarized current, is incomplete. Measuring the velocity can give insights into the physics of the DW motion. Here we demonstrate DW velocity measurements in permalloy ( Ni80Fe20) nanowires (1500 nm width and 20 nm thickness) using the techniques of X-ray magnetic circular dichroism photoemission electron microscopy (XMCD-PEEM) to image the magnetic contrast in the nanowires, and single shot Kerr microscopy, which allows for dynamic measurements. The magnetic imaging yields the average velocity as well as information on the DW spin structure, whereas the single shot method highlights the stochastic nature of the DW motion.

  17. Origin of magnetic circular dichroism in soft x-ray fluorescence of Heusler alloys at threshold excitation

    Energy Technology Data Exchange (ETDEWEB)

    Yablonskikh, M. V.; Yarmoshenko, Yu. M.; Grebennikov, V. I.; Kurmaev, E. Z.; Butorin, S. M.; Duda, L.-C.; Nordgren, J.; Plogmann, S.; Neumann, M.

    2001-06-15

    The results of investigations of the Heusler alloys NiMnSb and Co{sub 2}MnSb by magnetic circular dichroism in soft x-ray emission spectroscopy (SXEMCD) are presented. The data obtained are in a good agreement with theoretical calculations of x-ray emission. A very intense resonant inelastic peak in the Mn L{sub 3} spectra in the region of states above the nominal Fermi level was observed and attributed to x-ray reemission. The interplay between the theoretically predicted half-metallic character of the Mn 3d valence band and the Mn L{sub 2},L{sub 3} SXEMCD spectra is discussed.

  18. To Avoid Chasing Incorrect Chemical Structures of Chiral Compounds: Raman Optical Activity and Vibrational Circular Dichroism Spectroscopies.

    Science.gov (United States)

    Polavarapu, Prasad L; Covington, Cody L; Raghavan, Vijay

    2017-09-20

    A chemical structure (CS) identifies the connectivities between atoms, and the nature of those connections, for a given elemental composition. For chiral molecules, in addition to the identification of CS, the identification of the correct absolute configuration (AC) is also needed. Several chiral natural products are known whose CSs were initially misidentified and later corrected, and these errors were often discovered during the total synthesis of natural products. In this work, we present a new and convenient approach that can be used with Raman optical activity (ROA) and vibrational circular dichroism (VCD) spectroscopies, to distinguish between the correct and incorrect CSs of chiral compounds. This approach involves analyzing the spectral similarity overlap between experimental spectra and those predicted with advanced quantum chemical theories. Significant labor needed for establishing the correct CSs via chemical syntheses of chiral natural products can thus be avoided. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Using circular dichroism collected as a function of temperature to determine the thermodynamics of protein unfolding and binding interactions

    Science.gov (United States)

    Greenfield, Norma J.

    2009-01-01

    Circular dichroism (CD) is an excellent spectroscopic technique for following the unfolding and folding of proteins as a function of temperature. One of its principal applications is to determine the effects of mutations and ligands on protein and polypeptide stability If the change in CD as a function of temperature is reversible, analysis of the data may be used to determined the van't Hoff enthalpy (ΔH) and entropy (ΔS) of unfolding, the midpoint of the unfolding transition (TM) and the free energy (ΔG) of unfolding. Binding constants of protein-protein and protein-ligand interactions may also be estimated from the unfolding curves. Analysis of CD spectra obtained as a function of temperature is also useful to determine whether a protein has unfolding intermediates. Measurement of the spectra of five folded proteins and their unfolding curves at a single wavelength takes approximately eight hours. PMID:17406506

  20. X-ray magnetic circular dichroism and small angle neutron scattering studies of thiol capped gold nanoparticles.

    Energy Technology Data Exchange (ETDEWEB)

    de la Venta, J.; Bouzas, V.; Pucci, A.; Laguna-Marco, M. A.; Haskel, D.; te Velthuis, S. G. E; Hoffmann, A.; Lal, J.; Bleuel, M.; Ruggeri, G.; de Julian Fernandez, C.; Garcia, M. A.; Univ.Complutense de Madrid; Inst. de Magnetismo Aplicado; Univ. of Pisa; Lab. di Magnetismo Molecolare

    2009-01-01

    X-ray magnetic circular dichroism (XMCD) and Small Angle Neutron Scattering (SANS) measurements were performed on thiol capped Au nanoparticles (NPs) embedded into polyethylene. An XMCD signal of 0.8 {center_dot} 10{sup -4} was found at the Au L{sub 3} edge of thiol capped Au NPs embedded in a polyethylene matrix for which Superconducting Quantum Interference Device (SQUID) magnetometry yielded a saturation magnetization, M{sub s}, of 0.06 emu/g{sub Au}. SANS measurements showed that the 3.2 nm average-diameter nanoparticles are 28% polydispersed, but no detectable SANS magnetic signal was found with the resolution and sensitivity accessible with the neutron experiment. A comparison with previous experiments carried out on Au NPs and multilayers, yield to different values between XMCD signals and magnetization measured by SQUID magnetometer. We discuss the origin of those differences.

  1. X-ray magnetic circular dichroism and small angle neutron scattering study of thiol capped gold nanoparticles.

    Energy Technology Data Exchange (ETDEWEB)

    de la Venta, J.; Bouzas, V.; Pucci, A.; Laguna-Marco, M. A.; Haskel, D.; Pinel, E. F.; te Velthuis, S. G. E.; Hoffmann, A.; Lal, J.; Bleuel, M.; Ruggeri, G.; de Julian, C.; Garcia, M. A.; Univ. Complutense de Madrid; Inst. de Magnetismo Aplicado UCM; Univ. Pisa; Univ. di Padova

    2009-11-01

    X-ray magnetic circular dichroism (XMCD) and Small Angle Neutron Scattering (SANS) measurements were performed on thiol capped Au nanoparticles (NPs) embedded into polyethylene. An XMCD signal of 0.8 {center_dot} 10{sup -4} was found at the Au L{sub 3} edge of thiol capped Au NPs embedded in a polyethylene matrix for which Superconducting Quantum Interference Device (SQUID) magnetometry yielded a saturation magnetization, M{sub s}, of 0.06 emu/g{sub Au}. SANS measurements showed that the 3.2 nm average-diameter nanoparticles are 28% polydispersed, but no detectable SANS magnetic signal was found with the resolution and sensitivity accessible with the neutron experiment. A comparison with previous experiments carried out on Au NPs and multilayers, yield to different values between XMCD signals and magnetization measured by SQUID magnetometer. We discuss the origin of those differences.

  2. Determination of levamisole and tetramisole in seized cocaine samples by enantioselective high-performance liquid chromatography and circular dichroism detection.

    Science.gov (United States)

    Bertucci, Carlo; Tedesco, Daniele; Fabini, Edoardo; Di Pietra, Anna Maria; Rossi, Francesca; Garagnani, Marco; Del Borrello, Elia; Andrisano, Vincenza

    2014-10-10

    Levamisole, an anthelmintic drug, has been increasingly employed as an adulterant of illicit street cocaine over the last decade; recently, the use of tetramisole, the racemic mixture of levamisole and its enantiomer dexamisole, was also occasionally observed. A new enantioselective high-performance liquid chromatography (HPLC) method, performed on cellulose tris(3,5-dimethylphenylcarbamate) chiral stationary phases in normal-phase mode, was validated to determine the enantiomeric composition of tetramisole enantiomers in seized cocaine samples. Furthermore, the hyphenation of the validated HPLC method with a circular dichroism (CD) detection system allowed the direct determination of elution order and a selective monitoring of levamisole and dexamisole in the presence of possible interferences. The method was applied to the identification and quantitation of the two enantiomers of tetramisole in seized street cocaine samples. Copyright © 2014 Elsevier B.V. All rights reserved.

  3. X-ray absorption and magnetic circular dichroism studies of Co2FeAl in magnetic tunnel junctions

    Energy Technology Data Exchange (ETDEWEB)

    Ebke, D.; Kugler, Z.; Thomas, P.; Schebaum, O.; Schafers, M.; Nissen, D.; Schmalhorst, J.; Hutten, A.; Arenholz, E.; Thomas, A.

    2010-01-11

    The bulk magnetic moment and the element specific magnetic moment of Co{sub 2}FeAl thin films were examined as a function of annealing temperature by alternating gradient magnetometer (AGM) and X-ray absorption spectroscopy (XAS)/X-ray magnetic circular dichroism (XMCD), respectively. A high magnetic moment can be achieved for all annealing temperatures and the predicted bulk and interface magnetic moment of about 5 {tilde A}{sub B} are reached via heating. We will also present tunnel magnetoresistance (TMR) values of up to 153% at room temperature and 260% at 13 K for MgO based magnetic tunnel junctions (MTJs) with Co{sub 2}FeAl and Co-Fe electrodes.

  4. Effective Fully Polarizable QM/MM Approach To Model Vibrational Circular Dichroism Spectra of Systems in Aqueous Solution.

    Science.gov (United States)

    Giovannini, Tommaso; Olszòwka, Marta; Cappelli, Chiara

    2016-11-08

    We propose a methodology, based on the combination of classical Molecular Dynamics (MD) simulations with a fully polarizable Quantum Mechanical (QM)/Molecular Mechanics (MM)/Polarizable Continuum Model (PCM) Hamiltonian, to calculate Vibrational Circular Dichroism (VCD) spectra of chiral systems in aqueous solution. Polarization effects are included in the MM force field by exploiting an approach based on Fluctuating Charges (FQ). By performing the MD, the description of the solvating environment is enriched by taking into account the dynamical aspects of the solute-solvent interactions. On the other hand, the QM/FQ/PCM calculation of the VCD spectrum ensures an accurate description of the electronic density of the solute and a proper account for the specific interactions in solution. The application of our approach to (R)-methyloxirane and (l)-alanine in aqueous solution gives calculated spectra in remarkable agreement with their experimental counterparts and a substantial improvement with respect to the same spectra calculated with the PCM.

  5. Method To Determine Protein Concentration in the Protein-Nanoparticle Conjugates Aqueous Solution Using Circular Dichroism Spectroscopy.

    Science.gov (United States)

    Li, Shanghao; Peng, Zhili; Leblanc, Roger M

    2015-07-07

    Considerable efforts have been made to synthesize and characterize protein-nanoparticle conjugates (protein-NPs) for their promising applications in bionanotechnology. However, protein concentration determination in the protein-NPs has so far not been reported. In this Letter, we present a simple and nondestructive approach to quantify the protein concentration in the protein-NPs aqueous solution using circular dichroism (CD) spectroscopy. Carbon dots (∼4 nm), gold nanoparticles (∼10 nm), and polyethylene glycol (PEG, molecular weight ∼3000) were either physically mixed or covalently conjugated (not in the case of gold nanoparticles) with proteins (human transferrin, human serum albumin, and ovalbumin). We were able to quantify the protein concentration in the protein-nanoparticle conjugates using a calibration curve from the CD spectra.

  6. Investigation of binding behaviour of procainamide hydrochloride with human serum albumin using synchronous, 3D fluorescence and circular dichroism

    Directory of Open Access Journals (Sweden)

    Kirthi Byadagi

    2017-04-01

    Full Text Available Interaction of procainamide hydrochloride (PAH with human serum albumin (HSA is of great significance in understanding the pharmacokinetic and pharmacodynamic mechanisms of the drug. Multi-spectroscopic techniques were used to investigate the binding mode of PAH to HSA and results revealed the presence of static type of quenching mechanism. The number of binding sites, binding constants and thermodynamic parameters were calculated. The results showed a spontaneous binding of PAH to HSA and hydrophobic interactions played a major role. In addition, the distance between PAH and the Trp–214 was estimated employing the Förster's theory. Site marker competitive experiments indicated that the binding of PAH to HSA primarily took place in subdomain IIA (Sudlow's site I. The influence of interference of some common metal ions on the binding of PAH to HSA was studied. Synchronous fluorescence spectra (SFS, 3D fluorescence spectra and circular dichroism (CD results indicated the conformational changes in the structure of HSA.

  7. Local X-ray magnetic circular dichroism study of Fe/Cu(111) using a tunneling smart tip

    Energy Technology Data Exchange (ETDEWEB)

    DiLullo, Andrew; Shirato, Nozomi; Cummings, Marvin [Argonne National Laboratory, 9700 South Cass Avenue, Argonne, IL 60439 (United States); Kersell, Heath; Chang, Hao [Argonne National Laboratory, 9700 South Cass Avenue, Argonne, IL 60439 (United States); Ohio University, Athens, OH 45701 (United States); Rosenmann, Daniel; Miller, Dean; Freeland, John W. [Argonne National Laboratory, 9700 South Cass Avenue, Argonne, IL 60439 (United States); Hla, Saw-Wai [Argonne National Laboratory, 9700 South Cass Avenue, Argonne, IL 60439 (United States); Ohio University, Athens, OH 45701 (United States); Rose, Volker, E-mail: vrose@anl.gov [Argonne National Laboratory, 9700 South Cass Avenue, Argonne, IL 60439 (United States); Argonne National Laboratory, 9700 South Cass Avenue, Argonne, IL 60439 (United States)

    2016-01-28

    A tunneling smart tip of a synchrotron X-ray scanning tunneling microscope provides simultaneously localized topographic, elemental and magnetic information. Localized spectroscopy with simultaneous topographic, elemental and magnetic information is presented. A synchrotron X-ray scanning tunneling microscope has been employed for the local study of the X-ray magnetic circular dichroism at the Fe L{sub 2,3}-edges of a thin iron film grown on Cu(111). Polarization-dependent X-ray absorption spectra have been obtained through a tunneling smart tip that serves as a photoelectron detector. In contrast to conventional spin-polarized scanning tunneling microscopy, X-ray excitations provide magnetic contrast even with a non-magnetic tip. Intensity variations in the photoexcited tip current point to chemical variations within a single magnetic Fe domain.

  8. Intrinsic and Extrinsic Ferromagnetism in Co-Doped Indium Tin Oxide Revealed Using X-Ray Magnetic Circular Dichroism

    Directory of Open Access Journals (Sweden)

    A. M. H. R. Hakimi

    2017-01-01

    Full Text Available The effects of high-temperature annealing on ferromagnetic Co-doped Indium Tin Oxide (ITO thin films have been investigated using X-ray diffraction (XRD, magnetometry, and X-Ray Magnetic Circular Dichroism (XMCD. Following annealing, the magnetometry results indicate the formation of Co clusters with a significant increase in the saturation magnetization of the thin films arising from defects introduced during cluster formation. However, sum rule analysis of the element-specific XMCD results shows that the magnetic moment at the Co sites is reduced after annealing. The effects of annealing demonstrate that the ferromagnetism observed in the as-deposited Co-doped ITO films arises from intrinsic defects and cannot be related to the segregation of metallic Co clusters.

  9. Circular dichroism study of the interaction between mutagens and bilirubin bound to different binding sites of serum albumins.

    Science.gov (United States)

    Orlov, Sergey; Goncharova, Iryna; Urbanová, Marie

    2014-05-21

    Although recent investigations have shown that bilirubin not only has a negative role in the organism but also exhibits significant antimutagenic properties, the mechanisms of interactions between bilirubin and mutagens are not clear. In this study, interaction between bilirubin bound to different binding sites of mammalian serum albumins with structural analogues of the mutagens 2-aminofluorene, 2,7-diaminofluorene and mutagen 2,4,7-trinitrofluorenone were investigated by circular dichroism and absorption spectroscopy. Homological human and bovine serum albumins were used as chiral matrices, which preferentially bind different conformers of bilirubin in the primary binding sites and make it observable by circular dichroism. These molecular systems approximated a real system for the study of mutagens in blood serum. Differences between the interaction of bilirubin bound to primary and to secondary binding sites of serum albumins with mutagens were shown. For bilirubin bound to secondary binding sites with low affinity, partial displacement and the formation of self-associates were observed in all studied mutagens. The associates of bilirubin bound to primary binding sites of serum albumins are formed with 2-aminofluorene and 2,4,7-trinitrofluorenone. It was proposed that 2,7-diaminofluorene does not interact with bilirubin bound to primary sites of human and bovine serum albumins due to the spatial hindrance of the albumins binding domains. The spatial arrangement of the bilirubin bound to serum albumin along with the studied mutagens was modelled using ligand docking, which revealed a possibility of an arrangement of the both bilirubin and 2-aminofluorene and 2,4,7-trinitrofluorenone in the primary binding site of human serum albumin. Copyright © 2014 Elsevier B.V. All rights reserved.

  10. Distinct circular dichroism spectroscopic signatures of polyproline II and unordered secondary structures: applications in secondary structure analyses.

    Science.gov (United States)

    Lopes, Jose L S; Miles, Andrew J; Whitmore, Lee; Wallace, B A

    2014-12-01

    Circular dichroism (CD) spectroscopy is a valuable method for defining canonical secondary structure contents of proteins based on empirically-defined spectroscopic signatures derived from proteins with known three-dimensional structures. Many proteins identified as being "Intrinsically Disordered Proteins" have a significant amount of their structure that is neither sheet, helix, nor turn; this type of structure is often classified by CD as "other", "random coil", "unordered", or "disordered". However the "other" category can also include polyproline II (PPII)-type structures, whose spectral properties have not been well-distinguished from those of unordered structures. In this study, synchrotron radiation circular dichroism spectroscopy was used to investigate the spectral properties of collagen and polyproline, which both contain PPII-type structures. Their native spectra were compared as representatives of PPII structures. In addition, their spectra before and after treatment with various conditions to produce unfolded or denatured structures were also compared, with the aim of defining the differences between CD spectra of PPII and disordered structures. We conclude that the spectral features of collagen are more appropriate than those of polyproline for use as the representative spectrum for PPII structures present in typical amino acid-containing proteins, and that the single most characteristic spectroscopic feature distinguishing a PPII structure from a disordered structure is the presence of a positive peak around 220nm in the former but not in the latter. These spectra are now available for inclusion in new reference data sets used for CD analyses of the secondary structures of soluble proteins. © 2014 The Protein Society.

  11. Advantages of electronic circular dichroism detection for the stereochemical analysis and characterization of drugs and natural products by liquid chromatography.

    Science.gov (United States)

    Bertucci, Carlo; Tedesco, Daniele

    2012-12-21

    The need for analytical methods for the determination of the enantiomeric excess of chiral compounds increased significantly in the last decades, and enantioselective separation techniques resulted particularly efficient to this purpose. Moreover, when detection systems based on chiroptical properties (optical rotation or circular dichroism) are employed in high-performance liquid chromatography (HPLC), the stereochemistry of a chiral analyte can be fully determined. Indeed, the coupling of HPLC with chiroptical detection systems allows the simultaneous assessment of the absolute configuration of stereoisomers and the evaluation of the enantiomeric/diastereomeric excess of samples. These features are particularly important in the study of drugs and natural products provided with biological activity, because the assignment of their absolute stereochemistry is essential to establish reliable structure-activity relationships. The following review aims to discuss the analytical advantages arising from the employment of electronic circular dichroism (ECD) detection systems in stereochemical analysis by HPLC upon chiral and non-chiral stationary phases and their use for the stereochemical characterization of chiral drugs and natural compounds. The different methods for the correlation between absolute stereochemistry and chiroptical properties are critically discussed. Relevant HPLC applications of ECD detection systems are then reported, and their analytical advantages are highlighted. For instance, the importance of the concentration-independent anisotropy factor (g-factor; g=Δɛ/ɛ) for the determination of the stereoisomeric composition of samples upon non-chiral stationary phases is underlined, since its sensitivity makes ECD detection very well suited for the enantioselective analysis of large libraries of chiral compounds in relatively short times. Copyright © 2012 Elsevier B.V. All rights reserved.

  12. Developing a Magnetic Circular Dichroism Apparatus Equipped with Neodymium Magnet for Students to Investigate the Electronic Structures of Transition Metals and Lanthanoids

    Science.gov (United States)

    Yakubu, Abdallah; Suzuki, Takayoshi; Kita, Masakazu

    2017-01-01

    This paper describes the development of a simple magnetic circular dichroism (MCD) apparatus from a wood base and neodymium magnets and its configuration in the Faraday alignment. The applicability and effectiveness of the apparatus for MCD spectra measurements have been examined. The apparatus was used by undergraduate students to conduct MCD…

  13. Developing a Magnetic Circular Dichroism Apparatus Equipped with Neodymium Magnet for Students to Investigate the Electronic Structures of Transition Metals and Lanthanoids

    Science.gov (United States)

    Yakubu, Abdallah; Suzuki, Takayoshi; Kita, Masakazu

    This paper describes the development of a simple magnetic circular dichroism (MCD) apparatus from a wood base and neodymium magnets and its configuration in the Faraday alignment. The applicability and effectiveness of the apparatus for MCD spectra measurements have been examined. The apparatus was used by undergraduate students to conduct MCD…

  14. Soft X-ray magnetic circular dichroism study of the colossal magnetoresistance compound La1-xSrxMnO3

    NARCIS (Netherlands)

    Pellegrin, E; Tjeng, LH; deGroot, FMF; Hesper, R; Sawatzky, GA; Moritomo, Y; Tokura, Y

    Soft X-ray magnetic circular dichroism (SXMCD) measurements are reported on the O K- and Mn L-absorption edges of La1-xSrxMnO3 (x = 0.15,0.18, and 0.4) single crystals in their ferromagnetic regime. This has been done using a recently developed experimental technique for magnetizing the samples

  15. X-ray magnetic circular dichroism study of Dy-doped Bi2Te3 topological insulator thin films

    Science.gov (United States)

    Figueroa, A. I.; Baker, A. A.; Harrison, S. E.; Kummer, K.; van der Laan, G.; Hesjedal, T.

    2017-01-01

    Magnetic doping of topological insulators (TIs) is crucial for unlocking novel quantum phenomena, paving the way for spintronics applications. Recently, we have shown that doping with rare earth ions introduces large magnetic moments and allows for high doping concentrations without the loss of crystal quality, however no long range magnetic order was observed. In Dy-doped Bi2Te3 we found a band gap opening above a critical doping concentration, despite the paramagnetic bulk behavior. Here, we present a surface-sensitive x-ray magnetic circular dichroism (XMCD) study of an in situ cleaved film in the cleanest possible environment. The Dy M4,5 absorption spectra measured with circularly polarized x-rays are fitted using multiplet calculations to obtain the effective magnetic moment. Arrott-Noakes plots, measured by the Dy M5 XMCD as a function of field at low temperatures, give a negative transition temperature. The evaporation of a ferromagnetic Co thin film did not introduce ferromagnetic ordering of the Dy dopants either; instead a lowering of the transition temperature was observed, pointing towards an antiferromagnetic ordering scenario. This result shows that there is a competition between the magnetic exchange interaction and the Zeeman interaction. The latter favors the Co and Dy magnetic moments to be both aligned along the direction of the applied magnetic field, while the exchange interaction is minimized if the Dy and Co atoms are antiferromagnetically coupled, as in zero applied field.

  16. Photodegradation of perfluorooctanoic acid by 185 nm vacuum ultraviolet light.

    Science.gov (United States)

    Chen, Jing; Zhang, Peng-yi; Liu, Jian

    2007-01-01

    The photodegradation of persistent and bioaccumulative perfluorooctanoic acid (PFOA) in water by 185 nm vacuum ultraviolet (VUV) light was examined to develop an effective technology to deal with PFOA pollution. PFOA degraded very slowly under irradiation of 254 nm UV light. However, 61.7% of initial PFOA was degraded by 185 nm VUV light within 2 h, and defluorination ratio reached 17.1%. Pseudo first-order-kinetics well simulated its degradation and defluorination. Besides, fluoride ion formed in water, 4 shorter-chain perfluorinated carboxylic acids (PFCAs), that is, perfluoroheptanoic acid, perfluorohexanoic acid, perfluoropentanoic acid, and perfluorobutanoic acid. These were identified as intermediates by LC-MS measurement. These PFCAs consecutively formed and further degraded with irradiation time. According to the mass balance calculation, no other byproducts were formed. It was proposed that PFCAs initially are decarboxylated by 185 nm light, and the radical thus formed reacts with water to form shorter-chain PFCA with one less CF2 unit.

  17. Control of the Polarization of a Vacuum-Ultraviolet, High-Gain, Free-Electron Laser

    Directory of Open Access Journals (Sweden)

    Enrico Allaria

    2014-12-01

    Full Text Available The two single-pass, externally seeded free-electron lasers (FELs of the FERMI user facility are designed around Apple-II-type undulators that can operate at arbitrary polarization in the vacuum ultraviolet-to-soft x-ray spectral range. Furthermore, within each FEL tuning range, any output wavelength and polarization can be set in less than a minute of routine operations. We report the first demonstration of the full output polarization capabilities of FERMI FEL-1 in a campaign of experiments where the wavelength and nominal polarization are set to a series of representative values, and the polarization of the emitted intense pulses is thoroughly characterized by three independent instruments and methods, expressly developed for the task. The measured radiation polarization is consistently >90% and is not significantly spoiled by the transport optics; differing, relative transport losses for horizontal and vertical polarization become more prominent at longer wavelengths and lead to a non-negligible ellipticity for an originally circularly polarized state. The results from the different polarimeter setups validate each other, allow a cross-calibration of the instruments, and constitute a benchmark for user experiments.

  18. Circular dichroism, magnetic knots and the spectropolarimetry of the Cosmic Microwave Background

    CERN Document Server

    Giovannini, Massimo

    2010-01-01

    When the last electron-photon scattering takes place in a magnetized environment, the degree of circular polarization of the outgoing radiation depends upon the magnetic field strength. After deriving the scattering matrix of the process, the generalized radiative transfer equations are deduced in the presence of the relativistic fluctuations of the geometry and for all the four brightness perturbations. The new system of equations is solved under the assumption that the incident radiation is not polarized. The induced V-mode polarization is analyzed both analytically and numerically. The corresponding angular power spectra are calculated and compared with the measured (or purported) values of the linear polarizations (i.e. E-mode and B-mode) as they arise in the concordance model and in its neighboring extensions. Possible connections between the V-mode polarization of the Cosmic Microwave background and the topological properties of the magnetic flux lines prior to equality are outlined and briefly explored...

  19. Co K-edge magnetic circular dichroism across the spin state transition in LaCoO3 single crystal

    Science.gov (United States)

    Efimov, V.; Ignatov, A.; Troyanchuk, I. O.; Sikolenko, V. V.; Rogalev, A.; Wilhelm, F.; Efimova, E.; Tiutiunnikov, S. I.; Karpinsky, D.; Kriventsov, V.; Yakimchuk, E.; Molodtsov, S.; Sainctavit, P.; Prabhakaran, D.

    2016-05-01

    We report on Co K-edge x-ray magnetic circular dichroism (XMCD) measurements of LaCoO3 single crystal in temperature range from 5 to 300 K and external magnetic field of 17 T. The response consists of pre-edge (at 7712 eV) and bi-polar peak (up at 7727, down at 7731 eV) with amplitudes, respectively, less than 10-3 and 10-2 of the Co K-edge jump. Using the sum rule the orbital magnetic moment of 4p Co is evaluated. Its temperature dependence reaches a maximum of (2.7 ± 0.9) x10-3 μB at 120 K, following the trend for the total magnetic moment on the Co obtained from the superconducting quantum interference device measurements. However, on warming from 25 to 120 K, the orbital magnetic moment of the 4p Co doubles while total magnetic moment of Co increases 10 times. First principle calculations are in order to relate the Co K-edge XMCD results to the orbital and spin moment of 3d Co.

  20. An atomic orbital based real-time time-dependent density functional theory for computing electronic circular dichroism band spectra.

    Science.gov (United States)

    Goings, Joshua J; Li, Xiaosong

    2016-06-21

    One of the challenges of interpreting electronic circular dichroism (ECD) band spectra is that different states may have different rotatory strength signs, determined by their absolute configuration. If the states are closely spaced and opposite in sign, observed transitions may be washed out by nearby states, unlike absorption spectra where transitions are always positive additive. To accurately compute ECD bands, it is necessary to compute a large number of excited states, which may be prohibitively costly if one uses the linear-response time-dependent density functional theory (TDDFT) framework. Here we implement a real-time, atomic-orbital based TDDFT method for computing the entire ECD spectrum simultaneously. The method is advantageous for large systems with a high density of states. In contrast to previous implementations based on real-space grids, the method is variational, independent of nuclear orientation, and does not rely on pseudopotential approximations, making it suitable for computation of chiroptical properties well into the X-ray regime.

  1. Comparative circular dichroism studies of an anti-fluorescein monoclonal antibody (Mab 4-4-20) and its derivatives.

    Science.gov (United States)

    Tetin SYu; Mantulin, W W; Denzin, L K; Weidner, K M; Voss, E W

    1992-12-08

    This study presents circular dichroism (CD) spectra of a high-affinity monoclonal anti-fluorescein antibody (Mab 4-4-20), its Fab fragments, and corresponding single-chain antibody (SCA). In the region 200-250 nm, the differences in the CD spectra between these proteins reflect the uneven distribution of chromophores (tryptophan and tyrosine) rather than a major conformational change. On the basis of near-UV CD spectra, binding of the hapten fluorescein to these protein antibodies elicits an increased asymmetry in the microenvironment of the chromophoric residues in contact with the hapten and also perturbs the interface between VL and VH domains. The hapten-binding site provides a chiral microenvironment for fluorescein that elicits a pronounced induced fluorescein CD spectrum in both the visible and UV regions. In contrast to the parent molecules, SCA is thermolabile. Our results demonstrate that (1) UV CD spectra are useful for assessing the chromophoric microenvironment in the binding portion of antibodies and (2) the extrinsic fluorescein hapten CD spectra provide information about the interaction of hapten with the binding pocket.

  2. Interstellar condensed (icy) amino acids and precursors: theoretical absorption and circular dichroism under UV and soft X-ray irradiation

    Science.gov (United States)

    Da Pieve, F.; Avendaño-Franco, G.; De Proft, F.; Geerlings, P.

    2014-05-01

    The photophysics of interstellar ices and condensed molecules adsorbed on grains is of primary importance for studies on the origin of the specific handedness of complex organic molecules delivered to the early Earth and of the homochirality of the building blocks of life. Here, we present quantum mechanical calculations based on time-dependent density functional theory for the absorption and circular dichroism (CD) of isovaline and its chiral precursor 5-ethyl-5-methylhydantoin, both observed in meteoritic findings. The systems are considered in their geometrical conformation as extracted from a full solid (icy) matrix, as a shortcut to understand the behaviour of molecules with fixed orientation, and/or taking into account the full solid matrix. In the context of a possible `condensation-warming plus hydrolysis-recondensation' process, we obtain that: (i) for low-energy excitations, the `condensed' precursor has a stronger CD with respect to the amino acid, suggesting that the handedness of the latter could be biased by asymmetric photolysis of the precursor in cold environments; (ii) enantiomeric excess could in principle be induced more efficiently in both systems for excitation at higher energies (VUV). X-ray absorption near-edge spectroscopy and related CD results could serve as support for future experiments on ionization channels.

  3. Hierarchy of stochastic Schrödinger equation towards the calculation of absorption and circular dichroism spectra

    Science.gov (United States)

    Ke, Yaling; Zhao, Yi

    2017-05-01

    A theoretically solid and numerically exact method is presented for the calculation of absorption and circular dichroism (CD) spectra of molecular aggregates immersed in a harmonic bath constituted as the combination of some prominent quantized vibrational modes and continuous overdamped Brownian oscillators. The feasibility and the validity of newly proposed method are affirmed in the analytical monomer spectra. To go beyond the independent local bath approximation, all the correlations of site energy fluctuations and excitonic coupling fluctuations are included in our strategy, and their influence on the absorption and CD spectra is investigated based on the Frenkel exciton model of homodimer. In the end, a good fit of the absorption and part of CD spectra for the entire B800-B850 ring in the light-harvesting complexes 2 of purple bacteria to the experimental data is given, and the simulation results suggest that the asymmetry in the 800 nm region of CD spectra is actually an indication of B800-B850 inter-ring coupling.

  4. Energy- and k -resolved mapping of the magnetic circular dichroism in threshold photoemission from Co films on Pt(111)

    Science.gov (United States)

    Staab, Maximilian; Kutnyakhov, Dmytro; Wallauer, Robert; Chernov, Sergey; Medjanik, Katerina; Elmers, Hans Joachim; Kläui, Mathias; Schönhense, Gerd

    2017-04-01

    The magnetic circular dichroism in threshold photoemission (TPMCD) for perpendicularly magnetized fcc Co films on Pt(111) has been revisited. A complete mapping of the spectral function I (EB,kx,ky) (binding energy EB, momentum parallel to surface kx, ky) and the corresponding TPMCD asymmetry distribution AMCD(EB,kx,ky) has been performed for one-photon and two-photon photoemission using time-of-flight momentum microscopy. The experimental results allow distinguishing direct from indirect transitions. The measurements reveal clear band features of direct transitions from bulk bands that show a nontrivial asymmetry pattern. A significant homogeneous background with substantial asymmetry stemming from indirect transitions superposes direct transitions. Two-photon photoemission reveals enhanced emission intensity via an image potential state, acting as intermediate state. The image potential state enhances not only intensity but also asymmetry. The present results demonstrate that two-photon photoemission is a powerful method for mapping the spin-polarized unoccupied band structures and points out pathways for applying TPMCD as a contrast mechanism for various classes of magnetic materials.

  5. TD-DFT investigation of the magnetic circular dichroism spectra of some purine and pyrimidine bases of nucleic acids.

    Science.gov (United States)

    Fahleson, Tobias; Kauczor, Joanna; Norman, Patrick; Santoro, Fabrizio; Improta, Roberto; Coriani, Sonia

    2015-05-28

    We present a computational study of the magnetic circular dichroism (MCD) spectra in the 200-300 nm wavelength region of purine and its derivative hypoxanthine, as well as of the pyrimidine bases of nucleic acids uracil, thymine, and cytosine, using the B3LYP and CAM-B3LYP functionals. Solvent effects are investigated within the polarizable continuum model and by inclusion of explicit water molecules. In general, the computed spectra are found to be in good agreement with the experimental ones, apart from some overall blue shifts. Both the pseudo-A term shape of the MCD spectra of the purines and the B term shape of the spectra of pyrimidine bases are reproduced. Our calculations also correctly reproduce the reversed phase of the MCD bands in purine compared to that of its derivatives present in nucleic acids. Solvent effects are sizable and system specific, but they do not in general alter the qualitative shape of the spectra. The bands are dominated by the bright π → π* transitions, and our calculations in solution nicely reproduce their energy differences, improving the estimates obtained in the gas phase. Shoulders are predicted for purine and uracil due to n → π* excitations, but they are too weak to be observed in the experiment.

  6. AB-INITIO CALCULATION OF ELECTRONIC CIRCULAR-DICHROISM FOR TRANS-CYCLOOCTENE USING LONDON ATOMIC ORBITALS

    DEFF Research Database (Denmark)

    Bak, Keld L.; Hansen, Aage E.; Ruud, K.

    1995-01-01

    The second-quantization magnetic dipole operator that arises when London atomic orbitals are used as basis functions is derived. In atomic units, the magnetic dipole operator is defined as the negative of the first derivative of the electronic Hamiltonian containing the interaction with the exter......The second-quantization magnetic dipole operator that arises when London atomic orbitals are used as basis functions is derived. In atomic units, the magnetic dipole operator is defined as the negative of the first derivative of the electronic Hamiltonian containing the interaction...... that the length expression for the rotatory strength in linear response calculations gives gauge-origin-independent results. Sample calculations on ti ans-cyclooctene and its fragments are presented. Compared to conventional orbitals, the basis set convergence of the rotatory strengths calculated in the length...... form using London atomic orbitals is favourable. The rotatory strength calculated for trans-cyclooctene agrees nicely with the corresponding experimental circular dichroism spectrum, but the spectra for the fragment molecules show little resemblance with that of trans-cyclooctene....

  7. Enhanced biocatalysis mechanism under microwave irradiation in isoquercitrin production revealed by circular dichroism and surface plasmon resonance spectroscopy.

    Science.gov (United States)

    Gong, An; Zhu, Dan; Mei, Yi-Yuan; Xu, Xiao-Hui; Wu, Fu-An; Wang, Jun

    2016-04-01

    An efficient and rapid process for isoquercitrin production by hesperidinase-catalyzed hydrolysis of rutin was successfully developed under microwave irradiation detecting the affinity by circular dichroism (CD) and surface plasmon resonance (SPR) spectroscopy. A maximum isoquercitrin yield of 91.5±2.7% was obtained in 10min with the conditions of 10g/L hesperidinase, 2g/L rutin, 30°C and microwave power density 88.9W/L. Enzymatic reaction rate and Vm/Km in the microwave reactor were 6.34-fold higher than in a continuous flow microreactor and 1.24-fold higher than in a biphasic system. CD and SPR analysis results also showed that hesperidinase has a better selectivity and affinity (3.3-fold than in a batch reactor) to generate isoquercitrin under microwave irradiation. Microwave irradiation greatly improved the reaction efficiency and productivity, leading to a more positive economical assessment. The binding affinity indicates the presence of strong multivalent interactions between rutin and hesperidinase under microwave irradiation. Copyright © 2016 Elsevier Ltd. All rights reserved.

  8. Probing Magnetism in the Vortex Phase of PuCoGa5 by X-Ray Magnetic Circular Dichroism

    Science.gov (United States)

    Magnani, N.; Eloirdi, R.; Wilhelm, F.; Colineau, E.; Griveau, J.-C.; Shick, A. B.; Lander, G. H.; Rogalev, A.; Caciuffo, R.

    2017-10-01

    We measure x-ray magnetic circular dichroism (XMCD) spectra at the Pu M4 ,5 absorption edges from a newly prepared high-quality single crystal of the heavy-fermion superconductor 242Pu CoGa5 , exhibiting a critical temperature Tc=18.7 K . The experiment probes the vortex phase below Tc and shows that an external magnetic field induces a Pu 5 f magnetic moment at 2 K equal to the temperature-independent moment measured in the normal phase up to 300 K by a superconducting quantum interference device. This observation is in agreement with theoretical models claiming that the Pu atoms in PuCoGa5 have a nonmagnetic singlet ground state resulting from the hybridization of the conduction electrons with the intermediate-valence 5 f electronic shell. Unexpectedly, XMCD spectra show that the orbital component of the 5 f magnetic moment increases significantly between 30 and 2 K; the antiparallel spin component increases as well, leaving the total moment practically constant. We suggest that this indicates a low-temperature breakdown of the complete Kondo-like screening of the local 5 f moment.

  9. Silica as a Matrix for Encapsulating Proteins: Surface Effects on Protein Structure Assessed by Circular Dichroism Spectroscopy

    Science.gov (United States)

    Calabretta, Phillip J.; Chancellor, Mitchell C.; Torres, Carlos; Abel, Gary R.; Niehaus, Clayton; Birtwhistle, Nathan J.; Khouderchah, Nada M.; Zemede, Genet H.; Eggers, Daryl K.

    2012-01-01

    The encapsulation of biomolecules in solid materials that retain the native properties of the molecule is a desired feature for the development of biosensors and biocatalysts. In the current study, protein entrapment in silica-based materials is explored using the sol-gel technique. This work surveys the effects of silica confinement on the structure of several model polypeptides, including apomyoglobin, copper-zinc superoxide dismutase, polyglutamine, polylysine, and type I antifreeze protein. Changes in the secondary structure of each protein following encapsulation are monitored by circular dichroism spectroscopy. In many cases, silica confinement reduces the fraction of properly-folded protein relative to solution, but addition of a secondary solute or modification of the silica surface leads to an increase in structure. Refinement of the glass surface by addition of a monosubstituted alkoxysilane during sol-gel processing is shown to be a valuable tool for testing the effects of surface chemistry on protein structure. Because silica entrapment prevents protein aggregation by isolating individual protein molecules in the pores of the glass material, one may monitor aggregation-prone polypeptides under solvent conditions that are prohibited in solution, as demonstrated with polyglutamine and a disease-related variant of superoxide dismutase. PMID:24955630

  10. Stability and Membrane Orientation of the Fukutin Transmembrane Domain: A Combined Multiscale Molecular Dynamics and Circular Dichroism Study

    Science.gov (United States)

    2010-01-01

    The N-terminal domain of fukutin-I has been implicated in the localization of the protein in the endoplasmic reticulum and Golgi Apparatus. It has been proposed to mediate this through its interaction with the thinner lipid bilayers found in these compartments. Here we have employed multiscale molecular dynamics simulations and circular dichroism spectroscopy to explore the structure, stability, and orientation of the short 36-residue N-terminus of fukutin-I (FK1TMD) in lipids with differing tail lengths. Our results show that FK1TMD adopts a stable helical conformation in phosphatidylcholine lipids when oriented with its principal axis perpendicular to the bilayer plane. The stability of the helix is largely insensitive to the lipid tail length, preventing hydrophobic mismatch by virtue of its mobility and ability to tilt within the lipid bilayers. This suggests that changes in FK1TMD tilt in response to bilayer properties may be implicated in the regulation of its trafficking. Coarse-grained simulations of the complex Golgi membrane suggest the N-terminal domain may induce the formation of microdomains in the surrounding membrane through its preferential interaction with 1,2-dipalmitoyl-sn-glycero-3-phosphatidylinositol 4,5-bisphosphate lipids. PMID:21105749

  11. Induced circular dichroism as a tool to investigate the binding of drugs to carrier proteins: Classic approaches and new trends.

    Science.gov (United States)

    Tedesco, Daniele; Bertucci, Carlo

    2015-09-10

    Induced circular dichroism (ICD) is a spectroscopic phenomenon that provides versatile and useful methods for characterizing the structural and dynamic properties of the binding of drugs to target proteins. The understanding of biorecognition processes at the molecular level is essential to discover and validate new pharmacological targets, and to design and develop new potent and selective drugs. The present article reviews the main applications of ICD to drug binding studies on serum carrier proteins, going from the classic approaches for the derivation of drug binding parameters and the identification of binding sites, to an overview of the emerging trends for the characterization of binding modes by means of quantum chemical (QC) techniques. The advantages and limits of the ICD methods for the determination of binding parameters are critically reviewed; the capability to investigate the binding interactions of drugs and metabolites to their target proteins is also underlined, as well as the possibility of characterizing the binding sites to obtain a complete picture of the binding mechanism and dynamics. The new applications of ICD methods to identify stereoselective binding modes of drug/protein complexes are then reviewed with relevant examples. The combined application of experimental ICD spectroscopy and QC calculations is shown to identify qualitatively the bound conformations of ligands to target proteins even in the absence of a detailed structure of the binding sites, either obtained from experimental X-ray crystallography and NMR measurements or from computational models of the complex. Copyright © 2015 Elsevier B.V. All rights reserved.

  12. Removal of the free cysteine residue reduces irreversible thermal inactivation of feruloyl esterase: evidence from circular dichroism and fluorescence spectra.

    Science.gov (United States)

    Li, Jingjing; Zhang, Shuaibing; Yi, Zhuolin; Pei, Xiaoqiong; Wu, Zhongliu

    2015-08-01

    Feruloyl esterase A from Aspergillus niger (AnFaeA) contains three intramolecular disulfide bonds and one free cysteine at position 235. Saturated mutagenesis at Cys235 was carried out to produce five active mutants, all of which displayed unusual thermal inactivation patterns with the most residual activity achieved at 75°C, much higher than the parental AnFaeA. But their optimal reaction temperatures were lower than the parental AnFaeA. Extensive investigation into their free thiol and disulfide bond, circular dichroism spectra and fluorescence spectra revealed that the unfolding of the parental enzyme was irreversible on all the tested conditions, while that of the Cys235 mutants was reversible, and their ability to refold was highly dependent on the denaturing temperature. Mutants denatured at 75°C were able to efficiently reverse the unfolding to regain native structure during the cooling process. This study provided valid evidence that free cysteine substitutions can reduce irreversible thermal inactivation of proteins. © The Author 2015. Published by ABBS Editorial Office in association with Oxford University Press on behalf of the Institute of Biochemistry and Cell Biology, Shanghai Institutes for Biological Sciences, Chinese Academy of Sciences.

  13. Chiral liquid chromatography-circular dichroism-NMR for estimating separation conditions of chiral HPLC without authentic samples.

    Science.gov (United States)

    Tokunaga, Takashi; Okamoto, Masahiko; Tanaka, Kozo; Tode, Chisato; Sugiura, Makiko

    2010-05-15

    Chiral separation by high performance liquid chromatography (Chiral HPLC) is one of the most powerful methods for estimating optical and chemical purity of chiral compounds. However, it has a weakness in that much time and effort are required to prepare authentic samples. A novel chiral liquid chromatography-circular dichroism-NMR (LC-CD-NMR) technique, on the other hand, requires only crude chiral compounds that include enantiomers as minor impurities. In this study, chiral LC-CD-NMR was constructed by connecting a conventional LC-NMR system with a CD detector. A pyridylalanine derivative mixture was prepared to mimic technical grade material in an early phase of development. By chiral LC-CD-NMR, the enantiomer peak is identified by an opposite sign of the CD Cotton effect curve and an identical (1)H NMR spectrum to that of the main component. Using NMR as a detector, this method is superior in ability to discriminate enantiomers from other isomers indistinguishable by MS. Furthermore, this method is also applicable for selecting the best separation conditions of chiral HPLC. The degrees of separation (Rs) between the main component and its enantiomer in several chiral columns were compared. Even with modern chromatographic methods, establishing the best chiral HPLC conditions in an early phase of development is difficult: chiral LC-CD-NMR is a suitable solution.

  14. Complexation behavior of gelatin with amphiphilic drug imipramine hydrochloride as studied by conductimetry, surface tensiometry and circular dichroism studies.

    Science.gov (United States)

    Ali, Mohd Sajid; Anjum, Kahkashan; Khan, Javed M; Khan, Rizwan H; Kabir-ud-Din

    2011-01-01

    Herein we report our studies carried out on the interaction between IMP and gelatin in aqueous medium at 25°C using conductimetry, surface tensiometry and circular dichroism (CD) techniques. Both surface tensiometry and conductimetry results indicate that the drug interacts with the gelatin in a surfactant-like manner, i.e., both critical aggregation (cac) and polymer saturation points (psp) were observed. The interaction starts with the formation of a highly surface-active complex as revealed by the lowering of surface tension on the addition of drug to the macromolecule. The decrease in cac on increasing gelatin concentration is an indication of the strong interaction between gelatin and IMP. However, at low concentration of gelatin the interaction was not much strong as exposed by surface tension study, i.e., the cac was not very clear (as with higher gelatin concentrations). As usual, the psp increased on increasing the gelatin concentration and was always higher than the critical micelle concentration of the drug in pure aqueous medium. Using CD measurements the influence of IMP on the secondary structure of gelatin in aqueous solutions was also investigated. CD studies (performed at very low drug concentrations) illustrated that the random coil content of gelatin increases with increasing drug concentration. Free energies of aggregation (ΔG(agg)) and micellization (ΔG(mic)) were computed with the help of degrees of micelle ionization obtained from the specific conductivity - [IMP] plots. Copyright © 2010 Elsevier B.V. All rights reserved.

  15. Interplay of Exciton Coupling and Large-Amplitude Motions in the Vibrational Circular Dichroism Spectrum of Dehydroquinidine.

    Science.gov (United States)

    Nicu, Valentin P; Domingos, Sérgio R; Strudwick, Benjamin H; Brouwer, Albert M; Buma, Wybren J

    2016-01-11

    A detailed analysis of the computed structure, energies, vibrational absorption (VA) and circular dichroism (VCD) spectra of 30 low-energy conformers of dehydroquinidine reveals the existence of families of pseudo-conformers, the structures of which differ mostly in the orientation of a single O-H bond. The pseudo-conformers in a family are separated by very small energy barriers (i.e., 1.0 kcal mol(-1) or smaller) and have very different VCD spectra. First, we demonstrate the unreliable character of the Boltzmann factors predicted with DFT. Then, we show that the large differences observed between the VCD spectra of the pseudo-conformers in a family are caused by large-amplitude motions involving the O-H bond, which trigger the appearance/disappearance of strong VCD exciton-coupling bands in the fingerprint region. This interplay between exciton coupling and large-amplitude-motion phenomena demonstrates that when dealing with flexible molecules with polar bonds, vibrational averaging of VCD spectra should not be neglected. In this regard, the dehydroquinidine molecule considered here is expected to be a typical example and not the exception to the rule. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. X-ray magnetic circular dichroism and reflection anisotropy spectroscopy Kerr effect studies of capped magnetic nanowires

    Energy Technology Data Exchange (ETDEWEB)

    Cunniffe, J. P.; McNally, D.E.; Liberati, M.; Arenholz, E.; McGuinness, C.; McGilp, J. F.

    2010-03-02

    Aligned Co wires grown on Pt(997) under ultra-high vacuum conditions have been capped successfully by the epitaxial growth of Au monolayers (ML) at room temperature. The samples were kept under vacuum except when transferring between apparatus or when making some of the measurements. No degradation of the Co wires was detected during the measurements. The magneto-optic response of the system was measured using X-ray magnetic circular dichroism (XMCD) at the Co L{sub 2,3} edge and reflection anisotropy spectroscopy (RAS) at near normal incidence, which is sensitive to the normal component of the out-of-plane magnetization via the Kerr effect (MOKE). Capping the wires significantly impacts their magnetic properties. Comparison of the magneto-optic response of the system at X-ray and optical energies reveals small differences that are attributed to the induced moment in the Pt substrate and Au capping layer not picked up by the element specific XMCD measurements. The sensitivity of RAS-MOKE is sufficient to allow the determination of the easy axis direction of the capped wires to within a few degrees. The results for a 6-atom-wide Co wire sample, capped with 6 ML of Au, are consistent with the capped wires possessing perpendicular magnetization.

  17. Silica as a Matrix for Encapsulating Proteins: Surface Effects on Protein Structure Assessed by Circular Dichroism Spectroscopy

    Directory of Open Access Journals (Sweden)

    Genet H. Zemede

    2012-08-01

    Full Text Available The encapsulation of biomolecules in solid materials that retain the native properties of the molecule is a desired feature for the development of biosensors and biocatalysts. In the current study, protein entrapment in silica-based materials is explored using the sol-gel technique. This work surveys the effects of silica confinement on the structure of several model polypeptides, including apomyoglobin, copper-zinc superoxide dismutase, polyglutamine, polylysine, and type I antifreeze protein. Changes in the secondary structure of each protein following encapsulation are monitored by circular dichroism spectroscopy. In many cases, silica confinement reduces the fraction of properly-folded protein relative to solution, but addition of a secondary solute or modification of the silica surface leads to an increase in structure. Refinement of the glass surface by addition of a monosubstituted alkoxysilane during sol-gel processing is shown to be a valuable tool for testing the effects of surface chemistry on protein structure. Because silica entrapment prevents protein aggregation by isolating individual protein molecules in the pores of the glass material, one may monitor aggregation-prone polypeptides under solvent conditions that are prohibited in solution, as demonstrated with polyglutamine and a disease-related variant of superoxide dismutase.

  18. Protein secondary structure prediction from circular dichroism spectra using a self-organizing map with concentration correction.

    Science.gov (United States)

    Hall, Vincent; Sklepari, Meropi; Rodger, Alison

    2014-09-01

    Collecting circular dichroism (CD) spectra for protein solutions is a simple experiment, yet reliable extraction of secondary structure content is dependent on knowledge of the concentration of the protein--which is not always available with accuracy. We previously developed a self-organizing map (SOM), called Secondary Structure Neural Network (SSNN), to cluster a database of CD spectra and use that map to assign the secondary structure content of new proteins from CD spectra. The performance of SSNN is at least as good as other available protein CD structure-fitting algorithms. In this work we apply SSNN to a collection of spectra of experimental samples where there was suspicion that the nominal protein concentration was incorrect. We show that by plotting the normalized root mean square deviation of the SSNN predicted spectrum from the experimental one versus a concentration scaling-factor it is possible to improve the estimate of the protein concentration while providing an estimate of the secondary structure. For our implementation (51 data points 240-190 nm in nm increments) good fits and structure estimates were obtained if the NRMSD (normalized root mean square displacement, RMSE/data range) is <0.03; reasonable for NRMSD <0.05; and variable above this. We also augmented the reference database with 100% helical spectra and truly random coil spectra. © 2014 Wiley Periodicals, Inc.

  19. Vibrational circular dichroism from ab initio molecular dynamics and nuclear velocity perturbation theory in the liquid phase

    Science.gov (United States)

    Scherrer, Arne; Vuilleumier, Rodolphe; Sebastiani, Daniel

    2016-08-01

    We report the first fully ab initio calculation of dynamical vibrational circular dichroism spectra in the liquid phase using nuclear velocity perturbation theory (NVPT) derived electronic currents. Our approach is rigorous and general and thus capable of treating weak interactions of chiral molecules as, e.g., chirality transfer from a chiral molecule to an achiral solvent. We use an implementation of the NVPT that is projected along the dynamics to obtain the current and magnetic dipole moments required for accurate intensities. The gauge problem in the liquid phase is resolved in a twofold approach. The electronic expectation values are evaluated in a distributed origin gauge, employing maximally localized Wannier orbitals. In a second step, the gauge invariant spectrum is obtained in terms of a scaled molecular moments, which allows to systematically include solvent effects while keeping a significant signal-to-noise ratio. We give a thorough analysis and discussion of this choice of gauge for the liquid phase. At low temperatures, we recover the established double harmonic approximation. The methodology is applied to chiral molecules ((S)-d2-oxirane and (R)-propylene-oxide) in the gas phase and in solution. We find an excellent agreement with the theoretical and experimental references, including the emergence of signals due to chirality transfer from the solute to the (achiral) solvent.

  20. Analysis of binding interaction between the natural apocarotenoid bixin and human serum albumin by circular dichroism and fluorescence spectroscopy.

    Science.gov (United States)

    Zsila, Ferenc; Molnár, Péter; Deli, József

    2005-06-01

    Bixin is an important, pharmacologically active dietary cis-carotenoid, but its interaction with potential macromolecular targets is completely unexplored. This work was aimed to study the binding of bixin to human serum albumin (HSA), the most abundant protein in blood plasma. Circular dichroism (CD) spectroscopy in combination with UV/VIS absorption spectroscopy and fluorescence quenching techniques were applied. Appearance of induced CD bands in the UV- and VIS-absorption spectral regions indicated the formation of non-covalent carotenoid-albumin complexes. Shape and spectral position of the extrinsic Cotton effects suggested the binding of a single bixin molecule to HSA in chiral conformation. Scatchard and non-linear regression analyses of CD titration data resulted in similar values for the association constant (Ka = 6.6 and 4.6x10(5) M(-1), resp.) and for the number of binding sites (n = 1). The binding interaction was independently confirmed by fluorescence-quenching experiment from which the binding parameters were also calculated. CD Displacement measurements performed with marker ligands established that the main drug binding sites of HSA are not involved in binding of bixin. Palmitic acid decreased the amplitude of the induced CD bands suggesting a common albumin binding site for bixin and long-chain fatty acids. The above data indicate that HSA plays a significant role in the plasma transportation of bixin and related dietary carboxylic acid carotenoids.

  1. X-ray magnetic circular dichroism study of epitaxial magnetite ultrathin film on MgO(100)

    Energy Technology Data Exchange (ETDEWEB)

    Liu, W. Q.; Xu, Y. B., E-mail: yongbing.xu@york.ac.uk, E-mail: rzhang@nju.edu.cn [York-Nanjing International Center for Spintronics (YNICS), School of Electronics Science and Engineering, Nanjing University, Nanjing 210093 (China); Spintronics and Nanodevice Laboratory, Department of Electronics, University of York, York YO10 5DD (United Kingdom); Song, M. Y.; Lin, J. G. [Center for Condensed Matter Sciences, National Taiwan University, Taipei 106, Taiwan (China); Maltby, N. J.; Li, S. P. [Spintronics and Nanodevice Laboratory, Department of Electronics, University of York, York YO10 5DD (United Kingdom); Samant, M. G.; Parkin, S. S. P. [IBM Research Division, Almaden Research Center, San Jose, California 95120 (United States); Bencok, P.; Steadman, Paul; Dobrynin, Alexey [Diamond Light Source, Didcot OX11 0DE (United Kingdom); Zhang, R., E-mail: yongbing.xu@york.ac.uk, E-mail: rzhang@nju.edu.cn [York-Nanjing International Center for Spintronics (YNICS), School of Electronics Science and Engineering, Nanjing University, Nanjing 210093 (China)

    2015-05-07

    The spin and orbital magnetic moments of the Fe{sub 3}O{sub 4} epitaxial ultrathin film synthesized by plasma assisted simultaneous oxidization on MgO(100) have been studied with X-ray magnetic circular dichroism. The ultrathin film retains a rather large total magnetic moment, i.e., (2.73 ± 0.15) μ{sub B}/f.u., which is ∼70% of that for the bulk-like Fe{sub 3}O{sub 4}. A significant unquenched orbital moment up to 0.54 ± 0.05 μ{sub B}/f.u. was observed, which could come from the symmetry breaking at the Fe{sub 3}O{sub 4}/MgO interface. Such sizable orbital moment will add capacities to the Fe{sub 3}O{sub 4}-based spintronics devices in the magnetization reversal by the electric field.

  2. Competitive binding of (-)-epigallocatechin-3-gallate and 5-fluorouracil to human serum albumin: A fluorescence and circular dichroism study

    Science.gov (United States)

    Yuan, Lixia; Liu, Min; Liu, Guiqin; Li, Dacheng; Wang, Zhengping; Wang, Bingquan; Han, Jun; Zhang, Min

    2017-02-01

    Combination therapy with more than one therapeutic agent can improve therapeutic efficiency and decrease drug resistance. In this study, the interactions of human serum albumin (HSA) with individual or combined anticancer drugs, (-)-epigallocatechin-3-gallate (EGCG) and 5-fluorouracil (FU), were investigated by fluorescence and circular dichroism (CD) spectroscopy. The results demonstrated that the interaction of EGCG or FU with HSA is a process of static quenching and EGCG formed a more stable complex. The competitive experiments of site markers suggested that both anti-carcinogens mainly bound to site I (subdomain IIA). The interaction forces which play important roles in the binding process were discussed based on enthalpy and entropy changes. Moreover, the competition binding model for a ternary system was proposed so as to precisely calculate the binding parameters. The results demonstrated that one drug decreased the binding affinity of another drug with HSA, resulting in the increasing free drug concentration at the action sites. CD studies indicated that there was an alteration in HSA secondary structure due to the binding of EGCG and FU. It can be concluded that the combination of EGCG with FU may enhance anticancer efficacy. This finding may provide a theoretical basis for clinical treatments.

  3. Dispersion Relations for X-Ray Faraday Rotation and Magnetic Circular Dichroism

    Science.gov (United States)

    Smith, D. Y.

    2003-03-01

    Experimental demonstration of Kramers-Kronig relations between XFR and XMCD has recently been reported. This is at variance with predictions^1 of a more complex relationship because of the lack of time-reversal symmetry in a magnetic field. Qualitatively, this corresponds to recognizing that real EM waves contain Fourier components with positive and negative frequencies, but that right-hand modes for positive frequencies are left-hand modes for negative frequencies, and vice versa. Formally, circular modes mix real and imaginary parts of dielectric tensor elements (which individually obey the K-K relations) so that symmetric and antisymmetric combinations of optical constants must be used in forming their dispersion relations. The difference between dispersion relations for the magnetic and magnetic-field-free cases should be most readily observed in the tails of the Faraday rotation. Reanalysis of published data shows that the difference is small and comparable to experimental uncertainty in the materials studied; hence, the experiments do not distinguish between the two forms. However, there is a slight statistical preference for the magnetic relations in one set of measurements. ^1 D. Y. Smith, J. Opt. Soc. Am. 66, 454 (1967).

  4. Spin state transition in LaCoO3 studied using soft x-ray absorption spectroscopy and magnetic circular dichroism.

    Science.gov (United States)

    Haverkort, M W; Hu, Z; Cezar, J C; Burnus, T; Hartmann, H; Reuther, M; Zobel, C; Lorenz, T; Tanaka, A; Brookes, N B; Hsieh, H H; Lin, H-J; Chen, C T; Tjeng, L H

    2006-10-27

    Using soft x-ray absorption spectroscopy and magnetic circular dichroism at the Co-L(2,3) edge, we reveal that the spin state transition in LaCoO3 can be well described by a low-spin ground state and a triply degenerate high-spin first excited state. From the temperature dependence of the spectral line shapes, we find that LaCoO3 at finite temperatures is an inhomogeneous mixed-spin state system. It is crucial that the magnetic circular dichroism signal in the paramagnetic state carries a large orbital momentum. This directly shows that the currently accepted low- or intermediate-spin picture is at variance. Parameters derived from these spectroscopies fully explain existing magnetic susceptibility, electron spin resonance, and inelastic neutron data.

  5. Solar CIV Vacuum-Ultraviolet Fabry-Perot Interferometers

    Science.gov (United States)

    Gary, G. Allen; West, Edward A.; Rees, David; McKay, Jack A.; Zukic, Maumer; Herman, Peter

    2006-01-01

    Aims: A tunable, high spectral resolution, high effective finesse, vacuum ultraviolet (VUV) Fabry-Perot interferometer (PPI) is designed for obtaining narrow-passband images, magnetograms, and Dopplergrams of the transition region emission line of CIV (155 nm). Methods: The integral part of the CIV narrow passband filter package (with a 2-10 pm FWHM) consists of a multiple etalon system composed of a tunable interferometer that provides high-spectral resolution and a static low-spectral resolution interferometer that allows a large effective free spectral range. The prefilter for the interferometers is provided by a set of four mirrors with dielectric high-reflective coatings. A tunable interferometer, a VUV piezoelectric-control etalon, has undergone testing using the surrogate F2 eximer laser line at 157 nm for the CIV line. We present the results of the tests with a description of the overall concept for a complete narrow-band CIV spectral filter. The static interferometer of the filter is envisioned as being hudt using a set of fixed MgF2 plates. The four-mirror prefilter is designed to have dielectric multilayer n-stacks employing the design concept used in the Ultraviolet Imager of NASA's Polar Spacecraft. A dual etalon system allows the effective free spectral range to be commensurate with the prefilter profile. With an additional etalon, a triple etalon system would allow a spectrographic resolution of 2 pm. The basic strategy has been to combine the expertise of spaceflight etalon manufacturing with VUV coating technology to build a VUV FPI which combines the best attributes of imagers and spectrographs into a single compact instrument. Results. Spectro-polarimetry observations of the transition region CIV emission can be performed to increase the understanding of the magnetic forces, mass motion, evolution, and energy release within the solar atmosphere at the base of the corona where most of the magnetic field is approximately force-free. The 2D imaging

  6. An optically transparent thin-layer electrochemical cell for the study of vibrational circular dichroism of chiral redox-active molecules.

    Science.gov (United States)

    Domingos, Sérgio R; Luyten, Henk; van Anrooij, Fred; Sanders, Hans J; Bakker, Bert H; Buma, Wybren J; Hartl, František; Woutersen, Sander

    2013-03-01

    An optically transparent thin-layer electrochemical (OTTLE) cell with a locally extended optical path has been developed in order to perform vibrational circular dichroism (VCD) spectroscopy on chiral molecules prepared in specific oxidation states by means of electrochemical reduction or oxidation. The new design of the electrochemical cell successfully addresses the technical challenges involved in achieving sufficient infrared absorption. The VCD-OTTLE cell proves to be a valuable tool for the investigation of chiral redox-active molecules.

  7. X-ray magnetic circular dichroism at IrL2,3 edges in Fe100−xIrx and ...

    Indian Academy of Sciences (India)

    X-ray magnetic circular dichroism at IrL2,3 edges in Fe100−xIrx and Co100−xIrx alloys: Magnetism of 5d electronic states. V V KRISHNAMURTHY1,∗. , M SUZUKI2, N KAWAMURA2 and T ISHIKAWA1,2. 1RIKEN Harima Institute, SPring8, 1-1-1 Kouto, Mikazuki, Sayo, Hyogo 679-5148, Japan. 2Japan Synchrotron Radiation ...

  8. X-ray magnetic circular dichroism measurements using an X-ray phase retarder on the BM25 A-SpLine beamline at the ESRF

    Science.gov (United States)

    Boada, Roberto; Laguna-Marco, María Ángeles; Gallastegui, Jon Ander; Castro, Germán R.; Chaboy, Jesús

    2010-01-01

    Circularly polarized X-rays produced by a diamond X-ray phase retarder of thickness 0.5 mm in the Laue transmission configuration have been used for recording X-ray magnetic circular dichroism (XMCD) on the bending-magnet beamline BM25A (SpLine) at the ESRF. Field reversal and helicity reversal techniques have been used to carry out the measurements. The performance of the experimental set-up has been demonstrated by recording XMCD in the energy range from 7 to 11 keV. PMID:20400827

  9. Theory of circular dichroism of nanomaterials comprising chiral molecules and nanocrystals: plasmon enhancement, dipole interactions, and dielectric effects.

    Science.gov (United States)

    Govorov, Alexander O; Fan, Zhiyuan; Hernandez, Pedro; Slocik, Joseph M; Naik, Rajesh R

    2010-04-14

    Our calculations show that a nonchiral nanocrystal is able to dramatically change the circular dichroism (CD) of a chiral molecule when the nanocrystal and molecule form a complex and couple via dipole and multipole Coulomb interactions. Plasmon resonances of metal nanocrystals in the nanocrystal-molecule complex result in both the resonant enhancement of CD signals of molecules and the appearance of new spectral structures. Two mechanisms, in which a nanocrystal can influence the CD effect, have been identified. The first mechanism is the plasmon-induced change in the electromagnetic field inside the chiral molecule. The second is the optical absorption of the nanocrystal-molecule complex due to the chiral currents inside the metal nanocrystal induced by the dipole of the chiral molecule. The first mechanism creates a change in the angle between the effective electric and magnetic dipoles of the molecule. This mechanism can lead to symmetry breaking and to a plasmon-induced CD signal of the nonchiral molecule. Both mechanisms create interesting Fano-like shapes in the CD spectra. Importantly, the second mechanism gives the main contribution to the CD signal at the plasmon frequency when the absorption band of the chiral molecule is far from the plasmon resonance. This may happen in many cases since many biomolecules are optically active in the UV range, whereas plasmon resonances in commonly used nanometals are found at longer wavelengths. As concrete examples, the paper describes alpha-helix and calixarene ligand molecules coupled with metal nanocrystals. The above results are also applied to complexes incorporating semiconductor nanocrystals. The results obtained here can be used to design a variety of hybrid nanostructures with enhanced and tailored optical chirality in the visible wavelength range.

  10. Surface plasmon resonance and circular dichroism characterization of cucurbitacins binding to serum albumins for early pharmacokinetic profiling.

    Science.gov (United States)

    Fabini, Edoardo; Fiori, Giovana Maria Lanchoti; Tedesco, Daniele; Lopes, Norberto Peporine; Bertucci, Carlo

    2016-04-15

    Cucurbitacins are a group of tetracyclic triterpenoids, known for centuries for their anti-cancer and anti-inflammatory properties, which are being actively investigated over the past decades in order to elucidate their mechanism of action. In perspective of being used as therapeutic molecules, a pharmacokinetic characterization is crucial to assess the affinity toward blood carrier proteins and extrapolate distribution volumes. Usually, pharmacokinetic data are first collected on animal models and later translated to humans; therefore, an early characterization of the interaction with carrier proteins from different species is highly desirable. In the present study, the interactions of cucurbitacins E and I with human and rat serum albumins (HSA and RSA) were investigated by means of surface plasmon resonance (SPR)-based optical biosensing and circular dichroism (CD) spectroscopy. Active HSA and RSA sensor chip surfaces were prepared through an amine coupling reaction protocol, and the equilibrium dissociation constants (Kd) for the different cucurbitacins-serum albumins complexes were then determined by SPR analysis. Further information on the binding of cucurbitacins to serum albumins was obtained by CD competition experiments with biliverdin, a specific marker binding to subdomain IB of HSA. SPR data unveiled a previously unreported binding event between CucI and HSA; the determined binding affinities of both compounds were slightly higher for RSA with respect to HSA, even though all the compounds can be ranked as high-affinity binders for both carriers. CD analysis showed that the two cucurbitacins modify the binding of biliverdin to serum albumins through opposite allosteric modulation (positive for HSA, negative for RSA), confirming the need for caution in the translation of pharmacokinetic data across species. Copyright © 2016 Elsevier B.V. All rights reserved.

  11. Polyglutamine- and Temperature-Dependent Conformational Rigidity in Mutant Huntingtin Revealed by Immunoassays and Circular Dichroism Spectroscopy

    Science.gov (United States)

    Fodale, Valentina; Kegulian, Natalie C.; Verani, Margherita; Cariulo, Cristina; Azzollini, Lucia; Petricca, Lara; Daldin, Manuel; Boggio, Roberto; Padova, Alessandro; Kuhn, Rainer; Pacifici, Robert; Macdonald, Douglas; Schoenfeld, Ryan C.; Park, Hyunsun; Isas, J. Mario; Langen, Ralf; Weiss, Andreas; Caricasole, Andrea

    2014-01-01

    Background In Huntington's disease, expansion of a CAG triplet repeat occurs in exon 1 of the huntingtin gene (HTT), resulting in a protein bearing>35 polyglutamine residues whose N-terminal fragments display a high propensity to misfold and aggregate. Recent data demonstrate that polyglutamine expansion results in conformational changes in the huntingtin protein (HTT), which likely influence its biological and biophysical properties. Developing assays to characterize and measure these conformational changes in isolated proteins and biological samples would advance the testing of novel therapeutic approaches aimed at correcting mutant HTT misfolding. Time-resolved Förster energy transfer (TR-FRET)-based assays represent high-throughput, homogeneous, sensitive immunoassays widely employed for the quantification of proteins of interest. TR-FRET is extremely sensitive to small distances and can therefore provide conformational information based on detection of exposure and relative position of epitopes present on the target protein as recognized by selective antibodies. We have previously reported TR-FRET assays to quantify HTT proteins based on the use of antibodies specific for different amino-terminal HTT epitopes. Here, we investigate the possibility of interrogating HTT protein conformation using these assays. Methodology/Principal Findings By performing TR-FRET measurements on the same samples (purified recombinant proteins or lysates from cells expressing HTT fragments or full length protein) at different temperatures, we have discovered a temperature-dependent, reversible, polyglutamine-dependent conformational change of wild type and expanded mutant HTT proteins. Circular dichroism spectroscopy confirms the temperature and polyglutamine-dependent change in HTT structure, revealing an effect of polyglutamine length and of temperature on the alpha-helical content of the protein. Conclusions/Significance The temperature- and polyglutamine-dependent effects

  12. Perpendicular magnetic anisotropy in amorphous NdxCo1 -x thin films studied by x-ray magnetic circular dichroism

    Science.gov (United States)

    Cid, R.; Alameda, J. M.; Valvidares, S. M.; Cezar, J. C.; Bencok, P.; Brookes, N. B.; Díaz, J.

    2017-06-01

    The origin of perpendicular magnetic anisotropy (PMA) in amorphous NdxCo1 -x thin films is investigated using x-ray magnetic circular dichroism (XMCD) spectroscopy at the Co L2 ,3 and Nd M4 ,5 edges. The magnetic orbital and spin moments of the 3 d cobalt and 4 f neodymium electrons were measured as a function of the magnetic field orientation, neodymium concentration, and temperature. In all the studied samples, the magnetic anisotropy of the neodymium subnetwork is always oriented perpendicular to the plane, whereas the anisotropy of the orbital moment of cobalt is in the basal plane. The ratio Lz/Sz of the neodymium 4 f orbitals changes with the sample orientation angle, being higher and closer to the atomic expected value at normal orientation and smaller at grazing angles. This result is well explained by assuming that the 4 f orbital is distorted by the effect of an anisotropic crystal field when it is magnetized along its hard axis, clearly indicating that the 4 f states are not rotationally invariant. The magnetic anisotropy energy associated to the neodymium subnetwork should be proportional to this distortion, which we demonstrate is accessible by applying the XMCD sum rules for the spin and intensity at the Nd M4 ,5 edges. The analysis unveils a significant portion of neodymium atoms magnetically uncoupled to cobalt, i.e., paramagnetic, confirming the inhomogeneity of the films and the presence of a highly disordered neodymium rich phase already detected by extended x-ray-absorption fine structure (EXAFS) spectroscopy. The presence of these inhomogeneities is inherent to the evaporation preparation method when the chosen concentration in the alloy is far from its eutectic concentrations. An interesting consequence of the particular way in which cobalt and neodymium segregates in this system is the enhancement of the cobalt spin moment which reaches 1.95 μB in the sample with the largest segregation.

  13. A combined binding mechanism of nonionic ethoxylated surfactants to bovine serum albumin revealed by fluorescence and circular dichroism.

    Science.gov (United States)

    Iovescu, Alina; Băran, Adriana; Stîngă, Gabriela; Cantemir-Leontieş, Anca Ruxandra; Maxim, Monica Elisabeta; Anghel, Dan Florin

    2015-12-01

    The study systematically investigates aqueous mixtures of fixed bovine serum albumin (BSA) and various ethoxylated nonionic surfactants belonging to a homologous series or not. Mono-disperse tetra-(C12E4), hexa-(C12E6) and octa-ethyleneglycol mono-n-dodecyl ether (C12E8), and poly-disperse eicosa-ethyleneglycol mono-n-tetradecyl ether (C14EO20) are respectively employed. Fluorescence and circular dichroism measurements are performed at surfactant/protein molar ratios (rm)s lower and higher than one. We aim to get new insights into the binding mechanism of these species and to differentiate among the interaction abilities of these surfactants. The relative magnitude of the binding thermodynamic parameters by fluorescence, and the increase of α-helix prove that hydrogen bonding drives the interaction next to the hydrophobic attraction. C12En (n=4,6,8) develop more H bonds with the albumin than C14EO20 owing to a zigzag conformation of their short ethyleneoxide chains. Among the homologous surfactants, C12E6 has a slightly stronger interaction with BSA due to a maximal number of H bonds at a minimal hindering. Static fluorescence and dynamic fluorescence indicate an inter-conversion between the tryptophan (Trp) rotamers which happens around the surfactants critical micellar concentration. For C14EO20, the meander conformation of the polar group determines a less evident conversion of the Trp rotamers and smaller α-helix rise. Binding isotherms of the homologous surfactants and the fluorescence quenching mechanism by C12E6 are also provided. Copyright © 2015 Elsevier B.V. All rights reserved.

  14. Synchrotron vacuum ultraviolet radiation studies of the D 1Πu state of H2

    NARCIS (Netherlands)

    Dickenson, G. D.; Ivanov, T. I.; Roudjane, M.; de Oliveira, N.; Joyeux, D.; Nahon, L.; Tchang-Brillet, W. Ü L; Glass-Maujean, M.; Haas, I.; Ehresmann, A.; Ubachs, W.

    2010-01-01

    The 3pπD 1Πu state of the H2 molecule was reinvestigated with different techniques at two synchrotron installations. The Fourier transform spectrometer in the vacuum ultraviolet wavelength range of the DESIRS beamline at the SOLEIL synchrotron was used for recording absorption spectra of the D Π1u

  15. Characteristics of the iron moment in Dy-Fe and Dy-FeCo amorphous alloys studied by X-ray magnetic circular dichroism

    Energy Technology Data Exchange (ETDEWEB)

    Fleury-Frenette, K.; Dhesi, S.S.; Laan, G. van der; Strivay, D.; Weber, G.; Delwiche, J. E-mail: jdelwiche@ulg.ac.be

    2000-10-01

    The local magnetic moment of Fe in Dy-Fe and Dy-FeCo amorphous alloys has been studied using X-ray absorption spectroscopy and X-ray magnetic circular dichroism (XMCD). The Fe orbital and spin magnetic moments have been obtained for a range of alloy compositions by applying the sum rules to the XMCD spectra. The room temperature variations of the average components of the Fe moments as a function of Dy concentration and with the substitution of Fe by Co have been determined. A sharp reversal of the total magnetic moment was found at 28{+-}1 at% Dy for both alloys.

  16. Lanthanide tris(β-diketonates) as useful probes for chirality determination of biological amino alcohols in vibrational circular dichroism: ligand to ligand chirality transfer in lanthanide coordination sphere.

    Science.gov (United States)

    Miyake, Hiroyuki; Terada, Keiko; Tsukube, Hiroshi

    2014-06-01

    A series of lanthanide tris(β-diketonates) functioned as useful chirality probes in the vibrational circular dichroism (VCD) characterization of biological amino alcohols. Various chiral amino alcohols induced intense VCD signals upon ternary complexation with racemic lanthanide tris(β-diketonates). The VCD signals observed around 1500 cm(-1) (β-diketonate IR absorption region) correlated well with the stereochemistry and enantiomeric purity of the targeted amino alcohol, while the corresponding monoalcohol, monoamine, and diol substrates induced very weak VCD signals. The high-coordination number and dynamic property of the lanthanide complex offer an effective chirality VCD probing of biological substrates. © 2014 Wiley Periodicals, Inc.

  17. Structures, vibrational absorption and vibrational circular dichroism spectra of L-alanine in aqueous solution: a density functional theory and RHF study

    DEFF Research Database (Denmark)

    Frimand, Kenneth; Bohr, Henrik; Jalkanen, Karl J.

    2000-01-01

    A detailed comparative study of structures, vibrational absorption (VA) and vibrational circular dichroism (VCD) spectra has been carried out for the zwitterionic structure of the amino acid L-alanine. Theoretically determined structures necessary for deriving VA and VCD spectra were calculated...... at the density functional theory level using the B3LYP functional with the 6-31G* basis set. The Hessians and atomic polar tensors and atomic axial tensors were all calculated at the B3LYP/6-31G* level of theory. An important result is the method of treating solvent effects by both adding explicit water...

  18. Vibrational analysis of various irotopes of L-alanyl-L-alanine in aqueous solution: Vibrational Absorption (VA), Vibrational Circular Dichroism (VCD), Raman and Raman Optical Activity (ROA) Spectra

    DEFF Research Database (Denmark)

    Jalkanen, Karl J.; Nieminen, R.M.; Knapp-Mohammady, M.

    2003-01-01

    been reported. Subsequently, the vibrational absorption (VA) and vibrational circular dichroism (VCD) and the Raman and Raman Optical Activity (ROA) spectra have been reported. In this work an analysis of the aqueous solution VA, VCD, Raman, and ROA spectra for various isotopomers of LALA are reported...... with the experimentally measured spectra. With the DFT, explicit water molecules, and a continuum solvent model we are better able to reproduce the vibrational absorption and Raman spectra than previously reported. The AAT have been implemented at the DFT level, although not within the continuum treatment. The VCD sign...

  19. Two-photon absorption and two-photon circular dichroism of L-tryptophan in the near to far UV region

    Science.gov (United States)

    Vesga, Yuly; Hernandez, Florencio E.

    2017-09-01

    Herein we report on the first measurements of the two-photon absorption (TPA) spectrum of L-tryptophan in DMSO solution in the near to far UV region and the two-photon circular dichroism (TPCD) signal corresponding to a transition at 200 nm. We demonstrate the application of the Double L-scan technique in the near to far UV region to perform polarization dependent TPA measurements of chiral molecules. TPCD measurements below 400 nm reveal that chiral molecules in solution, such as tryptophan/DMSO, can undergo photochemical reactions in front of prolonged exposure to UV radiation.

  20. Circular dichroism and optical absorption spectra of mononuclear and trinuclear chiral Cu(II) amino-alcohol coordinated compounds: A combined theoretical and experimental study

    Science.gov (United States)

    Valencia, Israel; Ávila-Torres, Yenny; Barba-Behrens, Norah; Garzón, Ignacio L.

    2015-04-01

    Studies on the physicochemical properties of biomimetic compounds of multicopper oxidases are fundamental to understand their reaction mechanisms and catalytic behavior. In this work, electronic, optical, and chiroptical properties of copper(II) complexes with amino-alcohol chiral ligands are theoretically studied by means of time-dependent density functional theory. The calculated absorption and circular dichroism spectra are compared with experimental measurements of these spectra for an uncoordinated pseudoephedrine derivative, as well as for the corresponding mononuclear and trinuclear copper(II)-coordinated complexes. This comparison is useful to gain insights into their electronic structure, optical absorption and optical activity. The optical absorption and circular dichroism bands of the pseudoephedrine derivative are located in the UV-region. They are mainly due to transitions originated from n to π anti-bonding orbitals of the alcohol and amino groups, as well as from π bonding to π anti-bonding orbitals of carboxyl and phenyl groups. In the case of the mononuclear and trinuclear compounds, additional signals in the visible spectral region are present. In both systems, the origin of these bands is due to charge transfer from ligand to metal and d-d transitions.

  1. Characterization of interactions between methoxatin disodium salt and human serum albumin by pressure-assisted capillary electrophoresis/frontal analysis and circular dichroism spectroscopy.

    Science.gov (United States)

    Zhao, Lijuan; Chen, Dongying

    2015-01-01

    Pressure-assisted capillary electrophoresis (PACE)/frontal analysis (FA) and circular dichroism spectroscopy were utilized to investigate the interactions between methoxatin disodium salt (PQQ-2Na) and human serum albumin (HSA). With the PACE/FA method, sodium phosphate buffer solution (67 mm, pH 7.4) was used as the background electrolyte. Hydrodynamic injection at 50 mbar for 50 s and external pressure of 50 mbar were applied. The binding constant and the number of primary binding sites to HSA were obtained under fixed concentration of PQQ-2Na (100 µm) and increasing HSA concentration (0~475 µm). The thermodynamic parameters characterized the main acting forces of hydrophobic and electrostatic interactions. The displacement experiments using phenylbutazone and flurbiprofen as ligand markers suggested that the binding site was the Sudlow site I of the HSA molecule. Circular dichroism spectroscopy was further employed to evaluate the conformation changes of HSA under the interaction of PQQ-2Na. This work provides comprehensive information for understanding the interactions between PQQ-2Na and HSA. Copyright © 2014 John Wiley & Sons, Ltd.

  2. Chemoenzymatic approach to optically active 4-hydroxy-5-alkylcyclopent-2-en-1-one derivatives: an application of a combined circular dichroism spectroscopy and DFT calculations to assignment of absolute configuration.

    Science.gov (United States)

    Frelek, Jadwiga; Karchier, Michał; Madej, Daria; Michalak, Karol; Różański, Paweł; Wicha, Jerzy

    2014-06-01

    A series of representative optically active derivatives of 4-hydroxy-5-alkylcyclopent-2-en-1-one were prepared from the respective 2-furyl methyl carbinols via the Piancatelli rearrangement followed by the enzymatic kinetic resolution of racemates. Applicability of chiroptical methods (experimental and calculated electronic circular dichroism [ECD] and vibrational circular dichroism [VCD] spectra) to determine the absolute configuration of both stereogenic centers in 4-hydroxy-5-methylcyclopent-2-en-1-one was demonstrated. It was also demonstrated that the concurrent application of ECD and VCD spectroscopy can be used for the determination of the configuration of two stereogenic centers. © 2014 Wiley Periodicals, Inc.

  3. Resolution of isomeric new designer stimulants using gas chromatography - Vacuum ultraviolet spectroscopy and theoretical computations.

    Science.gov (United States)

    Skultety, Ludovit; Frycak, Petr; Qiu, Changling; Smuts, Jonathan; Shear-Laude, Lindsey; Lemr, Karel; Mao, James X; Kroll, Peter; Schug, Kevin A; Szewczak, Angelica; Vaught, Cory; Lurie, Ira; Havlicek, Vladimir

    2017-06-08

    Distinguishing isomeric representatives of "bath salts", "plant food", "spice", or "legal high" remains a challenge for analytical chemistry. In this work, we used vacuum ultraviolet spectroscopy combined with gas chromatography to address this issue on a set of forty-three designer drugs. All compounds, including many isomers, returned differentiable vacuum ultraviolet/ultraviolet spectra. The pair of 3- and 4-fluoromethcathinones (m/z 181.0903), as well as the methoxetamine/meperidine/ethylphenidate (m/z 247.1572) triad, provided very distinctive vacuum ultraviolet spectral features. On the contrary, spectra of 4-methylethcathinone, 4-ethylmethcathinone, 3,4-dimethylmethcathinone triad (m/z 191.1310) displayed much higher similarities. Their resolution was possible only if pure standards were probed. A similar situation occurred with the ethylone and butylone pair (m/z 221.1052). On the other hand, majority of forty-three drugs was successfully separated by gas chromatography. The detection limits for all the drug standards were in the 2-4 ng range (on-column amount), which is sufficient for determinations of seized drugs during forensics analysis. Further, state-of-the-art time-dependent density functional theory was evaluated for computation of theoretical absorption spectra in the 125-240 nm range as a complementary tool. Copyright © 2017 Elsevier B.V. All rights reserved.

  4. Heats of vaporization of room temperature ionic liquids by tunable vacuum ultraviolet photoionization

    Energy Technology Data Exchange (ETDEWEB)

    Chambreau, Steven D.; Vaghjiani, Ghanshyam L.; To, Albert; Koh, Christine; Strasser, Daniel; Kostko, Oleg; Leone, Stephen R.

    2009-11-25

    The heats of vaporization of the room temperature ionic liquids (RTILs) N-butyl-N-methylpyrrolidinium bistrifluorosulfonylimide, N-butyl-N-methylpyrrolidinium dicyanamide, and 1-butyl-3-methylimidazolium dicyanamide are determined using a heated effusive vapor source in conjunction with single photon ionization by a tunable vacuum ultraviolet synchrotron source. The relative gas phase ionic liquid vapor densities in the effusive beam are monitored by clearly distinguished dissociative photoionization processes via a time-of-flight mass spectrometer at a tunable vacuum ultraviolet beamline 9.0.2.3 (Chemical Dynamics Beamline) at the Advanced Light Source synchrotron facility. Resulting in relatively few assumptions, through the analysis of both parent cations and fragment cations, the heat of vaporization of N-butyl-N-methylpyrrolidinium bistrifluorosulfonylimide is determined to be Delta Hvap(298.15 K) = 195+-19 kJ mol-1. The observed heats of vaporization of 1-butyl-3-methylimidazolium dicyanamide (Delta Hvap(298.15 K) = 174+-12 kJ mol-1) and N-butyl-N-methylpyrrolidinium dicyanamide (Delta Hvap(298.15 K) = 171+-12 kJ mol-1) are consistent with reported experimental values using electron impact ionization. The tunable vacuum ultraviolet source has enabled accurate measurement of photoion appearance energies. These appearance energies are in good agreement with MP2 calculations for dissociative photoionization of the ion pair. These experimental heats of vaporization, photoion appearance energies, and ab initio calculations corroborate vaporization of these RTILs as intact cation-anion ion pairs.

  5. Angle-resolved soft X-ray magnetic circular dichroism in a monatomic Fe layer facing an MgO(0 0 1) tunnel barrier

    Energy Technology Data Exchange (ETDEWEB)

    Mamiya, K. [Photon Factory, Institute of Materials Structure Science (IMSS), High Energy Accelerator Research Organization, 1-1 Oho, Tsukuba, Ibaraki 305-0801 (Japan); Koide, T. [Photon Factory, Institute of Materials Structure Science (IMSS), High Energy Accelerator Research Organization, 1-1 Oho, Tsukuba, Ibaraki 305-0801 (Japan)]. E-mail: tsuneharu.koide@kek.jp; Ishida, Y. [Department of Complexity Science and Engineering, University of Tokyo, 5-1-5 Kashiwanoha, Kashiwa, Chiba 277-8561 (Japan); Osafune, Y. [Department of Complexity Science and Engineering, University of Tokyo, 5-1-5 Kashiwanoha, Kashiwa, Chiba 277-8561 (Japan); Fujimori, A. [Department of Complexity Science and Engineering, University of Tokyo, 5-1-5 Kashiwanoha, Kashiwa, Chiba 277-8561 (Japan); Suzuki, Y. [Graduate School of Engineering Science, Osaka University, 1-3 Toyonaka, Osaka 560-8531 (Japan); NanoElectronics Research Institute, National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba, Ibaraki 305-8568 (Japan); Katayama, T. [NanoElectronics Research Institute, National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba, Ibaraki 305-8568 (Japan); Yuasa, S. [NanoElectronics Research Institute, National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba, Ibaraki 305-8568 (Japan)

    2006-11-15

    The electronic and magnetic states of a monatomic Fe(0 0 1) layer directly facing an MgO(0 0 1) tunnel barrier were studied by angle-resolved X-ray magnetic circular dichroism (XMCD) at the Fe L {sub 2,3} edges in the longitudinal (L) and transverse (T) arrangements. A strong XMCD reveals no oxidation of the 1-ML Fe, showing its crucial role in giant tunnel magnetoresistance effects in Fe/MgO/Fe magnetic tunnel junctions. Sum-rule analyses of the angle-resolved XMCD give values of a spin moment, in-plane and out-of-plane orbital and magnetic dipole moments. Argument is given on their physical implication.

  6. Ga+ ion irradiation-induced changes in magnetic anisotropy of a Pt/Co/Pt thin film studied by X-ray magnetic circular dichroism

    Directory of Open Access Journals (Sweden)

    Liedke M. O.

    2013-01-01

    Full Text Available Ga+ ion irradiation-induced changes in magnetic anisotropy of a Pt/Co/Pt ultrathin film are investigated by means of the X-ray magnetic circular dichroism (XMCD technique. A large difference in the Co orbital moment is observed between out-of-plane and in-plane directions of the film at moderate Ga+ fluences of ~1-2×1014 ions/cm2, which corresponds to the perpendicular magnetic anisotropy (PMA, while further increased fluences reduce the orbital moment difference, resulting in in-plane magnetization. In contrast, at much higher Ga+ fluences of ~5×1015 ions/cm2, at which PMA is observed again, no significant difference is found in the orbital moment of Co between out-of-plane and in-plane directions. Different origins are thus suggested for the appearance of PMA induced by the irradiation between moderate and high Ga+ fluences.

  7. Application of Circular Dichroism Spectroscopy to the Analysis of the Interaction Between the Estrogen Receptor Alpha and Coactivators: The Case of Calmodulin.

    Science.gov (United States)

    Miclet, Emeric; Bourgoin-Voillard, Sandrine; Byrne, Cillian; Jacquot, Yves

    2016-01-01

    The estrogen receptor α ligand-binding domain (ERα-LBD) binds the natural hormone 17β-estradiol (E2) to induce transcription and cell proliferation. This process occurs with the contribution of protein and peptide partners (also called coactivators) that can modulate the structure of ERα, and therefore its specificity of action. As with most transcription factors, ERα exhibits a high content of α helix, making it difficult to routinely run spectroscopic studies capable of deciphering the secondary structure of the different partners under binding conditions. Ca(2+)-calmodulin, a protein also highly structured in α-helix, is a key coactivator for ERα activity. Here, we show how circular dichroism can be used to study the interaction of ERα with Ca(2+)-calmodulin. Our approach allows the determination not only of the conformational changes induced upon complex formation but also the dissociation constant (K d) of this interaction.

  8. Direct Observation of High-Spin States in Manganese Dimer and Trimer Cations by X-ray Magnetic Circular Dichroism Spectroscopy in an Ion Trap

    CERN Document Server

    Zamudio-Bayer, Vicente; Langenberg, Andreas; Kossick, Martin; Ławicki, Arkadiusz; Terasaki, Akira; von Issendorff, Bernd; Lau, J Tobias

    2015-01-01

    The electronic structure and magnetic moments of free Mn$_2^+$ and Mn$_3^+$ are characterized by $2p$ x-ray absorption and x-ray magnetic circular dichroism spectroscopy in a cryogenic ion trap that is coupled to a synchrotron radiation beamline. Our results show directly that localized magnetic moments of 5 $\\mu_B$ are created by $3d^5 (^6\\mathrm{S})$ states at each ionic core, which are coupled in parallel to form molecular high-spin states via indirect exchange that is mediated in both cases by a delocalized valence electron in a singly-occupied $4s$ derived orbital with an unpaired spin. This leads to total magnetic moments of 11 $\\mu_B$ for Mn$_2^+$ and 16 $\\mu_B$ for Mn$_3^+$, with no contribution of orbital angular momentum.

  9. Nuclear velocity perturbation theory for vibrational circular dichroism: An approach based on the exact factorization of the electron-nuclear wave function

    CERN Document Server

    Scherrer, Arne; Sebastiani, Daniel; Gross, E K U; Vuilleumier, Rodolphe

    2015-01-01

    The nuclear velocity perturbation current-density theory (NVPT) for vibrational circular dichroism (VCD) is derived from the exact factorization of the electron-nuclear wave function. This new formalism offers an exact starting point to include correction terms to the Born-Oppenheimer (BO) form of the molecular wave function, similarly to the complete-adiabatic approximation. The corrections depend on a small parameter that, in a classical treatment of the nuclei, is identified as the nuclear velocity. Apart from proposing a rigorous basis for the NVPT, we show that the rotational strength, related to the intensity of the VCD signal, contain a new contribution beyond-BO that can be evaluated with the NVPT and that only arises when the exact factorization approach is employed. Numerical results are presented for chiral and non-chiral systems to test the validity of the approach.

  10. A high-performance liquid chromatography with circular dichroism detector for determination of stereochemistry of 6, 9-oxygen bridge dibenzocyclooctadiene lignans from kadsura coccinea.

    Science.gov (United States)

    Zhu, Hui; Xu, Liang; Yang, Shi-Lin; Li, He-Ran

    2015-10-01

    The stereochemistry of two 6, 9-oxygen bridge dibenzocyclooctadiene lignans from Kadsura coccinea, are difficult to separate and very unstable. The present study was designed to develop a high-performance liquid chromatography using circular dichroism detection for the analysis of the stereochemistry. A new 6, 9-oxygen bridge dibenzocyclooctadiene lignans named Kadsulignan Q was firstly found with an S-biphenyl configuration. The other compound was identified as Kadsulignan L with an R- biphenyl configuration. In order to obtain kinetic data on their reversible interconversion, the stability was measured at different deuterated solvents such as deuterated methanol, deuterated chloroform and deuterated dimethylsulfoxide. The lignans were more unstable and converted more easily in deuterated methanol than in deuterated chloroform and deuterated dimethylsulfoxide. Copyright © 2015 China Pharmaceutical University. Published by Elsevier B.V. All rights reserved.

  11. Experimental observation of temperature and magnetic-field evolution of the 4 f states in CeFe2 revealed by soft x-ray magnetic circular dichroism

    Science.gov (United States)

    Saitoh, Y.; Yasui, A.; Fuchimoto, H.; Nakatani, Y.; Fujiwara, H.; Imada, S.; Narumi, Y.; Kindo, K.; Takahashi, M.; Ebihara, T.; Sekiyama, A.

    2017-07-01

    We revisit the delocalized character of the 4 f states of CeFe2 in the ferromagnetically ordered phase by x-ray magnetic circular dichroism (XMCD) in x-ray absorption spectroscopy (XAS) with improved data quality using single crystals. Surprisingly, the Ce M4 ,5 XMCD spectral shape changes significantly as a function of temperature and applied magnetic field, with no concomitant changes in the spectral shape of the Ce M4 ,5 XAS as well as the Fe L2 ,3 XAS and XMCD. This unusual behavior is characterized by the J =7 /2 states in a 4 f1 configuration mixed into the J =5 /2 ground state. Such extreme sensitivity of the Ce 4 f states to the external perturbations can be related to the magnetic instability toward an antiferromagnetic phase in CeFe2. Our experimental data presented here provide valuable insights into the underlying physics in strongly hybridized ferromagnetic Ce compounds.

  12. Magnetic circular dichroism of LaMn sub 1 sub - sub x Al sub x O sub 3 sub + subdelta series of samples

    CERN Document Server

    Banerjee, A; Krishnan, R V; Dasannacharya, B A; Muro, T; Saitoh, Y; Imada, S; Suga, S

    2003-01-01

    We report magnetic circular dichroism (MCD) studies on the polycrystalline LaMn sub 1 sub - sub x Al sub x O sub 3 sub + subdelta series with x=0-0.2. The Mn-2p MCD was recorded in the temperature range from 45 to 300 K for samples with x=0, 0.075, 0.1 and 0.15. It was seen that unlike ac-susceptibility no second transition in MCD was observed at lower temperatures in the samples with x>=0.075 indicating that it is not intrinsic to the samples but arise out of the dynamics of ferromagnetic clusters in the polycrystalline sample. More significantly, the MCD signal persists even 100 K above the ferromagnetic T sub C confirming that the observation of the magnetic correlation above T sub C in bulk measurement is intrinsic to this type of systems.

  13. Time-resolved demagnetization of Co{sub 2}MnSi observed using x-ray magnetic circular dichroism and an ultrafast streak camera

    Energy Technology Data Exchange (ETDEWEB)

    Opachich, Y P; Young, A T; Scholl, A; Feng, J; Engelhorn, K; Padmore, H A [Lawrence Berkeley National Laboratory, Berkeley, CA 94720-8099 (United States); Comin, A; Reiss, G [Italian Institute of Technology, Nanophys, 16163 Genova GE (Italy); Bartelt, A F [Department of Materials for Photovoltaics, Helmholtz Center Berlin for Materials and Energy, 14109 Berlin (Germany); Schmalhorst, J [Department of Physics, Bielefeld University, 33501 Bielefeld (Germany); Shin, H J [Pohang Accelerator Laboratory, Pohang University of Science and Technology, Kyungbuk 790-784 (Korea, Republic of); Risbud, S H, E-mail: YPOpachich@gmail.co [Department of Chemical Engineering and Materials Science, University of California at Davis, Davis, CA 95616 (United States)

    2010-04-21

    The demagnetization dynamics of the Heusler alloy Co{sub 2}MnSi was studied using picosecond time-resolved x-ray magnetic circular dichroism. The sample was excited using femtosecond laser pulses. In contrast to the sub-picosecond demagnetization of the metal ferromagnet Ni, substantially slower demagnetization with a time constant of 3.5 +- 0.5 ps was measured. This could be explained by a spin-dependent band gap inhibiting the spin-flip scattering of hot electrons in Co{sub 2}MnSi, which is predicted to be half-metallic. A universal demagnetization time constant was measured across a range of pump power levels.

  14. Investigation of the electronic absorption spectra and the circular dichroism spectra of binuclear tetra-. mu. -mandelato complexes of Mo/sub 2//sup 4 +/

    Energy Technology Data Exchange (ETDEWEB)

    Golovaneva, I.F.; Akhmedov, E.L.; Kotel' nikova, A.S.

    1987-05-01

    The IR, electronic absorption, and circular dichroism spectra of the binuclear tetra-..mu..-mandelates of molybdenum(II) (Mo/sub 2//D-(-)-OOCCH(OH)C/sub 6/H/sub 5///sub 4/) and (Mo/sub 2//L-(+)-OOCCH(OH)C/sub 6/H/sub 5///sub 4/) have been studied. It has been established that Cotton effects are induced in all the electronic transitions of the symmetric (Mo/sub 2/O/sub 8/)chromophore under the influence of the asymmetric atom of the optically active mandelato ligand. The observed electronic transitions have been assigned on the basis of an analysis of the spectroscopic data obtained.

  15. A compact permanent-magnet system for measuring magnetic circular dichroism in resonant inelastic soft X-ray scattering.

    Science.gov (United States)

    Miyawaki, Jun; Suga, Shigemasa; Fujiwara, Hidenori; Niwa, Hideharu; Kiuchi, Hisao; Harada, Yoshihisa

    2017-03-01

    A compact and portable magnet system for measuring magnetic dichroism in resonant inelastic soft X-ray scattering (SX-RIXS) has been developed at the beamline BL07LSU in SPring-8. A magnetic circuit composed of Nd-Fe-B permanent magnets, which realised ∼0.25 T at the center of an 11 mm gap, was rotatable around the axis perpendicular to the X-ray scattering plane. Using the system, a SX-RIXS spectrum was obtained under the application of the magnetic field at an angle parallel, nearly 45° or perpendicular to the incident X-rays. A dedicated sample stage was also designed to be as compact as possible, making it possible to perform SX-RIXS measurements at arbitrary incident angles by rotating the sample stage in the gap between the magnetic poles. This system enables facile studies of magnetic dichroism in SX-RIXS for various experimental geometries of the sample and the magnetic field. A brief demonstration of the application is presented.

  16. Absolute vacuum ultraviolet flux in inductively coupled plasmas and chemical modifications of 193 nm photoresist

    Science.gov (United States)

    Titus, M. J.; Nest, D.; Graves, D. B.

    2009-04-01

    Vacuum ultraviolet (VUV) photons in plasma processing systems are known to alter surface chemistry and may damage gate dielectrics and photoresist. We characterize absolute VUV fluxes to surfaces exposed in an inductively coupled argon plasma, 1-50 mTorr, 25-400 W, using a calibrated VUV spectrometer. We also demonstrate an alternative method to estimate VUV fluence in an inductively coupled plasma (ICP) reactor using a chemical dosimeter-type monitor. We illustrate the technique with argon ICP and xenon lamp exposure experiments, comparing direct VUV measurements with measured chemical changes in 193 nm photoresist-covered Si wafers following VUV exposure.

  17. Note: Hollow cathode lamp with integral, high optical efficiency isolation valve: a modular vacuum ultraviolet source.

    Science.gov (United States)

    Roberts, F Sloan; Anderson, Scott L

    2013-12-01

    The design and operating conditions of a hollow cathode discharge lamp for the generation of vacuum ultraviolet radiation, suitable for ultrahigh vacuum (UHV) application, are described in detail. The design is easily constructed, and modular, allowing it to be adapted to different experimental requirements. A thin isolation valve is built into one of the differential pumping stages, isolating the discharge section from the UHV section, both for vacuum safety and to allow lamp maintenance without venting the UHV chamber. The lamp has been used both for ultraviolet photoelectron spectroscopy of surfaces and as a "soft" photoionization source for gas-phase mass spectrometry.

  18. Note: Hollow cathode lamp with integral, high optical efficiency isolation valve: A modular vacuum ultraviolet source

    Energy Technology Data Exchange (ETDEWEB)

    Sloan Roberts, F.; Anderson, Scott L. [Department of Chemistry, University of Utah, 315 S. 1400 E., Salt Lake City, Utah 84112 (United States)

    2013-12-15

    The design and operating conditions of a hollow cathode discharge lamp for the generation of vacuum ultraviolet radiation, suitable for ultrahigh vacuum (UHV) application, are described in detail. The design is easily constructed, and modular, allowing it to be adapted to different experimental requirements. A thin isolation valve is built into one of the differential pumping stages, isolating the discharge section from the UHV section, both for vacuum safety and to allow lamp maintenance without venting the UHV chamber. The lamp has been used both for ultraviolet photoelectron spectroscopy of surfaces and as a “soft” photoionization source for gas-phase mass spectrometry.

  19. Vacuum ultraviolet spectroscopy in detached plasmas with impurity gas seeding in LHD

    Energy Technology Data Exchange (ETDEWEB)

    Suzuki, C., E-mail: csuzuki@nifs.ac.jp; Murakami, I.; Akiyama, T.; Masuzaki, S.; Funaba, H.; Yoshinuma, M.

    2015-08-15

    We have carried out vacuum ultraviolet (VUV) spectroscopy of impurity ions in detached plasmas with impurity gas seeding in the Large Helical Device (LHD). In neon (Ne) gas seeding experiments, temporal evolutions of VUV spectral lines from Ne IV–VIII were recorded by a grazing incidence spectrometer. In addition, spatial profiles of fully ionized Ne density were measured by charge exchange spectroscopy. An electron temperature range where each ion emits is inferred based on the comparisons of the measured line intensity ratios with the calculations using collisional-radiative models.

  20. CIV Polarization Measurements using a Vacuum Ultraviolet Fabry-Perot Interferometer

    Science.gov (United States)

    West, Edward; Gary, G. Allen; Cirtain, Jonathan; David, John; Kobayashi, Ken; Pietraszewski, Chris

    2009-01-01

    Marshall Space Flight Center's (MSFC) is developing a Vacuum Ultraviolet (VUV) Fabry-P rot Interferometer that will be launched on a sounding rocket for high throughput, high-cadence, extended field of view CIV (155nm) measurements. These measurements will provide (i) Dopplergrams for studies of waves, oscillations, explosive events, and mass motions through the transition region, and, (ii), polarization measurements to study the magnetic field in the transition region. This paper will describe the scientific goals of the instrument, a brief description of the optics and the polarization characteristics of the VUV Fabry P rot.

  1. Vacuum ultraviolet light source utilizing rare gas scintillation amplification sustained by photon positive feedback

    Science.gov (United States)

    Aprile, Elena (Inventor); Chen, Danli (Inventor)

    1995-01-01

    A source of light in the vacuum ultraviolet (VUV) spectral region includes a reflective UV-sensitive photocathode supported in spaced parallel relationship with a mesh electrode within a rare gas at low pressure. A high positive potential applied to the mesh electrode creates an electric field which causes drifting of free electrons occurring between the electrodes and producing continuous VUV light output by electric field-driven scintillation amplification sustained by positive photon feedback mediated by photoemission from the photocathode. In one embodiment the lamp emits a narrow-band continuum peaked at 175 nm.

  2. Vacuum ultraviolet and infrared spectra of condensed methyl acetate on cold astrochemical dust analogs

    Energy Technology Data Exchange (ETDEWEB)

    Sivaraman, B. [Space and Atmospheric Sciences Division, Physical Research Laboratory, Ahmedabad 380009 (India); Nair, B. G.; Mason, N. J. [Department of Physical Sciences, The Open University, Walton Hall, Milton Keynes MK7 6AA (United Kingdom); Lo, J.-I.; Cheng, B.-M. [National Synchrotron Radiation Research Center, 101 Hsin-Ann Road, Hsinchu Science Park, Hsinchu 30076, Taiwan (China); Kundu, S.; Davis, D.; Prabhudesai, V.; Krishnakumar, E. [Department of Nuclear and Atomic Physics, Tata Institute of Fundamental Research, Mumbai 400005 (India); Raja Sekhar, B. N., E-mail: bhala@prl.res.in [B-4, Indus-1, BARC Spectroscopy Lab at Indus-1, Atomic and Molecular Physics Division, BARC, Mumbai and RRCAT, Indore 452013 (India)

    2013-12-01

    Following the recent report of the first identification of methyl acetate (CH{sub 3}COOCH{sub 3}) in the interstellar medium (ISM), we have carried out vacuum ultraviolet (VUV) and infrared (IR) spectroscopy studies on methyl acetate from 10 K until sublimation in an ultrahigh vacuum chamber simulating astrochemical conditions. We present the first VUV and IR spectra of methyl acetate relevant to ISM conditions. Spectral signatures clearly showed molecular reorientation to have started in the ice by annealing the amorphous ice formed at 10 K. An irreversible phase change from amorphous to crystalline methyl acetate ice was found to occur between 110 K and 120 K.

  3. Energetics, ionization, and expansion dynamics of atomic clusters irradiated with short intense vacuum-ultraviolet pulses.

    Science.gov (United States)

    Ziaja, B; Wabnitz, H; Wang, F; Weckert, E; Möller, T

    2009-05-22

    Kinetic equations are used to model the dynamics of Xe clusters irradiated with short, intense vacuum-ultraviolet pulses. Various cluster size and pulse fluences are considered. It is found that the highly charged ions observed in the experiments are mainly due to Coulomb explosion of the outer cluster shell. Ions within the cluster core predominantly recombine with plasma electrons, forming a large fraction of neutral atoms. To our knowledge, our model is the first and only one that gives an accurate description of all of the experimental data collected from atomic clusters at 100 nm photon wavelength.

  4. CIV Vacuum Ultraviolet Fabry-Perot Interferometers for Transition-Region Magnetography

    Science.gov (United States)

    Gary, G. Allen; West, Edward A.; Rees, David; Zukic, Maumer; Herman, Peter; Li, Jianzhao

    2006-01-01

    The vacuum ultraviolet region allows remote sensing of the upper levels of the solar atmosphere where the magnetic field dominates the physics. Obtaining an imaging interferometer that observes the transition region is the goal of this program. This paper gives a summary of our instrument development program (1998-2005) for a high-spectral-resolution, piezoelectric tunable Vacuum Ultraviolet Fabry-Perot Interferometer (VUV FPI) for obtaining narrow-passband images, magnetograms, and Dopplergrams of the transition region emission line of CN (155nm). A VUV interferometer will allow us to observe the magnetic field, flows, and heating events in the mid-transition region. The MSFC VUV FPI has measured values of FWHM approx. 9pm, FSR approx. 62pm, finesse approx. 5.3 and transmittance approx. 50% at 157nm. For the measurements, the University of Toronto's F2 eximer laser was used as an appropriate proxy for CIV 155nm. This has provided the first tunable interferometer with a FWHM compatible to VUV filter magnetograph.

  5. [Design and study of a high resolution vacuum ultraviolet imaging spectrometer carried by satellite].

    Science.gov (United States)

    Yu, Lei; Lin, Guan-yu; Qu, Yi; Wang, Shu-rong; Wang, Long-qi

    2011-12-01

    A high resolution vacuum ultraviolet imaging spectrometer prototype carried by satellite applied to the atmosphere detection of particles distribution in 115-300 nm was developed for remote sensing. First, based on the analysis of advanced loads, the optical system including an off-axis parabolic mirror as the telescope and Czerny-Turner structure as the imaging spectrometer was chosen Secondly, the 2-D photon counting detector with MCP was adopted for the characteristic that the radiation is weak in vacuum ultraviolet waveband. Then the geometric method and 1st order differential calculation were introduced to improve the disadvantages that aberrations in the traditional structure can not be corrected homogeneously to achieve perfect broadband imaging based on the aberration theory. At last, an advanced example was designed. The simulation and calculation of results demonstrate that the modulation transfer function (MTF) of total field of view is more than 0.6 in the broadband, and the spectral resolution is 1.23 nm. The structure is convenient and predominant. It proves that the design is feasible.

  6. Simultaneous removal of NO and SO2 using vacuum ultraviolet light (VUV)/heat/peroxymonosulfate (PMS).

    Science.gov (United States)

    Liu, Yangxian; Wang, Yan; Wang, Qian; Pan, Jianfeng; Zhang, Jun

    2018-01-01

    Simultaneous removal process of SO2 and NO from flue gas using vacuum ultraviolet light (VUV)/heat/peroxymonosulfate (PMS) in a VUV spraying reactor was proposed. The key influencing factors, active species, reaction products and mechanism of SO2 and NO simultaneous removal were investigated. The results show that vacuum ultraviolet light (185 nm) achieves the highest NO removal efficiency and yield of and under the same test conditions. NO removal is enhanced at higher PMS concentration, light intensity and oxygen concentration, and is inhibited at higher NO concentration, SO2 concentration and solution pH. Solution temperature has a double impact on NO removal. CO2 concentration has no obvious effect on NO removal. and produced from VUV-activation of PMS play a leading role in NO removal. O3 and ·O produced from VUV-activation of O2 also play an important role in NO removal. SO2 achieves complete removal under all experimental conditions due to its very high solubility in water and good reactivity. The highest simultaneous removal efficiency of SO2 and NO reaches 100% and 91.3%, respectively. Copyright © 2017 Elsevier Ltd. All rights reserved.

  7. Laser Desorption Postionization Mass Spectrometry of Antibiotic-Treated Bacterial Biofilms using Tunable Vacuum Ultraviolet Radiation

    Energy Technology Data Exchange (ETDEWEB)

    Gasper, Gerald L; Takahashi, Lynelle K; Zhou, Jia; Ahmed, Musahid; Moore, Jerry F; Hanley, Luke

    2010-08-04

    Laser desorption postionization mass spectrometry (LDPI-MS) with 8.0 ? 12.5 eV vacuum ultraviolet synchrotron radiation is used to single photon ionize antibiotics andextracellular neutrals that are laser desorbed both neat and from intact bacterial biofilms. Neat antibiotics are optimally detected using 10.5 eV LDPI-MS, but can be ionized using 8.0 eV radiation, in agreement with prior work using 7.87 eV LDPI-MS. Tunable vacuum ultraviolet radiation also postionizes laser desorbed neutrals of antibiotics and extracellular material from within intact bacterial biofilms. Different extracellular material is observed by LDPI-MS in response to rifampicin or trimethoprim antibiotic treatment. Once again, 10.5 eV LDPI-MS displays the optimum trade-off between improved sensitivity and minimum fragmentation. Higher energy photons at 12.5 eV produce significant parent ion signal, but fragment intensity and other low mass ions are also enhanced. No matrix is added to enhance desorption, which is performed at peak power densities insufficient to directly produce ions, thus allowing observation of true VUV postionization mass spectra of antibiotic treated biofilms.

  8. Absolute calibration of a hydrogen discharge lamp in the vacuum ultraviolet

    Science.gov (United States)

    Nealy, J. E.

    1975-01-01

    A low-pressure hydrogen discharge lamp was calibrated for radiant intensity in the vacuum ultraviolet spectral region on an absolute basis and was employed as a laboratory standard source in spectrograph calibrations. This calibration was accomplished through the use of a standard photodiode detector obtained from the National Bureau of Standards together with onsite measurements of spectral properties of optical components used. The stability of the light source for use in the calibration of vacuum ultraviolet spectrographs and optical systems was investigated and found to be amenable to laboratory applications. The lamp was studied for a range of operating parameters; the results indicate that with appropriate peripheral instrumentation, the light source can be used as a secondary laboratory standard source when operated under preset controlled conditions. Absolute intensity measurements were recorded for the wavelengths 127.7, 158.0, 177.5, and 195.0 nm for a time period of over 1 month, and the measurements were found to be repeatable to within 11 percent.

  9. Luminescence properties of organic–inorganic layered perovskite-type compounds under vacuum ultraviolet irradiation

    Science.gov (United States)

    Kawano, Naoki; Koshimizu, Masanori; Okada, Go; Fujimoto, Yutaka; Kawaguchi, Noriaki; Yanagida, Takayuki; Asai, Keisuke

    2018-02-01

    We investigated the luminescence properties of organic–inorganic layered perovskite-type compounds under vacuum ultraviolet irradiation. A crystal of (C6H5C2H4NH3)2PbBr4 was fabricated by the poor-solvent diffusion method. Exciton emissions from the inorganic layer were observed at 410 nm under ultraviolet irradiation (excitation wavelengths: 180 and 300 nm). The rise time behavior observed in the luminescence decay curve showed no difference among the excitation wavelengths of 60–300 nm. In addition, no excitation peak of benzene such as an intense peak at 180 nm (1A1g → 1E1u) in the vacuum ultraviolet region was observed in the excitation spectra measured while monitoring the exciton emissions from the inorganic layer. These results indicate that the effect of energy transfer from the organic layer to the inorganic layer has negligible contribution to the luminescence properties of organic–inorganic layered perovskite-type compounds.

  10. Nonthermal combined ultraviolet and vacuum-ultraviolet curing process for organosilicate dielectrics

    Energy Technology Data Exchange (ETDEWEB)

    Zheng, H.; Guo, X.; Pei, D.; Li, W.; Blatz, J.; Hsu, K.; Benjamin, D.; Shohet, J. L., E-mail: shohet@engr.wisc.edu [Plasma Processing and Technology Laboratory and Department of Electrical and Computer Engineering, University of Wisconsin-Madison, Madison, Wisconsin 53706 (United States); Lin, Y.-H.; Fung, H.-S.; Chen, C.-C. [National Synchrotron Radiation Research Center, Hsinchu 30076, Taiwan (China); Nishi, Y. [Stanford University, Stanford, California 94305 (United States)

    2016-06-13

    Porous SiCOH films are of great interest in semiconductor fabrication due to their low-dielectric constant properties. Post-deposition treatments using ultraviolet (UV) light on organosilicate thin films are required to decompose labile pore generators (porogens) and to ensure optimum network formation to improve the electrical and mechanical properties of low-k dielectrics. The goal of this work is to choose the best vacuum-ultraviolet photon energy in conjunction with vacuum ultraviolet (VUV) photons without the need for heating the dielectric to identify those wavelengths that will have the most beneficial effect on improving the dielectric properties and minimizing damage. VUV irradiation between 8.3 and 8.9 eV was found to increase the hardness and elastic modulus of low-k dielectrics at room temperature. Combined with UV exposures of 6.2 eV, it was found that this “UV/VUV curing” process is improved compared with current UV curing. We show that UV/VUV curing can overcome drawbacks of UV curing and improve the properties of dielectrics more efficiently without the need for high-temperature heating of the dielectric.

  11. Reflection of circularly polarized light and the effect of particle distribution on circular dichroism in evaporation induced self-assembled cellulose nanocrystal thin films

    Science.gov (United States)

    Hewson, D.; Vukusic, P.; Eichhorn, S. J.

    2017-06-01

    Evaporation induced self-assembled (EISA) thin films of cellulose nanocrystals (CNCs) have shown great potential for displaying structural colour across the visible spectrum. They are believed primarily to reflect left handed circularly polarised (LCP) light due to their natural tendency to form structures comprising left handed chirality. Accordingly the fabrication of homogenously coloured CNC thin films is challenging. Deposition of solid material towards the edge of a dried droplet, via the coffee-stain effect, is one such difficulty in achieving homogenous colour across CNC films. These effects are most easily observed in films prepared from droplets where observable reflection of visible light is localised around the edge of the dry film. We report here, the observation of both left and right hand circularly polarised (LCP/RCP) light in reflection from distinct separate regions of CNC EISA thin films and we elucidate how these reflections are dependent on the distribution of CNC material within the EISA thin film. Optical models of reflection are presented which are based on structures revealed using high resolution transmission electron microscopy (TEM) images of film cross sections. We have also employed spectroscopic characterisation techniques to evaluate the distribution of solid CNC material within a selection of CNC EISA thin films and we have correlated this distribution with polarised light spectra collected from each film. We conclude that film regions from which RCP light was reflected were associated with lower CNC concentrations and thicker film regions.

  12. Reflection of circularly polarized light and the effect of particle distribution on circular dichroism in evaporation induced self-assembled cellulose nanocrystal thin films

    Directory of Open Access Journals (Sweden)

    D. Hewson

    2017-06-01

    Full Text Available Evaporation induced self-assembled (EISA thin films of cellulose nanocrystals (CNCs have shown great potential for displaying structural colour across the visible spectrum. They are believed primarily to reflect left handed circularly polarised (LCP light due to their natural tendency to form structures comprising left handed chirality. Accordingly the fabrication of homogenously coloured CNC thin films is challenging. Deposition of solid material towards the edge of a dried droplet, via the coffee-stain effect, is one such difficulty in achieving homogenous colour across CNC films. These effects are most easily observed in films prepared from droplets where observable reflection of visible light is localised around the edge of the dry film. We report here, the observation of both left and right hand circularly polarised (LCP/RCP light in reflection from distinct separate regions of CNC EISA thin films and we elucidate how these reflections are dependent on the distribution of CNC material within the EISA thin film. Optical models of reflection are presented which are based on structures revealed using high resolution transmission electron microscopy (TEM images of film cross sections. We have also employed spectroscopic characterisation techniques to evaluate the distribution of solid CNC material within a selection of CNC EISA thin films and we have correlated this distribution with polarised light spectra collected from each film. We conclude that film regions from which RCP light was reflected were associated with lower CNC concentrations and thicker film regions.

  13. Generation of a vacuum ultraviolet to visible Raman frequency comb in H2-filled kagomé photonic crystal fiber.

    Science.gov (United States)

    Mridha, M K; Novoa, D; Bauerschmidt, S T; Abdolvand, A; St J Russell, P

    2016-06-15

    We report on the generation of a purely vibrational Raman comb, extending from the vacuum ultraviolet (184 nm) to the visible (478 nm), in hydrogen-filled kagomé-style photonic crystal fiber pumped at 266 nm. Stimulated Raman scattering and molecular modulation processes are enhanced by higher Raman gain in the ultraviolet. Owing to the pressure-tunable normal dispersion landscape of the "fiber + gas" system in the ultraviolet, higher-order anti-Stokes bands are generated preferentially in higher-order fiber modes. The results pave the way toward tunable fiber-based sources of deep and vacuum ultraviolet light for applications in, e.g., spectroscopy and biomedicine.

  14. Exchange-spring-driven spin flop in an ErFe2/YFe2 multilayer studied by x-ray magnetic circular dichroism

    Science.gov (United States)

    Stenning, G. B. G.; Buckingham, A. R.; Bowden, G. J.; Ward, R. C. C.; van der Laan, G.; Shelford, L. R.; Maccherozzi, F.; Dhesi, S. S.; de Groot, P. A. J.

    2011-09-01

    X-ray magnetic circular dichroism at the Er M4,5 edge is used to study the switching behavior of the hard ErFe2 layers in an epitaxial [ErFe2(70 Å)/YFe2(150 Å)] × 25 exchange-spring superlattice. Magnetic hysteresis loops for the Er magnetization, at temperatures T 200 K reveal a crossover to a regime with two irreversible switching processes. Computational modeling for this system gives good agreement with the experiment, revealing that the observed high-temperature switching behavior is due to an exchange-spring-driven spin-flop-like transition. In contrast to the conventional spin-flop transition in an antiferromagnet, the increase in anisotropy energy of the hard magnetic ErFe2 layers and Fe-Fe exchange energy is overcome by a decrease in overall Zeeman energy. Computational studies also reveal two types of transitions between vertical exchange-spring and spin-flop states with first-order and second-order character.

  15. Residual structures in the unfolded state of starch-binding domain of glucoamylase revealed by near-UV circular dichroism and protein engineering techniques.

    Science.gov (United States)

    Ota, Chiaki; Ikeguchi, Masamichi; Tanaka, Akiyoshi; Hamada, Daizo

    2016-10-01

    Protein folding is a thermodynamic process driven by energy gaps between the native and unfolded states. Although a wealth of information is available on the structure of folded species, there is a paucity of data on unfolded species. Here, we analyzed the structural properties of the unfolded state of the starch-binding domain of glucoamylase from Aspergillus niger (SBD) formed in the presence of guanidinium hydrochloride (GuHCl). Although far-UV CD and intrinsic tryptophan fluorescence spectra as well as small angle X-ray scattering suggested that SBD assumes highly unfolded structures in the presence of GuHCl, near-UV circular dichroism of wild-type SBD suggested the presence of residual structures in the unfolded state. Analyses of the unfolded states of tryptophan mutants (W543L, W563A, W590A and W615L) using Similarity Parameter, a modified version of root mean square deviation as a measure of similarity between two spectra, suggested that W543 and W563 have preferences to form native-like residual structures in the GuHCl-unfolded state. In contrast, W615 was entirely unstructured, while W590 tended to form non-native ordered structures in the unfolded state. These data and the amino acid sequence of SBD suggest that local structural propensities in the unfolded state can be determined by the probability of the presence of hydrophobic or charged residues nearby tryptophan residues. Copyright © 2016 Elsevier B.V. All rights reserved.

  16. A circular dichroism sensor for selective detection of Cd2 + and S2 - based on the in-situ generation of chiral CdS quantum dots

    Science.gov (United States)

    Sianglam, Pradthana; Kulchat, Sirinan; Tuntulani, Thawatchai; Ngeontae, Wittaya

    2017-08-01

    We demonstrate an advance in the fabrication of circular dichroism (CD) sensors for detection of Cd2 + and S2 - based on chiral CdS quantum dots (QDs) generated by a facile in-situ reaction. The chiral quantum dots are generated in solutions composed of Cd2 +, S2 -, cysteamine (CA) and L-penicillamine (L-PA), with the number of the generated particles limited by either the Cd2 + or S2 - concentration. We show that the magnitude of the CD signal produced by the QDs is linearly related to the initial concentration of Cd2 + and S2 -, with excellent selectivity over other ions. Our sensor functions over concentration ranges of 65-200 μM and 7-125 μM with detection limits of 59.7 and 1.6 μM for Cd2 + and S2 -, respectively. The sensor is applied in real water samples with results comparing favorably with those obtained from ICP-OES (for Cd2 +) and HPLC (for S2 -).

  17. Synchrotron radiation circular dichroism spectroscopy-defined structure of the C-terminal domain of NaChBac and its role in channel assembly

    Science.gov (United States)

    Powl, Andrew M.; O’Reilly, Andrias O.; Miles, Andrew J.; Wallace, B. A.

    2010-01-01

    Extramembranous domains play important roles in the structure and function of membrane proteins, contributing to protein stability, forming association domains, and binding ancillary subunits and ligands. However, these domains are generally flexible, making them difficult or unsuitable targets for obtaining high-resolution X-ray and NMR structural information. In this study we show that the highly sensitive method of synchrotron radiation circular dichroism (SRCD) spectroscopy can be used as a powerful tool to investigate the structure of the extramembranous C-terminal domain (CTD) of the prokaryotic voltage-gated sodium channel (NaV) from Bacillus halodurans, NaChBac. Sequence analyses predict its CTD will consist of an unordered region followed by an α-helix, which has a propensity to form a multimeric coiled-coil motif, and which could form an association domain in the homotetrameric NaChBac channel. By creating a number of shortened constructs we have shown experimentally that the CTD does indeed contain a stretch of ∼20 α-helical residues preceded by a nonhelical region adjacent to the final transmembrane segment and that the efficiency of assembly of channels in the membrane progressively decreases as the CTD residues are removed. Analyses of the CTDs of 32 putative prokaryotic NaV sequences suggest that a CTD helical bundle is a structural feature conserved throughout the bacterial sodium channel family. PMID:20663949

  18. Interactions of the organogold(III) compound Aubipyc with the copper chaperone Atox1: a joint mass spectrometry and circular dichroism investigation.

    Science.gov (United States)

    Marzo, Tiziano; Scaletti, Federica; Michelucci, Elena; Gabbiani, Chiara; Pescitelli, Gennaro; Messori, Luigi; Massai, Lara

    2015-12-01

    The so called "copper trafficking system" in mammalian cells is primarily devoted to the regulation of copper transport and homeostasis. This system, now well characterized, consists of a few strictly interconnected proteins that assist copper entrance inside cells and then promote metal transfer and delivery to essential copper-dependent cellular proteins (Boal and Rosenzweig 2009a; Banci et al., Mol Life Sci 67:2563-2589, 2010). Yet, the "copper trafficking system" may also facilitate the entrance inside cells of non-physiological metal species such as clinically established platinum drugs. ESI and MALDI MS methods are exploited here to characterize the interactions occurring between the experimental anticancer organogold(III) drug, Aubipyc, and the copper chaperone Atox1, a key protein of the copper trafficking system. The nature of the adducts that are formed when reacting Aubipyc with Atox1 is elucidated in detail. Characterization of the Aubipyc/Atox1 system is further supported by circular dichroism experiments. Binding competitions with mercury and bismuth ions were also explored. The relevance and the biological implications of the present results are discussed.

  19. Origin of anomalous electronic circular dichroism spectrum of RuPt2(tppz)2Cl2(PF6)4 in acetonitrile.

    Science.gov (United States)

    Yu, Hua-Gen

    2014-07-24

    We report a theoretical study of the structures, energetics, and electronic spectra of the Pt(II)/Ru(II) mixed-metal complex RuPt2(tppz)2Cl2(PF6)4 (tppz = 2,3,5,6-tetra(2-pyridyl)pyrazine) in acetonitrile. The hybrid B3LYP density functional theory and its TDDFT methods were used with a complete basis set (CBS) extrapolation scheme and a conductor polarizable continuum model (C-PCM) for solvation effects. Results showed that the trinuclear complex has four types of stable conformers and/or enantiomers. They are separated by high barriers owing to the repulsive H/H geometrical constraints in tppz. A strong entropy effect was found for the dissociation of RuPt2(tppz)2Cl2(PF6)n in acetonitrile. The UV-visible and emission spectra of the complex were also simulated. They are in good agreement with experiments. In this work we have largely focused on exploring the origin of anomalous electronic circular dichroism (ECD) spectra of the RuPt2(tppz)2Cl2(PF6)4 complex in acetonitrile. As a result, a new mechanism has been proposed together with a clear illustration by using a physical model.

  20. Identification of nitric oxide synthase as a thiolate-ligated heme protein using magnetic circular dichroism spectroscopy. Comparison with cytochrome P-450-CAM and chloroperoxidase.

    Science.gov (United States)

    Sono, M; Stuehr, D J; Ikeda-Saito, M; Dawson, J H

    1995-08-25

    Nitric oxide (NO) has recently been recognized as an important biomolecule playing diverse physiological roles. It is synthesized in several different tissues from L-Arg and O2, using NADPH as an electron donor, by a family of heme-containing catalytically self-sufficient monooxygenases known as nitric oxide synthases (NOS). Recently, the CO complex of reduced NOS has been shown to exhibit an absorption maximum near 450 nm, a characteristic spectral feature of cytochrome P-450 (P-450). Yet, the amino acid sequences of NOS and P-450 have no homology. To further probe the active site heme coordination structure and the heme environment of NOS, we have employed magnetic circular dichroism (MCD) and CD spectroscopy in the present study. MCD spectra of several derivatives of rat brain neuronal NOS strikingly resemble those of analogous derivatives of bacterial P-450-CAM and fungal chloroperoxidase, two known thiolate-ligated heme proteins. Given the proven fingerprinting capability of MCD spectroscopy, this provides convincing evidence for endogenous thiolate (cysteinate) ligation to the heme iron of NOS. Furthermore, the heme-related Soret CD bands of NOS (positive) and P-450s (negative), as represented by P-450-CAM, are almost mirror images, whereas chloroperoxidase exhibits totally different CD band shapes. This suggests that the active sites of NOS and P-450 may share some common structural features, but significant distinctions exist between their heme environments in certain aspects such as hydrophobicity or size.

  1. Ratio of ellipticities between 192 and 208 nm (R1): An effective electronic circular dichroism parameter for characterization of the helical components of proteins and peptides.

    Science.gov (United States)

    Banerjee, Raja; Sheet, Tridip

    2017-11-01

    Circular dichroism (CD) spectroscopy represents an important tool for characterization of the peptide and protein secondary structures that mainly arise from the conformational disposition of the peptide backbone in solution. In 1991 Manning and Woody proposed that, in addition to the signal intensity, the ratio between [θ]nπ* and [θ]ππ*ǁ ((R 2 ) ≅ [θ] 222 /[θ] 208 ), along with [θ]ππ*⊥ and [θ]ππ*ǁ ((R 1 ) ≅ [θ] 192 /[θ] 208 ), may be utilized towards identifying the peptide/protein conformation (especially 3 10 - and α-helices). However, till date the use of the ratiometric ellipticity component for helical structure analysis of peptides and proteins has not been reported. We studied a series of temperature dependent CD spectra of a thermally stable, model helical peptide and its related analogs in water as a function of added 2,2,2-trifluoroethanol (TFE) in order to explore their landscape of helicity. For the first time, we have experimentally shown here that the R 1 parameter can characterize better the individual helices, while the other parameter R 2 and the signal intensity do not always converge. We emphasize the use of the R 1 ratio of ellipticities for helical characterization because of the common origin of these two bands (exciton splitting of the amide π→ π* transition in a helical polypeptide). This approach may become worthwhile and timely with the increasing accessibility of CD synchrotron sources. © 2017 Wiley Periodicals, Inc.

  2. Probing the Interaction of Human Serum Albumin with Norfloxacin in the Presence of High-Frequency Electromagnetic Fields: Fluorescence Spectroscopy and Circular Dichroism Investigations

    Directory of Open Access Journals (Sweden)

    Jamshidkhan Chamani

    2011-11-01

    Full Text Available The present study describes an investigation by fluorescence quenching, circular dichroism and UV-visible spectroscopy of the interaction between norfloxacin (NRF and human serum albumin (HSA in the presence of electromagnetic fields (EMFs. The results obtained from this study indicated that NRF had a strong ability to quench HSA at λex = 280 nm. In addition, a slight blue shift occurred, which suggested that the microenvironment of the protein became more hydrophobic after addition of NRF. The interaction between the NRF and HSA, whether in the absence or presence of an EMF, was considered to be a static quenching mechanism. Moreover, synchronous fluorescence demonstrated that the microenvironment around Trp became modified. Data of HSA-NRF in the presence of EMFs between 1 Hz–1 MHz confirmed the results of quenching and blue shifts. Corresponding Stern-Volmer plots were also drawn and the resultant Ksv and kq values were compared. Moreover, the binding parameters, including the number of binding sites, the binding constant and the distance, r, between donor and acceptor, were calculated based on Förster’s non-radiative energy transfer theory. According to far and near UV-CD, the formation of the complex caused changes of the secondary and tertiary structures of HSA. The obtained results are significant for patients who are subjected to high-frequency radiation as this was found to reduce the affinity of NRF to HSA.

  3. Infrared and circular dichroism spectroscopic characterisation of secondary structure components of a water treatment coagulant protein extracted from Moringa oleifera seeds.

    Science.gov (United States)

    Kwaambwa, H M; Maikokera, R

    2008-06-15

    The secondary structure of a water treatment coagulant protein extracted from Moringa oleifera (MO) seeds has been investigated by Fourier transform infrared spectroscopy (FTIR) in the dried state, and by circular dichroism (CD) spectroscopy. The FTIR and CD spectra indicate that the secondary structure of the protein is dominated by alpha-helix. The FTIR spectrum recorded two distinct and strong absorption bands at 1656 cm(-1) and 1542 cm(-1), in the usual range of absorption of helices of proteins. The CD spectrum showed the shape of mainly alpha-helical secondary structure (estimated to be 58+/-4%) characteristic of negative ellipticity bands near 222 nm and 208 nm and a positive band at 192 nm. The beta-sheet structure composition was estimated to be 10+/-3% whereas unordered structures were around 33%. Changes in solution pH affected the protein secondary structure significantly only at pH values above 10, as indicated by CD spectra, whereas ionic strength had minimal effect. CD data also showed that sodium dodecyl sulphate (SDS) interacts with the coagulant protein and modifies the protein conformation. The surfactant-induced conformational change of the coagulant protein was confirmed by quenching of tryptophan fluorescence of the protein.

  4. Oriented circular dichroism analysis of chiral surface-anchored metal-organic frameworks grown by liquid-phase epitaxy and upon loading with chiral guest compounds

    KAUST Repository

    Gu, Zhigang

    2014-06-17

    Oriented circular dichroism (OCD) is explored and successfully applied to investigate chiral surface-anchored metal-organic frameworks (SURMOFs) based on camphoric acid (D- and Lcam) with the composition [Cu2(Dcam) 2x(Lcam)2-2x(dabco)]n (dabco=1,4-diazabicyclo- [2.2.2]-octane). The three-dimensional chiral SURMOFs with high-quality orientation were grown on quartz glass plates by using a layer-by-layer liquid-phase epitaxy method. The growth orientation, as determined by X-ray diffraction (XRD), could be switched between the [001] and [110] direction by using either OH- or COOH-terminated substrates. These SURMOFs were characterized by using OCD, which confirmed the ratio as well as the orientation of the enantiomeric linker molecules. Theoretical computations demonstrate that the OCD band intensities of the enantiopure [Cu2(Dcam)2(dabco)] n grown in different orientations are a direct result of the anisotropic nature of the chiral SURMOFs. Finally, the enantiopure [Cu 2(Dcam)2(dabco)]n and [Cu2(Lcam) 2(dabco)]n SURMOFs were loaded with the two chiral forms of ethyl lactate [(+)-ethyl-D-lactate and (-)-ethyl-L-lactate)]. An enantioselective enrichment of >60 % was observed by OCD when the chiral host scaffold was loaded from the racemic mixture. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Importance of C*-H based modes and large amplitude motion effects in vibrational circular dichroism spectra: the case of the chiral adduct of dimethyl fumarate and anthracene.

    Science.gov (United States)

    Passarello, Marco; Abbate, Sergio; Longhi, Giovanna; Lepri, Susan; Ruzziconi, Renzo; Nicu, Valentin Paul

    2014-06-19

    The role played by the C*-H based modes (C* being the chiral carbon atom) and the large amplitude motions in the vibrational absorption (VA) and vibrational circular dichroism (VCD) spectra is investigated. The example of an adduct of dimethyl fumarate and anthracene, i.e., dimethyl-(+)-(11R,12R)-9,10-dihydro-9,10-ethanoanthracene-11,12-dicarboxylate, and two deuterated isotopomers thereof specially synthesized for this goal, are considered. By comparing the experimental and DFT calculated spectra of the undeuterated and deuterated species, we demonstrate that the C*-H bending, rocking, and stretching modes in the VA and VCD spectra are clearly identified in well defined spectroscopic features. Further, significant information about the conformer distribution is gathered by analyzing the VA and VCD data of both the fingerprint and the C-H stretching regions, with particular attention paid to the band shape data. Effects related to the large amplitude motions of the two methoxy moieties have been simulated by performing linear transit (LT) calculations, which consists of varying systematically the relative positions of the two methoxy moieties and calculating VCD spectra for the partially optimized structures obtained in this way. The LT method allows one to improve the quality of calculated spectra, as compared to experimental results, especially in regard to relative intensities and bandwidths.

  6. Origin-independent sum over states simulations of magnetic and electronic circular dichroism spectra via the localized orbital/local origin method.

    Science.gov (United States)

    Štěpánek, Petr; Bouř, Petr

    2015-04-15

    Although electronic and magnetic circular dichroism (ECD, MCD) spectra reveal valuable details about molecular geometry and electronic structure, quantum-chemical simulations significantly facilitate their interpretation. However, the simulated results may depend on the choice of coordinate origin. Previously (Štěpánek and Bouř, J. Comput. Chem. 2013, 34, 1531), the sum-over-states (SOS) methodology was found useful for efficient MCD computations. Approximate wave functions were "resolved" using time-dependent density functional theory, and the origin-dependence was avoided by placing the origin to the center of mass of the investigated molecule. In this study, a more elegant way is proposed, based on the localized orbital/local origin (LORG) formalism, and a similar approach is also applied to generate ECD intensities. The LORG-like approach yields fully origin-independent ECD and MCD spectra. The results thus indicate that the computationally relatively cheap SOS simulations open a new way of modeling molecular properties, including those involving the origin-dependent magnetic dipole moment operator. © 2015 Wiley Periodicals, Inc.

  7. Circular dichroism and absorption spectroscopic data reveal binding of the natural cis-carotenoid bixin to human alpha1-acid glycoprotein.

    Science.gov (United States)

    Zsila, Ferenc; Molnár, Péter; Deli, József; Lockwood, Samuel F

    2005-08-01

    Using circular dichroism (CD) and electronic absorption spectroscopy techniques, interaction of the natural dietary cis-carotenoid bixin with an important human plasma protein in vitro was demonstrated for the first time. The induced CD spectra of bixin obtained under physiological conditions (pH 7.4, 37 degrees C) revealed its binding to the serum acute-phase reactant alpha(1)-acid glycoprotein (AGP), a member of the lipocalin protein family. Spectral features of the extrinsic Cotton effects of bixin suggested the inclusion of a single, chirally distorted ligand molecule into the asymmetric protein environment. Compared with the absorption spectra obtained in ethanol and benzene, the strong red shift of the main absorption peak of AGP-bound bixin indicated that the proposed binding site was rich in aromatic residues, and also suggested that hydrophobic interactions were involved in the binding. Using the data obtained from the CD titration experiments, the association constant (Ka=4.5x10(5)M-1) and stoichiometry of the binding (0.15) were calculated. The low value of the stoichiometry was attributed to the structural polymorphism of AGP. To the authors' knowledge, the current study represents the first human lipocalin protein for which carotenoid binding affinity has been explored in vitro with these techniques.

  8. Effects of spin-orbit interaction in chromium on oxygen K -edge x-ray magnetic circular dichroism spectra in CrO2

    Science.gov (United States)

    Koide, Akihiro; Yokoyama, Toshihiko

    2017-10-01

    We calculate the oxygen K -edge x-ray magnetic circular dichroism (XMCD) spectra of CrO2 to investigate the origin of light-element XMCD. The XMCD spectra evaluated by using a multiple scattering theory are interpreted in terms of the spin-orbit interaction (SOI) at each atomic site. We find that the SOI at the nearest-neighbor Cr atoms dominantly contributes to the oxygen K -edge XMCD. Since it has been speculated that XMCD originates from the spin polarization and the SOI at the x-ray-absorbing atom, the present finding may lead to modification of the previously speculated mechanism underlying K -edge XMCD. We also perform calculations with a small CrO2 cluster to examine how the O-p and Cr-d states are hybridized and how oxygen atoms acquire orbital angular momentum density. Strong K -edge XMCD features reflect the character of the d states of neighboring magnetic atoms and do not directly connect to the orbital magnetic moments of light-element p states.

  9. Possibility of using sources of vacuum ultraviolet irradiation to solve problems of space material science

    Science.gov (United States)

    Verkhoutseva, E. T.; Yaremenko, E. I.

    1974-01-01

    An urgent problem in space materials science is simulating the interaction of vacuum ultraviolet (VUV) of solar emission with solids in space conditions, that is, producing a light source with a distribution that approximates the distribution of solar energy. Information is presented on the distribution of the energy flux of VUV of solar radiation. Requirements that must be satisfied by the VUV source used for space materials science are formulated, and a critical evaluation is given of the possibilities of using existing sources for space materials science. From this evaluation it was established that none of the sources of VUV satisfies the specific requirements imposed on the simulator of solar radiation. A solution to the problem was found to be in the development of a new type of source based on exciting a supersonic gas jet flowing into vacuum with a sense electron beam. A description of this gas-jet source, along with its spectral and operation characteristics, is presented.

  10. Metallic Na formation in NaCl crystals with irradiation of electron or vacuum ultraviolet photon

    Energy Technology Data Exchange (ETDEWEB)

    Owaki, Shigehiro [Osaka Prefecture Univ., Sakai, Osaka (Japan). Coll. of Integrated Arts and Sciences; Koyama, Shigeko; Takahashi, Masao; Kamada, Masao; Suzuki, Ryouichi

    1997-03-01

    Metallic Na was formed in NaCl single crystals with irradiation of a variety of radiation sources and analyzed the physical states with several methods. In the case of irradiation of 21 MeV electron pulses to the crystal blocks, the optical absorption and lifetime measurement of positron annihilation indicated appearance of Na clusters inside. Radiation effects of electron beam of 30 keV to the crystals in vacuum showed the appearance of not only metallic Na but atomic one during irradiation with Auger electron spectroscopy. Intense photon fluxes in vacuum ultraviolet region of synchrotron radiation were used as another source and an analyzing method of ultraviolet photoelectron spectroscopy. The results showed the metallic Na layered so thick that bulk plasmon can exist. (author)

  11. Photofragmentation of gas-phase acetic acid and acetamide clusters in the vacuum ultraviolet region

    Science.gov (United States)

    Berholts, Marta; Myllynen, Hanna; Kooser, Kuno; Itälä, Eero; Granroth, Sari; Levola, Helena; Laksman, Joakim; Oghbaiee, Shabnam; Oostenrijk, Bart; Nõmmiste, Ergo; Kukk, Edwin

    2017-11-01

    Photofragmentation of gas-phase acetamide and acetic acid clusters produced by a supersonic expansion source has been studied using time-of-flight mass spectrometry and the partial ion yield (PIY) technique combined with tunable vacuum-ultraviolet synchrotron radiation. Appearance energies of the clusters and their fragments were experimentally determined from the PIY measurements. The effect of clusterization conditions on the formation and fragmentation of acetic acid clusters was investigated. Ab initio quantum mechanical calculations were performed on both samples' dimers to find their neutral and ionized geometries as well as proton transfer energy barriers leading to the optimal geometries. In the case of the acetamide dimer, the reaction resulting in the production of ammoniated acetamide was probed, and the geometry of the obtained ion was calculated.

  12. Fragmentation and dimerization of aliphatic amino acid films induced by vacuum ultraviolet irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Tanaka, Masahito [Research Institute of Instrumentation Frontier, National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba Tyuou-2, AIST, Umezono 1-1-1, Tsukuba, Ibaraki, 305-8568 (Japan)], E-mail: masahito-tanaka@aist.go.jp; Kaneko, Fusae [Graduate School of Science and Technology, Kobe University, Tsurukabuto 3-11, Nada-ku, Kobe 657-8501 (Japan); Koketsu, Toshiyuki [Graduate School of Human Development and Environment, Kobe University, Tsurukabuto 3-11, Nada-ku, Kobe 657-8501 (Japan); Nakagawa, Kazumichi [Graduate School of Science and Technology, Kobe University, Tsurukabuto 3-11, Nada-ku, Kobe 657-8501 (Japan); Graduate School of Human Development and Environment, Kobe University, Tsurukabuto 3-11, Nada-ku, Kobe 657-8501 (Japan); Yamada, Toru [Neuroscience Research Institute, National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba Tyuou-2, AIST, Umezono 1-1-1, Tsukuba, Ibaraki 305-8568 (Japan)

    2008-10-15

    The chemical reaction of aliphatic amino acid, such as alanine (Ala) and leucine (Leu), in the solid phase induced by vacuum ultraviolet (VUV) irradiation was studied by high-performance liquid chromatography technique and mass spectroscopic method. Quantum efficiencies of dimerization of Ala in the solid phase obviously showed irradiated VUV wavelength dependence. The values of quantum efficiencies of formation of Ala dimer were determined to be 5.7x10{sup -5}, 1.3x10{sup -3}, and 2.4x10{sup -4} for 208, 183, and 87 nm irradiation, respectively. VUV-induced fragment desorption from Ala and Leu films has also been examined by mass spectroscopic method. Observed mass spectra clearly indicated that both the deamination and decarboxylation reactions were common in both Ala and Leu films, and the dissociation of side chain occurred only in Leu film.

  13. Vacuum ultraviolet and visible spectra of ZnO:Eu{sup 3+} prepared by combustion synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Cheng Bingming [National Synchrotron Radiation Research Centre, Hsinchu, Taiwan (China); Yu Lixin; Duan Changkui; Wang, Huaishan; Tanner, Peter A [Department of Biology and Chemistry, City University of Hong Kong, Kowloon (Hong Kong)], E-mail: bhtan@cityu.edu.hk

    2008-08-27

    Zinc oxide doped with 1 at.% Eu{sup 3+} has been prepared by combustion synthesis using several different reductants. Samples sintered at 800 deg. C were {approx}30 nm in size and Fourier transform IR spectra demonstrated that they were relatively free of contaminants. Ultraviolet and near-ultraviolet laser excited emission spectra showed that Eu{sup 3+} ions are disordered and not situated at discrete lattice sites in ZnO and consequently no evidence for energy transfer from the host to Eu{sup 3+} was found. Vacuum ultraviolet (VUV) excitation produced defect site emission in addition to near-band-edge emission but the intensity of the Eu{sup 3+} visible emission was very weak. Bands between 6.2 and 9.1 eV in the VUV excitation spectra have been assigned to electric dipole allowed transitions, 3d-4p.

  14. Two-dimensional vacuum ultraviolet images in different MHD events on the EAST tokamak

    Science.gov (United States)

    Zhijun, WANG; Xiang, GAO; Tingfeng, MING; Yumin, WANG; Fan, ZHOU; Feifei, LONG; Qing, ZHUANG; EAST Team

    2018-02-01

    A high-speed vacuum ultraviolet (VUV) imaging telescope system has been developed to measure the edge plasma emission (including the pedestal region) in the Experimental Advanced Superconducting Tokamak (EAST). The key optics of the high-speed VUV imaging system consists of three parts: an inverse Schwarzschild-type telescope, a micro-channel plate (MCP) and a visible imaging high-speed camera. The VUV imaging system has been operated routinely in the 2016 EAST experiment campaign. The dynamics of the two-dimensional (2D) images of magnetohydrodynamic (MHD) instabilities, such as edge localized modes (ELMs), tearing-like modes and disruptions, have been observed using this system. The related VUV images are presented in this paper, and it indicates the VUV imaging system is a potential tool which can be applied successfully in various plasma conditions.

  15. Tunable vacuum ultraviolet laser based spectrometer for angle resolved photoemission spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Jiang, Rui; Mou, Daixiang; Wu, Yun; Huang, Lunan; Kaminski, Adam [Division of Materials Science and Engineering, Ames Laboratory, Ames, Iowa 50011 (United States); Department of Physics and Astronomy, Iowa State University, Ames, Iowa 50011 (United States); McMillen, Colin D.; Kolis, Joseph [Department of Chemistry, Clemson University, Clemson, South Carolina 29634 (United States); Giesber, Henry G.; Egan, John J. [Advanced Photonic Crystals LLC, Fort Mill, South Carolina 29708 (United States)

    2014-03-15

    We have developed an angle-resolved photoemission spectrometer with tunable vacuum ultraviolet laser as a photon source. The photon source is based on the fourth harmonic generation of a near IR beam from a Ti:sapphire laser pumped by a CW green laser and tunable between 5.3 eV and 7 eV. The most important part of the set-up is a compact, vacuum enclosed fourth harmonic generator based on potassium beryllium fluoroborate crystals, grown hydrothermally in the US. This source can deliver a photon flux of over 10{sup 14} photon/s. We demonstrate that this energy range is sufficient to measure the k{sub z} dispersion in an iron arsenic high temperature superconductor, which was previously only possible at synchrotron facilities.

  16. Selective irradiation of radicals for biomedical treatment using vacuum ultraviolet light from an excimer lamp

    Science.gov (United States)

    Ono, Ryo; Tokumitsu, Yusuke; Zen, Shungo; Yonemori, Seiya

    2014-10-01

    In plasma medicine, radicals are considered to play important roles. However, the medical effect of each radical, such as OH and O, is unknown. To examine the effect of each radical, selective production of radicals is needed. We developed selective production of radicals for biomedical treatment using a vacuum ultraviolet (VUV) light emitted from an excimer lamp. Selective irradiation of OH radicals can be achieved by irradiating the 172-nm VUV light from a Xe2 excimer lamp to a humid helium flow in a quartz tube. The water molecules are strongly photodissociated by the VUV light to produce OH radicals. A photochemical simulation for the selective OH production is developed to calculate the OH density. The calculated OH density is compared with OH density measured using laser-induced fluorescence (LIF). Selective production of other radicals than OH is also discussed.

  17. Vacuum Ultraviolet Field Emission Lamp Consisting of Neodymium Ion Doped Lutetium Fluoride Thin Film as Phosphor

    Directory of Open Access Journals (Sweden)

    Masahiro Yanagihara

    2014-01-01

    Full Text Available A vacuum ultraviolet (VUV field emission lamp was developed by using a neodymium ion doped lutetium fluoride (Nd3+ : LuF3 thin film as solid-state phosphor and carbon nanofiber field electron emitters. The thin film was synthesized by pulsed laser deposition and incorporated into the lamp. The cathodoluminescence spectra of the lamp showed multiple emission peaks at 180, 225, and 255 nm. These emission spectra were in good agreement with the spectra reported for the Nd3+ : LuF3 crystal. Moreover, application of an acceleration voltage effectively increased the emission intensity. These results contribute to the performance enhancement of the lamp operating in the VUV region.

  18. Si nanocrystals embedded in SiO2: Optical studies in the vacuum ultraviolet range

    DEFF Research Database (Denmark)

    Pankratov, V.; Osinniy, Viktor; Kotlov, A.

    2011-01-01

    Photoluminescence excitation and transmission spectra of Si nanocrystals of different diameters embedded in a SiO2 matrix have been investigated in the broad visible-vacuum ultraviolet spectral range using synchrotron radiation. The dependence of the photoluminescence excitation spectra...... on the nanocrystals size was experimentally established. It is shown that the photoluminescence excitation and absorption spectra are significantly blueshifted with decreasing Si nanocrystal size. A detailed comparison of photoluminescence excitation and absorption spectra with data from theoretical modeling has been...... done. It is demonstrated that the experimentally determined blueshift of the photoluminescence excitation and absorption spectra is larger than the theoretical predictions. The influence of point defects in the SiO2 matrix on the optical and luminescence properties of the embedded Si nanocrystals...

  19. Synchrotron Vacuum Ultraviolet Light and Soft X-Ray Radiation Effects on Aluminized Teflon FEP Investigated

    Science.gov (United States)

    Dever, Joyce A.; Townsend, Jacqueline A.; Gaier, James R.; Jalics, Alice I.

    1999-01-01

    Since the Hubble Space Telescope (HST) was deployed in low Earth orbit in April 1990, two servicing missions have been conducted to upgrade its scientific capabilities. Minor cracking of second-surface metalized Teflon FEP (DuPont; fluorinated ethylene propylene) surfaces from multilayer insulation (MLI) was first observed upon close examination of samples with high solar exposure retrieved during the first servicing mission, which was conducted 3.6 years after deployment. During the second HST servicing mission, 6.8 years after deployment, astronaut observations and photographic documentation revealed significant cracks in the Teflon FEP layer of the MLI on both the solar- and anti-solar-facing surfaces of the telescope. NASA Goddard Space Flight Center directed the efforts of the Hubble Space Telescope MLI Failure Review Board, whose goals included identifying the low-Earth-orbit environmental constituent(s) responsible for the cracking and embrittling of Teflon FEP which was observed during the second servicing mission. The NASA Lewis Research Center provided significant support to this effort. Because soft x-ray radiation from solar flares had been considered as a possible cause for the degradation of the mechanical properties of Teflon FEP (ref. 1), the effects of soft xray radiation and vacuum ultraviolet light on Teflon FEP were investigated. In this Lewisled effort, samples of Teflon FEP with a 100-nm layer of vapor-deposited aluminum (VDA) on the backside were exposed to synchrotron radiation of various vacuum ultraviolet and soft x-ray wavelengths between 18 nm (69 eV) and 0.65 nm (1900 eV). Synchrotron radiation exposures were conducted using the National Synchrotron Light Source at Brookhaven National Laboratory. Samples of FEP/VDA were exposed with the FEP surface facing the synchrotron beam. Doses and fluences were compared with those estimated for the 20-yr Hubble Space Telescope mission.

  20. Permanent hydrophilic modification of polypropylene and poly(vinyl alcohol) films by vacuum ultraviolet radiation

    Energy Technology Data Exchange (ETDEWEB)

    Belmonte, Guilherme Kretzmann [Instituto de Química, Universidade Federal do Rio Grande do Sul (UFRGS), Avenida Bento Gonçalves 9500, 91501-970 Porto Alegre, RS (Brazil); Charles, German [Centro de Química Aplicada (CEQUIMAP), Facultad de Ciencias Químicas, Unversidad Nacional de Córdoba, Haya de la Torre y Medina Allende, Edificio de Ciencias II, Ciudad Universitaria, Córdoba 5000 (Argentina); Strumia, Miriam Cristina [Departamento de Química Orgánica, Facultad de Ciencias Químicas, Universidad Nacional de Córdoba, IPQA-Conicet, Haya de la Torre y Medina Allende, Edificio de Ciencias II, Ciudad Universitaria, Córdoba 5000 (Argentina); Weibel, Daniel Eduardo, E-mail: danielw@iq.ufrgs.br [Instituto de Química, Universidade Federal do Rio Grande do Sul (UFRGS), Avenida Bento Gonçalves 9500, 91501-970 Porto Alegre, RS (Brazil)

    2016-09-30

    Highlights: • Polypropylene and Poly(vinyl alcohol) were surface modified by vacuum ultraviolet (VUV) irradiation. • The hydrophilicity of the treated films was permanent and resisted aging for several months. • Grafting of styrene monomer was only observed in the VUV irradiated regions. • The obtained results showed the potential in the use of VUV treatment for surface modification and processing of polymers which lack chromophores in the UV region. - Abstract: Polypropylene (PP) and Poly(vinyl alcohol) (PVA) both synthetics polymers but one of them biodegradable, were surface modified by vacuum ultraviolet (VUV) irradiation. After VUV irradiation in an inert nitrogen atmosphere, the films were exposed to oxygen gas. The treated films were characterized by water contact angle measurements (WCA), optical profilometry, FTIR-ATR, XPS, UPS and NEXAFS techniques. PP and PVA VUV-treated films reached superhydrophilic conditions (WCAs <10°) in about 30 min of irradiation under our experimental conditions. It was observed that when the WCAs reached about 35–40° the hydrophilicity was permanent in both polymers. These results contrasted with typical plasma treatments were a rapid hydrophobic recovery with aging time is usually observed. UPS and XPS data showed the presence of new functionalities on the PP and PVA surfaces that were assigned to COO, C=O, C−O and C=C functional groups. Finally, grafting of styrene (ST) as a typical monomer was tested on PP films. It was confirmed that only in the VUV irradiated region an efficient grafting of ST or polymerized ST was found. Outside the irradiated regions no ST grafted was observed. Our results showed the potential use of VUV treatment for surface modification and processing of polymers which lack chromophores in the UV region.

  1. A Physico-Chemical Study of Some Areas of Fundamental Significance to Biophysics

    Energy Technology Data Exchange (ETDEWEB)

    Kumar, Devendra; McGlynn, S. P.

    1999-04-01

    This report covers: Radiation Signatures; Electronic Structure of Steroids, Vitamins, and others; Laser Optogalvanic Effect; Vacuum Ultraviolet Spectroscopy, including Electron Scattering, Photochemistry, and Magnetic Circular Dichroism; and Ozone.

  2. Investigation of the Surface of Poly(ethylene terephthalate) Films Modified by Vacuum Ultraviolet Irradiation in Air

    NARCIS (Netherlands)

    Mitrofanov, A. V.; Karban, O. V.; Sugonyako, A.; Lubomska, M.

    This paper reports on the results of measuring the changes in the characteristics of the surface of poly(ethylene terephthalate) films upon radiation-induced oxidation of the polymer under vacuum ultraviolet irradiation in an oxygen-containing medium. The films were irradiated by light from a

  3. Effects of plasma and vacuum-ultraviolet exposure on the mechanical properties of low-k porous organosilicate glass

    Science.gov (United States)

    X. Guo; J.E. Jakes; S. Banna; Y. Nishi; J.L. Shohet

    2014-01-01

    The effects of plasma exposure and vacuum-ultraviolet (VUV) irradiation on the mechanical properties of low-k porous organosilicate glass (SiCOH) dielectric films were investigated. Nanoindentation measurements were made on SiCOH films before and after exposure to an electron-cyclotron-resonance plasma or a monochromatic synchrotron VUV beam, to determine the changes...

  4. Absorption and magnetic circular dichroism (MCD) studies of 1,4,5,8-naphthalenetetracarboxy diimides in terms of CASSCF method and FC theory

    Energy Technology Data Exchange (ETDEWEB)

    Sterzel, Mariusz; Andrzejak, Marcin; Pawlikowski, Marek T.; Gawronski, J

    2004-05-10

    The electronic and geometrical structures of the low-energy states of 1,4,5,8-naphthalenetetracarboxylic dianhydride parent diimide (1) are studied in terms of the complete active space self-consistent field (CASSCF) method employed at different level with respect to the size and the quality of the active space. In the framework of the vibronic model based on the Franck-Condon (FC) effect the absorption and magnetic circular dichroism (MCD) spectra are studied in the excitation region corresponding to two low-energy 1{sup 1}A{sub g} {yields} 1{sup 1}B{sub 2u} and 1{sup 1}A{sub g} {yields} 1{sup 1}B{sub 3u} electronic transitions in diimides. In that (visible) excitation region the CASSCF computations with the 5{pi}[4n]5{pi} active space (i.e., the naphthalene-like {pi} orbitals enriched by the four lone pair orbitals of the oxygen atoms) were found to reproduce very well the empirical absorption and the MCD spectra measured for the dicyclohexyl-N,N{sup '}-substituted diimide (2). At the same CASSCF/5{pi}[4n]5{pi} level, the electronic absorption of diimides in the near UV excitation region were attributed to the 1{sup 1}A{sub g} {yields} 2{sup 1}B{sub 1u}, 1{sup 1}A{sub g} {yields} 2{sup 1}B{sub 3u} and 1{sup 1}A{sub g} {yields} 2{sup 1}B{sub 2u} electronic transitions; the latter two are mostly localized on the ''diimide chromophore''. For these transitions the calculated magneto-optical characteristics, such as sign pattern and intensity distribution in the MCD spectrum, were found to be consistent with that experimentally observed for the diimide 2 compound.

  5. Absorption and magnetic circular dichroism (MCD) studies of 1,4,5,8-naphthalenetetracarboxy diimides in terms of CASSCF method and FC theory

    Science.gov (United States)

    Sterzel, Mariusz; Andrzejak, Marcin; Pawlikowski, Marek T.; Gawroński, J.

    2004-05-01

    The electronic and geometrical structures of the low-energy states of 1,4,5,8-naphthalenetetracarboxylic dianhydride parent diimide ( 1) are studied in terms of the complete active space self-consistent field (CASSCF) method employed at different level with respect to the size and the quality of the active space. In the framework of the vibronic model based on the Franck-Condon (FC) effect the absorption and magnetic circular dichroism (MCD) spectra are studied in the excitation region corresponding to two low-energy 1 1A g → 1 1B 2u and 1 1A g → 1 1B 3u electronic transitions in diimides. In that (visible) excitation region the CASSCF computations with the 5π[4n]5π active space (i.e., the naphthalene-like π orbitals enriched by the four lone pair orbitals of the oxygen atoms) were found to reproduce very well the empirical absorption and the MCD spectra measured for the dicyclohexyl- N, N'-substituted diimide ( 2). At the same CASSCF/5π[4n]5π level, the electronic absorption of diimides in the near UV excitation region were attributed to the 1 1A g → 2 1B 1u, 1 1A g → 2 1B 3u and 1 1A g → 2 1B 2u electronic transitions; the latter two are mostly localized on the "diimide chromophore". For these transitions the calculated magneto-optical characteristics, such as sign pattern and intensity distribution in the MCD spectrum, were found to be consistent with that experimentally observed for the diimide 2 compound.

  6. Biomolecular and structural analyses of cauliflower-like DNAs by ultraviolet, circular dichroism, and fluorescence spectroscopies in comparison with natural DNA.

    Science.gov (United States)

    Gill, Pooria; Ranjbar, Bijan; Saber, Reza; Khajeh, Khosro; Mohammadian, Mehdi

    2011-07-01

    Cauliflower-like DNAs are stem-loop DNAs that are fabricated periodically in inverted repetitions from deoxyribonucleic acid phosphates (dNTPs) by loop-mediated isothermal amplification (LAMP). Cauliflower-like DNAs have ladder-shape behaviors on gel electrophoresis, and increasing the time of LAMP leads to multiplying the repetitions, stem-loops, and electrophoretic bands. Cauliflower-like DNAs were fabricated via LAMP using two loop primers, two bumper primers, dNTPs, a λ-phage DNA template, and a Bst DNA polymerase in 75- and 90-min periods. These times led to manufacturing two types of cauliflower-like DNAs with different contents of inverted repetitions and stem-loops, which were clearly indicated by two comparable electrophoresis patterns in agarose gel. LAMP-fabricated DNAs and natural dsB-DNA (salmon genomic DNA) were dialyzed in Gomori phosphate buffer (10 mM, pH 7.4) to be isolated from salts, nucleotides, and primers. Dialyzed DNAs were studied using UV spectroscopy, circular dichroism spectropolarimetry, and fluorescence spectrophotometry. Structural analyses indicated reduction of the molecular ellipticity and extinction coefficients in comparison with B-DNA. Also, cauliflower-like DNAs demonstrated less intrinsic and more extrinsic fluorescence in comparison with natural DNA. The overwinding and lengthening of the cauliflower-like configurations of LAMP DNAs led to changes in physical parameters of this type of DNA in comparison with natural DNA. The results obtained introduced new biomolecular characteristics of DNA macromolecules fabricated within a LAMP process and show the effects of more inverted repeats and stem-loops, which are manufactured by lengthening the process.

  7. Detailed assignment of the magnetic circular dichroism and UV-vis spectra of five-coordinate high-spin ferric [Fe(TPP)(Cl)].

    Science.gov (United States)

    Paulat, Florian; Lehnert, Nicolai

    2008-06-02

    High-spin (hs) ferric heme centers occur in the catalytic or redox cycles of many metalloproteins and exhibit very complicated magnetic circular dichroism (MCD) and UV-vis absorption spectra. Therefore, detailed assignments of the MCD spectra of these species are missing. In this study, the electronic spectra (MCD and UV-vis) of the five-coordinate hs ferric model complex [Fe(TPP)(Cl)] are analyzed and assigned for the first time. A correlated fit of the absorption and low-temperature MCD spectra of [Fe(TPP)(Cl)] lead to the identification of at least 20 different electronic transitions. The assignments of these spectra are based on the following: (a) variable temperature and variable field saturation data, (b) time-dependent density functional theory calculations, (c) MCD pseudo A-terms, and (d) correlation to resonance Raman (rRaman) data to validate the assignments. From these results, a number of puzzling questions about the electronic spectra of [Fe(TPP)(Cl)] are answered. The Soret band in [Fe(TPP)(Cl)] is split into three components because one of its components is mixed with the porphyrin A2u72-->Eg82/83 (pi-->pi*) transition. The broad, intense absorption feature at higher energy from the Soret band is due to one of the Soret components and a mixed sigma and pi chloro to iron CT transition. The high-temperature MCD data allow for the identification of the Q v band at 20 202 cm(-1), which corresponds to the C-term feature at 20 150 cm(-1). Q is not observed but can be localized by correlation to rRaman data published before. Finally, the low energy absorption band around 650 nm is assigned to two P-->Fe charge transfer transitions, one being the long sought after A1u(HOMO)-->d pi transition.

  8. Towards an exact theory of linear absorbance and circular dichroism of pigment-protein complexes: importance of non-secular contributions.

    Science.gov (United States)

    Dinh, Thanh-Chung; Renger, Thomas

    2015-01-21

    A challenge for the theory of optical spectra of pigment-protein complexes is the equal strength of the pigment-pigment and the pigment-protein couplings. Treating both on an equal footing so far can only be managed by numerically costly approaches. Here, we exploit recent results on a normal mode analysis derived spectral density that revealed the dominance of the diagonal matrix elements of the exciton-vibrational coupling in the exciton state representation. We use a cumulant expansion technique that treats the diagonal parts exactly, includes an infinite summation of the off-diagonal parts in secular and Markov approximations, and provides a systematic perturbative way to include non-secular and non-Markov corrections. The theory is applied to a model dimer and to chlorophyll (Chl) a and Chl b homodimers of the reconstituted water-soluble chlorophyll-binding protein (WSCP) from cauliflower. The model calculations reveal that the non-secular/non-Markov effects redistribute oscillator strength from the strong to the weak exciton transition in absorbance and they diminish the rotational strength of the exciton transitions in circular dichroism. The magnitude of these corrections is in a few percent range of the overall signal, providing a quantitative explanation of the success of time-local convolution-less density matrix theory applied earlier. A close examination of the optical spectra of Chl a and Chl b homodimers in WSCP suggests that the opening angle between Qy transition dipole moments in Chl b homodimers is larger by about 9(∘) than for Chl a homodimers for which a crystal structure of a related WSCP complex exists. It remains to be investigated whether this change is due to a different mutual geometry of the pigments or due to the different electronic structures of Chl a and Chl b.

  9. Mapping the Anopheles gambiae odorant binding protein 1 (AgamOBP1) using modeling techniques, site directed mutagenesis, circular dichroism and ligand binding assays.

    Science.gov (United States)

    Rusconi, B; Maranhao, A C; Fuhrer, J P; Krotee, P; Choi, S H; Grun, F; Thireou, T; Dimitratos, S D; Woods, D F; Marinotti, O; Walter, M F; Eliopoulos, E

    2012-08-01

    The major malaria vector in Sub-Saharan Africa is the Anopheles gambiae mosquito. This species is a key target of malaria control measures. Mosquitoes find humans primarily through olfaction, yet the molecular mechanisms associated with host-seeking behavior remain largely unknown. To further understand the functionality of A. gambiae odorant binding protein 1 (AgamOBP1), we combined in silico protein structure modeling and site-directed mutagenesis to generate 16 AgamOBP1 protein analogues containing single point mutations of interest. Circular dichroism (CD) and ligand-binding assays provided data necessary to probe the effects of the point mutations on ligand binding and the overall structure of AgamOBP1. Far-UV CD spectra of mutated AgamOBP1 variants displayed both substantial decreases to ordered α-helix structure (up to22%) and increases to disordered α-helix structure(up to 15%) with only minimal changes in random coil (unordered) structure. In mutations Y54A, Y122A and W114Q, aromatic side chain removal from the binding site significantly reduced N-phenyl-1-naphthylamine binding. Several non-aromatic mutations (L15T, L19T, L58T, L58Y, M84Q, M84K, H111A, Y122A and L124T) elicited changes to protein conformation with subsequent effects on ligand binding. This study provides empirical evidence for the in silico predicted functions of specific amino acids in AgamOBP1 folding and ligand binding characteristics. Copyright © 2012 Elsevier B.V. All rights reserved.

  10. Combination of acoustic levitation with small angle scattering techniques and synchrotron radiation circular dichroism. Application to the study of protein solutions.

    Science.gov (United States)

    Cristiglio, Viviana; Grillo, Isabelle; Fomina, Margarita; Wien, Frank; Shalaev, Evgenyi; Novikov, Alexey; Brassamin, Séverine; Réfrégiers, Matthieu; Pérez, Javier; Hennet, Louis

    2017-01-01

    The acoustic levitation technique is a useful sample handling method for small solid and liquids samples, suspended in air by means of an ultrasonic field. This method was previously used at synchrotron sources for studying pharmaceutical liquids and protein solutions using x-ray diffraction and small angle x-ray scattering (SAXS). In this work we combined for the first time this containerless method with small angle neutron scattering (SANS) and synchrotron radiation circular dichroism (SRCD) to study the structural behavior of proteins in solutions during the water evaporation. SANS results are also compared with SAXS experiments. The aggregation behavior of 45μl droplets of lysozyme protein diluted in water was followed during the continuous increase of the sample concentration by evaporating the solvent. The evaporation kinetics was followed at different drying stage by SANS and SAXS with a good data quality. In a prospective work using SRCD, we also studied the evolution of the secondary structure of the myoglobin protein in water solution in the same evaporation conditions. Acoustic levitation was applied for the first time with SANS and the high performances of the used neutron instruments made it possible to monitor fast container-less reactions in situ. A preliminary work using SRCD shows the potentiality of its combination with acoustic levitation for studying the evolution of the protein structure with time. This multi-techniques approach could give novel insights into crystallization and self-assembly phenomena of biological compound with promising potential applications in pharmaceutical, food and cosmetics industry. This article is part of a Special Issue entitled "Science for Life" Guest Editor: Dr. Austen Angell, Dr. Salvatore Magazù and Dr. Federica Migliardo. Copyright © 2016 Elsevier B.V. All rights reserved.

  11. The location of the high- and low-affinity bilirubin-binding sites on serum albumin: ligand-competition analysis investigated by circular dichroism.

    Science.gov (United States)

    Goncharova, Iryna; Orlov, Sergey; Urbanová, Marie

    2013-01-01

    The locations of three bilirubin (BR)-binding sites with different affinities were identified as subdomains IB, IIA and IIIA for five mammalian serum albumins (SAs): human (HSA), bovine (BSA), rat, (RSA), rabbit (RbSA) and sheep (SSA). The stereoselectivity of a high-affinity BR-binding site was identified in the BR/SA=1/1 system by circular dichroism (CD) spectroscopy, the sites with low affinity to BR were analyzed using difference CD. Site-specific ligand-competition experiments with ibuprofen (marker for subdomain IIIA) and hemin (marker for subdomain IB) did not reveal any changes for the BR/SA=1/1 system and showed a decrease of the bound BR at BR/SA=3/1. Both sites were identified as sites with low affinity to BR. The correlation between stereoselectivity and the arrangement of Arg-Lys residues indicated similarity between the BR-binding sites in subdomain IIIA for all of the SAs studied. Subdomain IB in HSA, BSA, SSA and RbSA has P-stereoselectivity while in RSA it has M-selectivity toward BR. A ligand-competition experiment with gossypol shows a decrease of the CD signal of bound BR for the BR/SA=1/1 system as well as for BR/SA=3/1. Subdomain IIA was assigned as a high-affinity BR-binding site. The P-stereoselectivity of this site in HSA (and RSA, RbSA) was caused by the right-hand localization of charged residues R257/R218-R222, whereas the left-hand orientation of R257/R218-R199 led to the M-stereoselectivity of the primary binding site in BSA (and SSA). Copyright © 2013 Elsevier B.V. All rights reserved.

  12. Mapping the Anopheles gambiae Odorant Binding Protein 1 (AgamOBP1) using modeling techniques, site directed mutagenesis, circular dichroism and ligand binding assays

    Science.gov (United States)

    Rusconi, B; Maranhao, AC; Fuhrer, JP; Krotee, P; Choi, SH; Grun, F; Thireou, T; Dimitratos, SD; Woods, DF; Marinotti, O; Walter, MF; Eliopoulos, E

    2012-01-01

    The major malaria vector in Sub-Saharan Africa is the Anopheles gambiae mosquito. This species is a key target of malaria control measures. Mosquitoes find humans primarily through olfaction, yet the molecular mechanisms associated with host-seeking behavior remain largely unknown. To further understand the functionality of A. gambiae odorant binding protein 1 (AgamOBP1), we combined in silico protein structure modeling and site-directed mutagenesis to generate 16 AgamOBP1 protein analogues containing single point mutations of interest. Circular dichroism (CD) and ligand-binding assays provided data necessary to probe the effects of the point mutations on ligand binding and the overall structure of AgamOBP1. Far-UV CD spectra of mutated AgamOBP1 variants displayed both substantial decreases to ordered α-helix structure (up to 22%) and increases to disordered α-helix structure(up to 15%) with only minimal changes in random coil (unordered) structure. In mutations Y54A, Y122A and W114Q, aromatic side chain removal from the binding site significantly reduced N-phenyl-1-naphthylamine binding. Several non-aromatic mutations (L15T, L19T, L58T, L58Y, M84Q, M84K, H111A, Y122A and L124T) elicited changes to protein conformation with subsequent effects on ligand binding. This study provides empirical evidence for the in silico predicted functions of specific amino acids in AgamOBP1 folding and ligand binding characteristics. PMID:22564768

  13. Controlled cobalt doping in the spinel structure of magnetosome magnetite: new evidences from element- and site-specific X-ray magnetic circular dichroism analyses.

    Science.gov (United States)

    Li, Jinhua; Menguy, Nicolas; Arrio, Marie-Anne; Sainctavit, Philippe; Juhin, Amélie; Wang, Yinzhao; Chen, Haitao; Bunau, Oana; Otero, Edwige; Ohresser, Philippe; Pan, Yongxin

    2016-08-01

    The biomineralization of magnetite nanocrystals (called magnetosomes) by magnetotactic bacteria (MTB) has attracted intense interest in biology, geology and materials science due to the precise morphology of the particles, the chain-like assembly and their unique magnetic properties. Great efforts have been recently made in producing transition metal-doped magnetosomes with modified magnetic properties for a range of applications. Despite some successful outcomes, the coordination chemistry and magnetism of such metal-doped magnetosomes still remain largely unknown. Here, we present new evidences from X-ray magnetic circular dichroism (XMCD) for element- and site-specific magnetic analyses that cobalt is incorporated in the spinel structure of the magnetosomes within Magnetospirillum magneticum AMB-1 through the replacement of Fe(2+) ions by Co(2+) ions in octahedral (Oh) sites of magnetite. Both XMCD at Fe and Co L2,3 edges, and energy-dispersive X-ray spectroscopy on transmission electron microscopy analyses reveal a heterogeneous distribution of cobalt occurring either in different particles or inside individual particles. Compared with non-doped one, cobalt-doped magnetosome sample has lower Verwey transition temperature and larger magnetic coercivity, related to the amount of doped cobalt. This study also demonstrates that the addition of trace cobalt in the growth medium can significantly improve both the cell growth and the magnetosome formation within M. magneticum AMB-1. Together with the cobalt occupancy within the spinel structure of magnetosomes, this study indicates that MTB may provide a promising biomimetic system for producing chains of metal-doped single-domain magnetite with an appropriate tuning of the magnetic properties for technological and biomedical applications. © 2016 The Author(s).

  14. Fingerprinting the macro-organisation of pigment-protein complexes in plant thylakoid membranes in vivo by circular-dichroism spectroscopy.

    Science.gov (United States)

    Tóth, Tünde N; Rai, Neha; Solymosi, Katalin; Zsiros, Ottó; Schröder, Wolfgang P; Garab, Győző; van Amerongen, Herbert; Horton, Peter; Kovács, László

    2016-09-01

    Macro-organisation of the protein complexes in plant thylakoid membranes plays important roles in the regulation and fine-tuning of photosynthetic activity. These delicate structures might, however, undergo substantial changes during isolating the thylakoid membranes or during sample preparations, e.g., for electron microscopy. Circular-dichroism (CD) spectroscopy is a non-invasive technique which can thus be used on intact samples. Via excitonic and psi-type CD bands, respectively, it carries information on short-range excitonic pigment-pigment interactions and the macro-organisation (chiral macrodomains) of pigment-protein complexes (psi, polymer or salt-induced). In order to obtain more specific information on the origin of the major psi-type CD bands, at around (+)506, (-)674 and (+)690nm, we fingerprinted detached leaves and isolated thylakoid membranes of wild-type and mutant plants and also tested the effects of different environmental conditions in vivo. We show that (i) the chiral macrodomains disassemble upon mild detergent treatments, but not after crosslinking the protein complexes; (ii) in different wild-type leaves of dicotyledonous and monocotyledonous angiosperms the CD features are quite robust, displaying very similar excitonic and psi-type bands, suggesting similar protein composition and (macro-) organisation of photosystem II (PSII) supercomplexes in the grana; (iii) the main positive psi-type bands depend on light-harvesting protein II contents of the membranes; (iv) the (+)506nm band appears only in the presence of PSII-LHCII supercomplexes and does not depend on the xanthophyll composition of the membranes. Hence, CD spectroscopy can be used to detect different macro-domains in the thylakoid membranes with different outer antenna compositions in vivo. Copyright © 2016 Elsevier B.V. All rights reserved.

  15. Magnetic anisotropy of L 10 -ordered FePt thin films studied by Fe and Pt L2,3 -edges x-ray magnetic circular dichroism

    Science.gov (United States)

    Ikeda, K.; Seki, T.; Shibata, G.; Kadono, T.; Ishigami, K.; Takahashi, Y.; Horio, M.; Sakamoto, S.; Nonaka, Y.; Sakamaki, M.; Amemiya, K.; Kawamura, N.; Suzuki, M.; Takanashi, K.; Fujimori, A.

    2017-10-01

    The strong perpendicular magnetic anisotropy of L 10 -ordered FePt has been the subject of extensive studies for a long time. However, it is not known which element, Fe or Pt, mainly contributes to the magnetic anisotropy energy. We have investigated the anisotropy of the orbital magnetic moments of Fe 3d and Pt 5d electrons in L 10 -ordered FePt thin films by Fe and Pt L2 ,3 -edge x-ray magnetic circular dichroism (XMCD) measurements for samples with various degrees of long-range chemical order S. Fe L2 ,3 -edge XMCD showed that the orbital magnetic moment was larger when the magnetic field was applied perpendicular to the film than parallel to it and that the anisotropy of the orbital magnetic moment increased with S. Pt L2 ,3 -edge XMCD also showed that the orbital magnetic moment was smaller when the magnetic field was applied perpendicular to the film than parallel to it, opposite to the Fe L2 ,3 -edge XMCD results although the anisotropy of the orbital magnetic moment increases with S like the Fe edge. These results are qualitatively consistent with the first-principles calculation by Solovyev et al. [Phys. Rev. B 52, 13419 (1995)], which also predicts the dominant contributions of Pt 5d to the magnetic anisotropy energy rather than Fe 3d due to the strong spin-orbit coupling and the small spin splitting of the Pt 5d bands in L 10 -ordered FePt.

  16. The influence of carbon nanotubes on enzyme activity and structure: investigation of different immobilization procedures through enzyme kinetics and circular dichroism studies.

    Science.gov (United States)

    Cang-Rong, Jason Teng; Pastorin, Giorgia

    2009-06-24

    In the last decade, many environmental organizations have devoted their efforts to identifying renewable biosystems, which could provide sustainable fuels and thus enhance energy security. Amidst the myriad of possibilities, some biofuels make use of different types of waste biomasses, and enzymes are often employed to hydrolyze these biomasses and produce sugars that will be subsequently converted into ethanol. In this project, we aimed to bridge nanotechnology and biofuel production: here we report on the activity and structure of the enzyme amyloglucosidase (AMG), physically adsorbed or covalently immobilized onto single-walled carbon nanotubes (SWNTs) and multi-walled carbon nanotubes (MWNTs). In fact, carbon nanotubes (CNTs) present several properties that render them ideal support systems, without the diffusion limitations displayed by porous material and with the advantage of being further functionalizable at their surface. Chemical ligation was achieved both on oxidized nanotubes (via carbodiimide chemistry), as well as on amino-functionalized nanotubes (via periodate-oxidized AMG). Results showed that AMG retained a certain percentage of its specific activity for all enzyme-carbon nanotubes complexes prepared, with the physically adsorbed samples displaying better catalytic efficiency than the covalently immobilized samples. Analysis of the enzyme's structure through circular dichroism (CD) spectroscopy revealed significant structural changes in all samples, the degree of change being consistent with the activity profiles. This study proves that AMG interacts differently with carbon nanotubes depending on the method employed. Due to the higher activity reported by the enzyme physically adsorbed onto CNTs, these samples demonstrated a vast potential for further development. At the same time, the possibility of inducing magnetic properties into CNTs offers the opportunity to easily separate them from the original solution. Hence, substances to which they

  17. The influence of carbon nanotubes on enzyme activity and structure: investigation of different immobilization procedures through enzyme kinetics and circular dichroism studies

    Science.gov (United States)

    Cang-Rong, Jason Teng; Pastorin, Giorgia

    2009-06-01

    In the last decade, many environmental organizations have devoted their efforts to identifying renewable biosystems, which could provide sustainable fuels and thus enhance energy security. Amidst the myriad of possibilities, some biofuels make use of different types of waste biomasses, and enzymes are often employed to hydrolyze these biomasses and produce sugars that will be subsequently converted into ethanol. In this project, we aimed to bridge nanotechnology and biofuel production: here we report on the activity and structure of the enzyme amyloglucosidase (AMG), physically adsorbed or covalently immobilized onto single-walled carbon nanotubes (SWNTs) and multi-walled carbon nanotubes (MWNTs). In fact, carbon nanotubes (CNTs) present several properties that render them ideal support systems, without the diffusion limitations displayed by porous material and with the advantage of being further functionalizable at their surface. Chemical ligation was achieved both on oxidized nanotubes (via carbodiimide chemistry), as well as on amino-functionalized nanotubes (via periodate-oxidized AMG). Results showed that AMG retained a certain percentage of its specific activity for all enzyme-carbon nanotubes complexes prepared, with the physically adsorbed samples displaying better catalytic efficiency than the covalently immobilized samples. Analysis of the enzyme's structure through circular dichroism (CD) spectroscopy revealed significant structural changes in all samples, the degree of change being consistent with the activity profiles. This study proves that AMG interacts differently with carbon nanotubes depending on the method employed. Due to the higher activity reported by the enzyme physically adsorbed onto CNTs, these samples demonstrated a vast potential for further development. At the same time, the possibility of inducing magnetic properties into CNTs offers the opportunity to easily separate them from the original solution. Hence, substances to which they

  18. Vacuum Ultraviolet Radiation and Atomic Oxygen Durability Evaluation of HST Bi-Stem Thermal Shield Materials

    Science.gov (United States)

    Dever, Joyce; deGroh, Kim K.

    2002-01-01

    Bellows-type thermal shields were used on the bi-stems of replacement solar arrays installed on the Hubble Space Telescope (HST) during the first HST servicing mission (SMI) in December 1993. These thermal shields helped reduce the problem of thermal gradient- induced jitter observed with the original HST solar arrays during orbital thermal cycling and have been in use on HST for eight years. This paper describes ground testing of the candidate solar array bi-stem thermal shield materials including backside aluminized Teflon(R)FEP (fluorinated ethylene propylene) with and without atomic oxygen (AO) and ultraviolet radiation protective surface coatings for durability to AO and combined AO and vacuum ultraviolet (VOV) radiation. NASA Glenn Research Center (GRC) conducted VUV and AO exposures of samples of candidate thermal shield materials at HST operational temperatures and pre- and post-exposure analyses as part of an overall program coordinated by NASA Goddard Space Flight Center (GSFC) to determine the on-orbit durability of these materials. Coating adhesion problems were observed for samples having the AO- and combined AO/UV-protective coatings. Coating lamination occurred with rapid thermal cycling testing which simulated orbital thermal cycling. This lack of adhesion caused production of coating flakes from the material that would have posed a serious risk to HST optics if the coated materials were used for the bi-stem thermal shields. No serious degradation was observed for the uncoated aluminized Teflon(R) as evaluated by optical microscopy, although atomic force microscopy (AFM) microhardness testing revealed that an embrittled surface layer formed on the uncoated Teflon(R) surface due to vacuum ultraviolet radiation exposure. This embrittled layer was not completely removed by AO erosion, No cracks or particle flakes were produced for the embrittled uncoated material upon exposure to VUV and AO at operational temperatures to an equivalent exposure of

  19. Cell patterning using a template of microstructured organosilane layer fabricated by vacuum ultraviolet light lithography.

    Science.gov (United States)

    Yamaguchi, Munehiro; Ikeda, Koji; Suzuki, Masaaki; Kiyohara, Ai; Kudoh, Suguru N; Shimizu, Kyoko; Taira, Toshio; Ito, Daisuke; Uchida, Tsutomu; Gohara, Kazutoshi

    2011-10-18

    Micropatterning techniques have become increasingly important in cellular biology. Cell patterning is achieved by various methods. Photolithography is one of the most popular methods, and several light sources (e.g., excimer lasers and mercury lamps) are used for that purpose. Vacuum ultraviolet (VUV) light that can be produced by an excimer lamp is advantageous for fabricating material patterns, since it can decompose organic materials directly and efficiently without photoresist or photosensitive materials. Despite the advantages, applications of VUV light to pattern biological materials are few. We have investigated cell patterning by using a template of a microstructured organosilane layer fabricated by VUV lithography. We first made a template of a microstructured organosilane layer by VUV lithography. Cell adhesive materials (poly(d-lysine) and polyethyleneimine) were chemically immobilized on the organosilane template, producing a cell adhesive material pattern. Primary rat cardiac and neuronal cells were successfully patterned by culturing them on the pattern substrate. Long-term culturing was attained for up to two weeks for cardiac cells and two months for cortex cells. We have discussed the reproducibility of cell patterning and made suggestions to improve it. © 2011 American Chemical Society

  20. Oxygen isotope fractionation in the vacuum ultraviolet photodissociation of carbon monoxide: Wavelength, pressure and temperature dependency.

    Energy Technology Data Exchange (ETDEWEB)

    Chakraborty, Subrata; Davis, Ryan; Ahmed, Musahid; Jackson, Teresa L.; Thiemens, Mark H.

    2012-01-03

    Several absorption bands exist in the VUV region of Carbon monoxide (CO). Emission spectra indicate that these bands are all predissociative. An experimental investigation of CO photodissociation by vacuum ultraviolet photons (90 to 108 nm; ~13 to 11 eV) from the Advanced Light Source Synchrotron and direct measurement of the associated oxygen isotopic composition of the products are presented here. A wavelength dependency of the oxygen isotopic composition in the photodissociation product was observed. Slope values (δ'{sup 18}O/ δ'{sup 17}O) ranging from 0.76 to 1.32 were observed in oxygen three-isotope space (δ'{sup 18}O vs. δ'{sup 17}O) which correlated with increasing synchrotron photon energy, and indicate a dependency of the upper electronic state specific dissociation dynamics (e.g., perturbation and coupling associated with a particular state). An unprecedented magnitude in isotope separation was observed for photodissociation at the 105 and 107 nm synchrotron bands and are found to be associated with accidental predissociation of the vibrational states ({nu} = 0 and 1) of the upper electronic state E{sup 1}Π. For each synchrotron band, a large (few hundred per mil) extent of isotopic fractionation was observed and the range of fractionation is a combination of column density and exposure time. A significant temperature dependency in oxygen isotopic fractionation was observed, indicating a rotational level dependency in the predissociation process.

  1. Vacuum ultraviolet spectroscopy of the lowest-lying electronic state in subcritical and supercritical water.

    Science.gov (United States)

    Marin, Timothy W; Janik, Ireneusz; Bartels, David M; Chipman, Daniel M

    2017-05-17

    The nature and extent of hydrogen bonding in water has been scrutinized for decades, including how it manifests in optical properties. Here we report vacuum ultraviolet absorption spectra for the lowest-lying electronic state of subcritical and supercritical water. For subcritical water, the spectrum redshifts considerably with increasing temperature, demonstrating the gradual breakdown of the hydrogen-bond network. Tuning the density at 381 °C gives insight into the extent of hydrogen bonding in supercritical water. The known gas-phase spectrum, including its vibronic structure, is duplicated in the low-density limit. With increasing density, the spectrum blueshifts and the vibronic structure is quenched as the water monomer becomes electronically perturbed. Fits to the supercritical water spectra demonstrate consistency with dimer/trimer fractions calculated from the water virial equation of state and equilibrium constants. Using the known water dimer interaction potential, we estimate the critical distance between molecules (ca. 4.5 Å) needed to explain the vibronic structure quenching.

  2. On-line product analysis of pine wood pyrolysis using synchrotron vacuum ultraviolet photoionization mass spectrometry.

    Science.gov (United States)

    Weng, Junjie; Jia, Liangyuan; Sun, Shaobo; Wang, Yu; Tang, Xiaofeng; Zhou, Zhongyue; Qi, Fei

    2013-09-01

    The pyrolysis process of pine wood, a promising biofuel feedstock, has been studied with tunable synchrotron vacuum ultraviolet photoionization mass spectrometry. The mass spectra at different photon energies and temperatures as well as time-dependent profiles of several selected species during pine wood pyrolysis process were measured. Based on the relative contents of three lignin subunits, the data indicate that pine wood is typical of softwood. As pyrolysis temperature increased from 300 to 700 °C, some more details of pyrolysis chemistry were observed, including the decrease of oxygen content in high molecular weight species, the observation of high molecular weight products from cellulose chain and lignin polymer, and potential pyrolysis mechanisms for some key species. The formation of polycyclic aromatic hydrocarbons (PAHs) was also observed, as well as three series of pyrolysis products derived from PAHs with mass difference of 14 amu. The time-dependent profiles show that the earliest products are formed from lignin, followed by hemicellulose products, and then species from cellulose.

  3. Comparison of surface vacuum ultraviolet emissions with resonance level number densities. I. Argon plasmas

    Energy Technology Data Exchange (ETDEWEB)

    Boffard, John B., E-mail: jboffard@wisc.edu; Lin, Chun C. [Department of Physics, University of Wisconsin, Madison, WI 53706 (United States); Culver, Cody [Materials Science Program, University of Wisconsin, Madison, WI 53706 (United States); Wang, Shicong; Wendt, Amy E. [Department of Electrical and Computer Engineering, University of Wisconsin, Madison, WI 53706 (United States); Radovanov, Svetlana; Persing, Harold [Varian Semiconductor Equipment, Applied Materials Inc., Gloucester, MA 01939 (United States)

    2014-03-15

    Vacuum ultraviolet (VUV) photons emitted from excited atomic states are ubiquitous in material processing plasmas. The highly energetic photons can induce surface damage by driving surface reactions, disordering surface regions, and affecting bonds in the bulk material. In argon plasmas, the VUV emissions are due to the decay of the 1s{sub 4} and 1s{sub 2} principal resonance levels with emission wavelengths of 104.8 and 106.7 nm, respectively. The authors have measured the number densities of atoms in the two resonance levels using both white light optical absorption spectroscopy and radiation-trapping induced changes in the 3p{sup 5}4p→3p{sup 5}4s branching fractions measured via visible/near-infrared optical emission spectroscopy in an argon inductively coupled plasma as a function of both pressure and power. An emission model that takes into account radiation trapping was used to calculate the VUV emission rate. The model results were compared to experimental measurements made with a National Institute of Standards and Technology-calibrated VUV photodiode. The photodiode and model results are in generally good accord and reveal a strong dependence on the neutral gas temperature.

  4. Transformation of porous structure under vacuum ultraviolet irradiation of the films based on silicon dioxide

    Energy Technology Data Exchange (ETDEWEB)

    Dultsev, F.N., E-mail: fdultsev@isp.nsc.ru [Institute of Semiconductor Physics SB RAS, Novosibirsk 630090, Lavrentiev ave., 13 (Russian Federation); Novosibirsk State University, 630090, Novosibirsk (Russian Federation); Nekrasov, D.V. [Novosibirsk State University, 630090, Novosibirsk (Russian Federation)

    2016-03-31

    Transformation of the films with the pores of different radii under the action of vacuum ultraviolet radiation was studied experimentally and theoretically. Simulation results showed that Si–O–Si angle depends on pore size. Fourier Transform infrared spectra provide indirect confirmation of this statement. The experimental data and calculation results suggest that methyl group decreases π bonding, which causes a decrease in Si–O–Si angle. The action of ultraviolet radiation is to be considered as a photochemical reaction; the fragments formed in this reaction (CH{sub 3}{sup ⁎}, CH{sub 2}{sup ⁎}) can participate in polymerization, which leads to pore sealing. - Highlights: • Irradiation with the energy of 10–20 eV causes pore sealing. • FTIR studies and simulation results show that Si–O–Si angle depends on pore size. • Fragments formed in photochemical reaction (CH{sub 2}{sup ⁎}) can participate in polymerization. • Polymerization probability is high because the process takes place in closed space.

  5. Photochemistry of solid interstellar molecular samples exposed to vacuum-ultraviolet synchrotron radiation

    Energy Technology Data Exchange (ETDEWEB)

    Lo, Jen-Iu; Chou, Sheng-Lung; Peng, Yu-Chain; Lin, Meng-Yeh; Lu, Hsiao-Chi; Cheng, Bing-Ming, E-mail: bmcheng@nsrrc.org.tw

    2014-10-15

    Highlights: • By means of an end station attached to synchrotron, we investigate the VUV photolysis of gaseous samples condensed at 3 K. • The end station is applicable to explore the VUV photochemistry of interstellar solid molecules. • We upgraded the end station with detection of absorption of IR light and of emission of UV–vis light. • As a demonstration, we recorded simultaneously absorption spectra of photoproduct N{sub 3} and emission from VUV excited N{sub 2}. • The end station is applicable to investigate cometary mixed-ice analogs excited with VUV light from the synchrotron. - Abstract: At the vacuum-ultraviolet (VUV) beamline of the Taiwan synchrotron, an end station for photochemistry coupled to instruments to record infrared absorption spectra and ultraviolet and visible emission spectra is used to investigate the photolysis of samples of gases condensed at 3 K. This end station is applicable to explore the VUV photochemistry of interstellar molecules in solid samples. For demonstration, we discuss the response of solid dinitrogen to VUV irradiation. In the future, the upgraded photochemistry end station is applicable to investigate the cometary mixed-ice analogs excited with VUV light from the synchrotron.

  6. High-accuracy measurement of the emission spectrum of liquid xenon in the vacuum ultraviolet region

    Energy Technology Data Exchange (ETDEWEB)

    Fujii, Keiko, E-mail: fujii-keiko-nv@ynu.jp [Faculty of Engineering, Yokohama National University, Yokohama, Kanagawa 240-8501 (Japan); Endo, Yuya; Torigoe, Yui; Nakamura, Shogo [Faculty of Engineering, Yokohama National University, Yokohama, Kanagawa 240-8501 (Japan); Haruyama, Tomiyoshi; Kasami, Katsuyu [High Energy Accelerator Research Organization (KEK), Tsukuba, Ibaraki 305-0801 (Japan); Mihara, Satoshi; Saito, Kiwamu; Sasaki, Shinichi [High Energy Accelerator Research Organization (KEK), Tsukuba, Ibaraki 305-0801 (Japan); The Graduate School of Advanced Studies, Hayama, Kanagawa 240-0193 (Japan); Tawara, Hiroko [High Energy Accelerator Research Organization (KEK), Tsukuba, Ibaraki 305-0801 (Japan)

    2015-09-21

    The emission spectrum of cryogenic liquid xenon in the vacuum ultraviolet region was measured by irradiating liquid xenon with gamma-rays from a radioactive source. To achieve a high signal-to-noise ratio, we employed coincident photon counting. Additionally, the charge of the photo-sensor signals was measured to estimate the number of detected photons accurately. In addition, proper corrections were incorporated for the wavelength; response functions of the apparatus obtained using a low-pressure mercury lamp, and photon detection efficiencies of the optical system were considered. The obtained emission spectrum is found to be in the shape of a Gaussian function, with the center at 57,199±34 (stat.)±33 (syst.) cm{sup −1} (174.8±0.1 (stat.)±0.1 (syst.) nm) and the full width at half maximum of 3328±72 (stat.)±65 (syst.) cm{sup −1} (10.2±0.2 (stat.)±0.2 (sys.) nm). These results are the most accurate values obtained in terms of the data acquisition method and the calibration for the experimental system and provide valuable information regarding the high-precision instruments that employ a liquid-xenon scintillator.

  7. [Luminescence properties of thenardite activated with Dy3+ under vacuum ultraviolet excitation].

    Science.gov (United States)

    Taximaiti, Yusufu; Ajimu, Abulai; Su, Zong-Cai; Aierken, Sidike

    2011-08-01

    Na2SO4: Dy3+ phosphors were prepared by heating pure natural thenardite (Na2SO4) with DyF3 at 900 degrees C for 25 min in air studied the Luminescence properties of Na2SO4: Dy3+ were studied by synchrotron radiation. Their photoluminescence (PL) spectra were also investigated under vacuum ultraviolet-ultraviolet (VUV-UV) at room temperature. According to the emission spectra, the yellow-blue ratio (Y/B) is different under different concentrations of Dy3+ and the position of excitation. And the excitation spectrum is consisted of strong bands assigned to the 4f9-->4f8 5d transition at 172 nm, the O(2-)- Tm3+ charge transfer band at 165 nm and weak bands assigned to host absorption (138, 245 nm) and the 6 H15/2-->4D7/2, 6H15/2-->6P3/2, and 6H15/2-->6P7/2 transition at 299, 325 and 351 nm respectively.

  8. Determination of ionization energies of small silicon clusters with vacuum?ultraviolet (VUV) radiation

    Energy Technology Data Exchange (ETDEWEB)

    Kostko, Oleg; Leone, Stephen R.; Duncan, Michael A.; Ahmed, Musahid

    2009-09-23

    In this work we report on single photon vacuum ultraviolet photoionization of small silicon clusters (n=1-7) produced via laser ablation of Si. The adiabatic ionization energies (AIE) are extracted from experimental photoionization efficiency (PIE) curves with the help of Frank?Condon simulations, used to interpret the shape and onset of the PIE curves. The obtained AIEs are (all energies are in eV): Si (8.13+-0.05), Si2 (7.92+-0.05), Si3 (8.12+-0.05), Si4 (8.2+-0.1), Si5 (7.96+-0.07), Si6 (7.8+-0.1), and Si7 (7.8+-0.1). Most of the experimental AIE values are in good agreement with ab initio electronic structure calculations. To explain observed deviations between the experimental and theoretical AIEs for Si4 and Si6, a theoretical search of different isomers of these species is performed. Electronic structure calculations aid in the interpretation of the a2PIu state of Si2+ dimer in the PIE spectrum. Time dependent density functional theory (TD-DFT) calculations are performed to reveal the energies of electronically excited states in the cations for a number of Si clusters.

  9. Photoluminescence excitation spectra of lanthanide doped YAlO3 in vacuum ultraviolet region

    Science.gov (United States)

    Shimizu, Yuhei; Ueda, Kazushige; Inaguma, Yoshiyuki

    2017-04-01

    To understand luminescent mechanisms of lanthanide (Ln) doped phosphors, it is important to know the energy positions of unoccupied Ln2+ 4f and Ln3+ 5d states, as well as occupied Ln3+ 4f states, relative to the energy bands of host materials. Photoluminescence excitation (PLE) spectra of Ln doped YAlO3 were measured in a vacuum ultraviolet (VUV) region and the energy positions of Ln2+ 4f and Ln3+ 5d states in the wide-gap YAlO3 were elucidated. Peaks assignable to host lattice excitation were observed in all samples at approximately 8 eV in the PLE spectra. PLE peaks derived from charge transfer (CT) and 4f-5d transitions were observed at lower energy than the bandgap energy. Ln2+ 4f energy levels were obtained from the PLE peak energies for the CT transitions along with the valence band maximum. In contrast, Ln3+ 5d energy levels were evaluated from those for the 4f-5d transitions along with the Ln3+ 4f energy levels, which were obtained previously from X-ray photoelectron spectroscopy measurements. The elucidated Ln2+ 4f and Ln3+ 5d energy levels were exhibited in an energy diagram together with Ln3+ 4f energy levels and host energy bands. The experimental Ln2+ 4f and Ln3+ 5d energy levels were in good agreement with the reported theoretical data.

  10. Flash vacuum-ultraviolet source utilizing a surface-discharge substrate

    Science.gov (United States)

    Sagae, Michiaki; Sato, Eiichi; Shikoda, Arimitsu; Oizumi, Teiji; Hayasi, Yasuomi; Shoji, Tetsuo; Shishido, Koro; Tamakawa, Yoshiharu; Yanagisawa, Toru

    1993-01-01

    The fundamental studies for the flash vacuum-ultraviolet (VUV) source utilizing a surface- discharge substrate are described. This flash VUV source consists of the following essential components: a high-voltage power supply, a polarity-inversion-type high-voltage pulser with a condenser capacity of 14.3 nF, an oil diffusion pump, and a flash VUV chamber with a glass body. The VUV chamber employed a surface-discharge ferrite substrate that's pattern was formed by means of the copper vacuum evaporation and was connected to an oil diffusion pump with a pressure of 1.3 X 10-3 Pa. The combined ceramic condenser in the pulser was charged from 10 to 30 kV by a power supply, and the electric charges in the condenser were discharged to the radiation chamber after closing a gap switch. Then the flash VUV rays were generated. The maximum values of the cathode voltage and the tube current were about -21 kV and 1.7 kA, respectively. The VUV outputs were measured by a combination of a plastic scintillator and a photomultiplier. The pulse durations of the VUV rays were nearly equivalent to the durations of the damped oscillations of the voltage and current, and their values were about 10 microsecond(s) .

  11. Identification and deconvolution of carbohydrates with gas chromatography-vacuum ultraviolet spectroscopy.

    Science.gov (United States)

    Schenk, Jamie; Nagy, Gabe; Pohl, Nicola L B; Leghissa, Allegra; Smuts, Jonathan; Schug, Kevin A

    2017-09-01

    Methodology for qualitative and quantitative determination of carbohydrates with gas chromatography coupled to vacuum ultraviolet detection (GC-VUV) is presented. Saccharides have been intently studied and are commonly analyzed by gas chromatography-mass spectrometry (GC-MS), but not always effectively. This can be attributed to their high degree of structural complexity: α/β anomers from their axial/equatorial hydroxyl group positioning at the C1-OH and flexible ring structures that lead to the open chain, five-membered ring furanose, and six-membered ring pyranose configurations. This complexity can result in convoluted chromatograms, ambiguous fragmentation patterns and, ultimately, analyte misidentification. In this study, mono-, di, and tri-saccharides were derivatized by two different methods-permethylation and oximation/pertrimethylsilylation-and analyzed by GC-VUV. These two derivatization methods were then compared for their efficiency, ease of use, and robustness. Permethylation proved to be a useful technique for the analysis of ketopentoses and pharmaceuticals soluble in dimethyl sulfoxide (DMSO), while the oximation/pertrimethylsilylation method prevailed as the more promising, overall, derivatization method. VUV spectra have been shown to be distinct and allow for efficient differentiation of isomeric species such as ketopentoses and reducing versus non-reducing sugars. In addition to identification, pharmaceutical samples containing several compounds were derivatized and analyzed for their sugar content with the GC-VUV technique to provide data for qualitative analysis. Copyright © 2017 Elsevier B.V. All rights reserved.

  12. The vacuum ultraviolet beamline/endstations at NSRL dedicated to combustion research.

    Science.gov (United States)

    Zhou, Zhongyue; Du, Xuewei; Yang, Jiuzhong; Wang, Yizun; Li, Chaoyang; Wei, Shen; Du, Liangliang; Li, Yuyang; Qi, Fei; Wang, Qiuping

    2016-07-01

    An undulator-based vacuum ultraviolet (VUV) beamline (BL03U), intended for combustion chemistry studies, has been constructed at the National Synchrotron Radiation Laboratory (NSRL) in Hefei, China. The beamline is connected to the newly upgraded Hefei Light Source (HLS II), and could deliver photons in the 5-21 eV range, with a photon flux of 10(13) photons s(-1) at 10 eV when the beam current is 300 mA. The monochromator of the beamline is equipped with two gratings (200 lines mm(-1) and 400 lines mm(-1)) and its resolving power is 3900 at 7.3 eV for the 200 lines mm(-1) grating and 4200 at 14.6 eV for the 400 lines mm(-1) grating. The beamline serves three endstations which are designed for respective studies of premixed flame, fuel pyrolysis in flow reactor, and oxidation in jet-stirred reactor. Each endstation contains a reactor chamber, an ionization chamber where the molecular beam intersects with the VUV light, and a home-made reflectron time-of-flight mass spectrometer. The performance of the beamline and endstations with some preliminary results is presented here. The ability to detect reactive intermediates (e.g. H, O, OH and hydroperoxides) is advantageous in combustion chemistry research.

  13. Sterilization of Bacillus atrophaeus using OH radicals supplied by vacuum ultraviolet method

    Science.gov (United States)

    Yonetamari, Kenta; Tokumitsu, Yusuke; Yonemori, Seiya; Ono, Ryo; Yasuda, Hachiro; Mizuno, Akira

    2015-09-01

    Sterilization by cold plasma has widely been performed. It is well known that reactive oxygen species (ROS) has a potential of sterilization. However, it is not clear which ROS is effective on sterilization because a lot of types of ROS are produced in plasma. In this study, sterilization effect of OH radicals by vacuum ultraviolet (VUV) method was investigated. This method utilizes photodissociation reaction to produce ROS so it can produce ROS selectively. Wet and dry helium with and without 1% O2 gas was used to demonstrate sterilization effect of OH radicals. Gases were flowed in a quartz tube (inner diameter 2 mm, outer diameter 4 mm) at a flow rate of 1.5 L/min. The produced ROS flowed out of the quartz tube nozzle. A Xe2 excimer lamp emitting 172 +/- 7 nm VUV light was placed parallel to the quartz tube with a distance of 8 mm. The distance between the lower end of the lamp and the nozzle of quartz tube was changed from 3 to 15 cm. As a target of sterilization, Bacillus atrophaeus (ATCC 9372) was used. The density of OH radicals was measured using laser-induced fluorescence (LIF). As a result, sterilization using VUV method was verified. This result showed that OH radicals sterilized the bacteria.

  14. Solid state direct bonding of polymers by vacuum ultraviolet light below 160 nm

    Science.gov (United States)

    Hashimoto, Yuki; Yamamoto, Takatoki

    2017-10-01

    This work investigated the application of vacuum ultraviolet (VUV) irradiation to the bonding of various substrates, including glass, polycarbonate (PC), cyclic olefin polymer (COP), polydimethylsiloxane (PDMS) and polymethyl methacrylate (PMMA). This method has the advantage of being able to bond various substrates without the application of heat or adhesives, and therefore may be very useful in the fabrication of micro/nanoscale structures composed of polymers. In contrast to previous applications of this technique, the present study used VUV radiation at wavelengths at and below 160 nm so as to take advantage of the higher energy in this range. Bonding was assessed based on measuring the shear stress of various test specimens subjected to VUV irradiation and then pressed together, and a number of analytical methods were also employed to examine the irradiated surfaces in order to elucidate the morphological and chemical changes following VUV treatment. These analyses included water contact angle measurements, attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), time of flight secondary ion mass spectrometry (TOF-SIMS) and atomic force microscopy (AFM). Poor bonding was identified between combinations consisting of PMMA/PC, PMMA/COP, PMMA/PMMA, PMMA/glass, and PC/COP, whereas all other combinations resulted in successful bonding with the bonding stress values such as PC/PC = 2.0 MPa, PC/glass = 10.7 MPa and COP/COP = 1.7 MPa, respectively.

  15. Internal Energies of Ion-Sputtered Neutral Tryptophan and Thymine Molecules Determined by Vacuum Ultraviolet Photoionization

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, Jia; Takahashi, Lynelle; Wilson, Kevin R.; Leone, Stephen R.; Ahmed, Musahid

    2010-03-11

    Vacuum ultraviolet photoionization coupled to secondary neutral mass spectrometry (VUV-SNMS) of deposited tryptophan and thymine films are performed at the Chemical Dynamics Beamline. The resulting mass spectra show that while the intensity of the VUV-SNMS signal is lower than the corresponding secondary ion mass spectroscopy (SIMS) signal, the mass spectra are significantly simplified in VUV-SNMS. A detailed examination of tryptophan and thymine neutral molecules sputtered by 25 keV Bi3 + indicates that the ion-sputtered parent molecules have ~;;2.5 eV of internal energy. While this internal energy shifts the appearance energy of the photofragment ions for both tryptophan and thymine, it does not change the characteristic photoionizaton efficiency (PIE) curves of thymine versus photon energy. Further analysis of the mass spectral signals indicate that approximately 80 neutral thymine molecules and 400 tryptophan molecules are sputtered per incident Bi3 + ion. The simplified mass spectra and significant characteristic ion contributions to the VUV-SNMS spectra indicate the potential power of the technique for organic molecule surface analysis.

  16. Structural and biophysical insight into dual site binding of the protoberberine alkaloid palmatine to parallel G-quadruplex DNA using NMR, fluorescence and circular dichroism spectroscopy.

    Science.gov (United States)

    Padmapriya, Kumar; Barthwal, Ritu

    2018-02-20

    Plant derived small molecules, which interact with and stabilize G-quadruplex DNA, act as inhibitors of telomere elongation and oncogene expression in humans. The inhibition of telomerase enzyme has immense potential since it is over expressed in most cancer cells. Interaction of palmatine, an antitumor alkaloid, to parallel G-quadruplex DNA, [d(TTGGGGT)] 4 and [d(TTAGGGT)] 4 , has been investigated using Nuclear Magnetic Resonance (NMR), fluorescence and Circular Dichroism (CD) spectroscopy. Titrations were monitored by recording 1 H and 31 P NMR spectra and solution structure of palmatine-[d(TTGGGGT)] 4 complex was obtained by restrained Molecular Dynamics (rMD) simulations using distance restraints from 2D NOESY spectra. Thermal stabilization of DNA was determined by CD, 1 H NMR and Differential Scanning Calorimetry (DSC). Binding of palmatine induces 98% enhancement of fluorescence accompanied by blue shift ∼8 nm. CD spectral bands of DNA show minor changes. Diffusion NMR studies confirm formation of a stable complex. Proton NMR signals of palmatine shift upfield upon binding and NOE cross peaks of H10, H3, H28, 5OCH 3 protons with T2, A3/G3, G6 and T7 residues reveal dual recognition sites in both G-quadruplex DNA sequences, resulting in thermal stabilization of G-quadruplex by ∼13-17 °C. Restrained molecular dynamics simulations using NOE distance restraints for 2:1 palmatine-[d(TTGGGGT)] 4 complex reveal end-stacking of palmatine at G6pT7 step and groove binding along T2pG3 step. Binding to [d(TTAGGGT)] 4 takes place at T2pA3pG4 and G6pT7 steps. Structural features of molecular recognition of two different G-quadruplex DNA sequences by palmatine have relevance in rational drug development for anti-cancer therapy. Copyright © 2018 Elsevier B.V. and Société Française de Biochimie et Biologie Moléculaire (SFBBM). All rights reserved.

  17. Elucidating the Role of the Proximal Cysteine Hydrogen Bonding Network in Ferric Cytochrome P450cam and corresponding mutants using Magnetic Circular Dichroism Spectroscopy†

    Science.gov (United States)

    Galinato, Mary Grace I.; Spolitak, Tatyana; Ballou, David P.; Lehnert, Nicolai

    2011-01-01

    Although there has been extensive research on various Cytochrome P450s, especially Cyt P450cam, there is much to be learned about the mechanism of how its functional unit, a heme b ligated by an axial cysteine, is finely tuned for catalysis by its second coordination sphere. Here we study how the hydrogen bonding network affects the proximal cysteine and the Fe-S(Cys) bond in ferric Cyt P450cam. This is accomplished using low-temperature magnetic circular dichroism (MCD) spectroscopy on wild-type (wt) Cyt P450cam, and on the mutants Q360P (pure ferric high-spin at low temperature) and L358P with which the “Cys pocket” has been altered (by removing amino acids involved in the hydrogen bonding network), and Y96W (pure ferric low-spin). The MCD spectrum of Q360P reveals fourteen electronic transitions between 15200 and 31050 cm-1. Variable-temperature variable-field (VTVH) saturation curves were used to determine the polarizations of these electronic transitions, with respect to in-plane (xy) and out-of-plane (z) polarization relative to the heme. The polarizations, oscillator strengths, and TD-DFT calculations were then used to assign the observed electronic transitions. In the lower energy region, prominent bands at 15909 and 16919 cm-1 correspond to porphyrin (P) → Fe charge transfer (CT) transitions. The band at 17881 cm-1 has distinct sulfur S(π)→ Fe CT contributions. The Q band is observed as a pseudo A-term (derivative shape) at 18604 and 19539 cm-1. In the case of the Soret band, the negative component of the expected pseudo A-term is split into two features due to mixing with another π → π* and potentially a P → Fe CT excited state. These features are observed at 23731, 24859, and 25618 cm-1. Most importantly, the broad, prominent band at 28570 cm-1 is assigned to the S(σ)→ Fe CT transition, whose intensity is generated through a multitude of CT transitions with strong iron character. For wt, Q360P, and L358P, this band occurs at 28724

  18. Characterization of the covalent and noncovalent adducts of Agp1 phytochrome assembled with biliverdin and phycocyanobilin by circular dichroism and flash photolysis.

    Science.gov (United States)

    Borucki, Berthold; Seibeck, Sven; Heyn, Maarten P; Lamparter, Tilman

    2009-07-14

    The functional role of the covalent attachment of the bilin chromophores biliverdin (BV) and phycocyanobilin (PCB) was investigated for phytochrome Agp1 from Agrobacterium tumefaciens using circular dichroism (CD) and transient absorption spectroscopy. Covalent and noncovalent adducts with these chromophores were prepared by using wild-type (WT) Agp1 (covalent BV and noncovalent PCB binding), mutant C20A in which the covalent BV binding site is eliminated, and mutant V249C in which the covalent PCB binding site is introduced. While the CD spectra of the P(r) forms of all these photochromic adducts are qualitatively the same, the CD spectrum of the P(fr) form of the covalent PCB adduct is unique in having a positive rotational strength in the Q-band which we assign to the Z-E isomerization of the C-D methine bridge. In the three other adducts, the Q-band CD in the P(fr) state is almost zero, suggesting that upon photoconversion a negative contribution from an out-of-plane rotation of the A ring of the chromophore compensates for the positive contribution from ring D. The contribution from ring A is absent or strongly reduced in the shorter pi-conjugation system of the covalent PCB adduct. The results from CD spectroscopy are consistent with a uniform geometry of the bilin chromophore in the covalent and noncovalent adducts. Transient absorption spectroscopy showed that the spectral changes and the kinetics of the P(r) to P(fr) photoconversion are not substantially affected by the covalent attachment of BV and PCB. The kinetics in the BV and PCB adducts mainly differ in the formation of P(fr) that is accelerated by 2 orders of magnitude in the PCB adducts, whereas the sequence of spectral transitions and the associated proton transfer processes are quite similar. We conclude that the P(r) to P(fr) photoconversion in the BV and PCB adducts of Agp1 involves the same relaxation processes and is thus governed by specific protein-cofactor interactions rather than by the

  19. Extending students' practice of metacognitive regulation strategies in the undergraduate chemistry laboratory and investigation of Pb2+ binding to calmodulin with circular dichroism and molecular dynamics modeling

    Science.gov (United States)

    Valencia Navarro, Laura N.

    The following dissertation was composed of two projects in chemistry education and benchwork/computational biochemistry. The chemistry education research explored students' practice of metacognitive strategies while solving open-ended laboratory problems when engaged in an instructional environment, the Science Writing Heuristic (SWH), that was characterized as supporting metacognitive regulation strategy use. Through in-depth interviews with students, results demonstrated that students in the SWH environment, compared to non-SWH students, used metacognitive strategies to a greater degree and to a greater depth when solving open-ended laboratory problems. As students engaged in higher levels of metacognitive regulation, their elective use of peers became a prominent path for supporting the practice of metacognitive strategies. Students claimed that the structure of the SWH weekly laboratory experiments improved their ability to solve open-ended lab problems. This research not only provided a lens into students' descriptions of their regulation strategy practices in the laboratory, but it also supported that the way that a laboratory environment is arranged can affect these regulation strategy practices and their transfer to new situations. In the biochemical study on the binding of Pb2+ to calmodulin (CaM), data was acquired via circular dichroism (CD) and molecular dynamics modeling. CD signal data indicated a unique signal from Pb-CaM and a significantly smaller ratio theta208/theta222 for Pb-CaM than Ca-CaM. An analysis of secondary structure content indicated that alpha-helical structure decreased and random coil structure increased when CaM was saturated with Pb2+ compared to Ca2+ saturated CaM. A molecular dynamics simulation of Pb2+ binding to CaM showed that Pb2+ ions bound to sites outside of the known canonical binding sites including the linker region, and indicated change in secondary structure. These results support the theory of opportunistic binding

  20. Study on the interaction of phthalate esters to human serum albumin by steady-state and time-resolved fluorescence and circular dichroism spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Xie, Xiaoyun [National Key Laboratory of Organic Chemistry, Lanzhou University, Lanzhou 730000 (China); College of Earth and Environmental Sciences, Lanzhou University, Lanzhou 730000 (China); Wang, Zhaowei [College of Earth and Environmental Sciences, Lanzhou University, Lanzhou 730000 (China); Zhou, Ximin; Wang, Xiaoru [National Key Laboratory of Organic Chemistry, Lanzhou University, Lanzhou 730000 (China); Chen, Xingguo, E-mail: chenxg@lzu.edu.cn [National Key Laboratory of Organic Chemistry, Lanzhou University, Lanzhou 730000 (China); Department of Chemistry, Lanzhou University, Lanzhou 730000 (China)

    2011-09-15

    Highlights: {center_dot} Molecular docking revealed PAEs to be located in the hydrophobic pocket of HSA. {center_dot} HSA-DMP had one class of binding sites while HSA-BBP and HSA-DEHP had two types. {center_dot} Hydrophobic and hydrogen interactions dominated in the association of HSA-PAEs. {center_dot} The lifetime of Trp residue of HSA decreased after the addition of PAEs. {center_dot} The presences of PAEs could alter the second structure of HSA. - Abstract: Phthalate esters (PAEs) are globally pervasive contaminants that are considered to be endocrine disruptor chemicals and toxic environmental priority pollutants. In this paper, the interactions between PAEs and human serum albumin (HSA) were examined by molecular modelling, steady state and time-resolved fluorescence, ultraviolet-visible spectroscopy (UV-vis) and circular dichroism spectroscopy (CD). The association constants between PAEs and HSA were determined using the Stern-Volmer and Scatchard equations. The binding of dimethyl phthalate (DMP) to HSA has a single class of binding site and its binding constants (K) are 4.08 x 10{sup 3}, 3.97 x 10{sup 3}, 3.45 x 10{sup 3}, and 3.20 x 10{sup 3} L mol{sup -1} at 289, 296, 303, and 310 K, respectively. The Stern-Volmer and Scatchard plots both had two regression curves for HSA-butylbenzyl phthalate (BBP) and HSA-di-2-ethylhexyl phthalate (DEHP), which indicated that these bindings were via two types of binding sites: the numbers of binding site for the first type were lower than for the second type. The binding constants of the first type binding site were higher than those of the second type binding site at corresponding temperatures, the results suggesting that the first type of binding site had high affinity and the second binding site involved other sites with lower binding affinity and selectivity. The thermodynamic parameters of the binding reactions ({Delta}G{sup o}, {Delta}H{sup o} and {Delta}S{sup o}) were measured, and they indicated the presences

  1. Electronic structure and x-ray magnetic circular dichroism in A2CrB'O6 (A = Ca, Sr; B' = W, Re, and Os) oxides

    Science.gov (United States)

    Antonov, V. N.; Bekenov, L. V.

    2017-05-01

    A systematic electronic structure study of A2CrB'O6 (A = Ca, Sr; B' = W, Re, and Os) has been performed by employing the local spin-density approximation (LSDA) as well as the GGA and LSDA + U methods using the fully relativistic spin-polarized Dirac linear muffin-tin orbital band-structure method. We investigated the effects of the subtle interplay among the spin-orbit coupling, electron correlations, and lattice distortion on the electronic structure of the double perovskites. First principles calculations predict that Sr2CrOsO6 is (before considering spin-orbit coupling) actually a ferrimagnetic semimetal with precisely compensating spin moments, or spin-asymmetric compensated semimetallic ferrimagnet in which the electrons and holes are each fully polarized and have opposite spin directions, in spite of a zero net moment and hence no macroscopic magnetic field. Spin-orbit coupling degrades this by giving a nonzero total moment, but the band structure is little changed. Therefore, the observed saturation moment of ferrimagnetic Sr2CrOsO6 is entirely due to spin-orbit coupling. The x-ray absorption spectra and x-ray magnetic circular dichroism at the W, Re, Os, and Cr L2,3, and Cr and O K edges were investigated theoretically from first principles. A qualitative explanation of the XMCD spectra shape is provided by the analysis of the corresponding selection rules, orbital character and occupation numbers of individual orbitals. The calculated results are in good agreement with experimental data. The complex fine structure of the Cr L2,3 XAS in Sr2CrWO6 and Sr2CrReO6 was found to be not compatible with a pure Cr3+ valency state. The interpretation demands mixed valent states. We found that possible oxygen vacancies lead to a mixed valency at the Cr site, double peak structure at the Cr L2,3 edges and reduce the saturation magnetization in Sr2CrWO6 and Sr2CrReO6.

  2. Interfacial chemistry of poly(methyl methacrylate) arising from exposure to vacuum-ultraviolet light and atomic oxygen.

    Science.gov (United States)

    Yuan, Hanqiu; Killelea, Daniel R; Tepavcevic, Sanja; Kelber, Scott I; Sibener, S J

    2011-04-28

    We herein report on the chemical and physical changes that occur in thin films of poly(methyl methacrylate), PMMA, induced by exposure to high-energy vacuum ultraviolet radiation and a supersonic beam of neutral, ground electronic state O((3)P) atomic oxygen. A combination of in situ quartz crystal microbalance and in situ Fourier-transform infrared reflection-absorption spectroscopy were used to determine the photochemical reaction kinetics and mechanisms during irradiation. The surface morphological changes were measured with atomic force microscopy. The results showed there was no enhancement in the mass loss rate during simultaneous exposure of vacuum ultraviolet (VUV) radiation and atomic oxygen. Rather, the rate of mass loss was impeded when the polymer film was exposed to both reagents. This study elucidates the kinetics of photochemical and oxidative reaction for PMMA, and shows that the synergistic effect involving VUV irradiation and exposure to ground state atomic oxygen depends substantially on the relative fluxes of these reagents.

  3. High orbital angular momentum quantum numbers in the electronic ground states of Fe$_2^+$ and Co$_2^+$ as determined by x-ray absorption and x-ray magnetic circular dichroism spectroscopy

    CERN Document Server

    Zamudio-Bayer, V; Langenberg, A; Lawicki, A; Terasaki, A; Issendorff, B v; Lau, J T

    2015-01-01

    The $^6\\Delta$ electronic ground state of the Co$_2^+$ diatomic molecular cation has been assigned experimentally by x-ray absorption and x-ray magnetic circular dichroism spectroscopy in a cryogenic ion trap. Three candidates, $^6\\Phi$, $^6\\Gamma$, and $^8\\Gamma$, for the electronic ground state of Fe$_2^+$ have been identified. These states carry sizable ground-state orbital angular momenta that disagree with theoretical predictions from multireference configuration interaction and density functional theory. Our results show that the ground states of neutral and cationic diatomic molecules of $3d$ elements cannot be assumed to be connected by a one-electron process.

  4. Absolute configuration determination through the unique intramolecular excitonic coupling in the circular dichroisms of o,p'-DDT and o,p'-DDD. A combined experimental and theoretical study.

    Science.gov (United States)

    Tanaka, Hiroki; Inoue, Yoshihisa; Nakano, Takeshi; Mori, Tadashi

    2017-04-12

    Circular dichroisms (CDs) of the o,p'-isomers of 1,1,1-trichloro- and 1,1-dichloro-2,2-bis(chlorophenyl)ethanes (DDT and DDD) were investigated experimentally and theoretically. A series of strong Cotton effect peaks in a characteristic negative-negative-positive-negative, or its mirror-imaged, pattern were observed in the CD spectra of these persistent organic pollutants. The theoretical CD spectra at the SAC-CI/B95(d) and RI-CC2/def2-TZVPP levels well reproduced the experimental ones, enabling us to unambiguously assign the absolute configuration of (+)-DDT and (-)-DDD as S.

  5. Vacuum ultraviolet spectroscopy and photochemistry of zinc dihydride and related molecules in low-temperature matrices.

    Science.gov (United States)

    Henchy, Chris; Kilmartin, Una; McCaffrey, John G

    2013-09-26

    Optical absorption spectra of thin film samples, formed by the codeposition of zinc vapor with D2 and CH4, have been recorded with synchrotron radiation. With sufficiently low metal vapor flux, samples deposited at 4 K were found to consist exclusively of isolated zinc atoms for both solids. The atomic absorption bands in the quantum solids D2 and CH4 were found to exhibit large bandwidths, behavior related to the high lattice frequencies of these low mass solids. The reactivity of atomic zinc was promoted with (1)P state photolysis leading to the first recording of electronic absorption spectra for the molecules ZnD2 and CH3ZnH in the vacuum ultraviolet (VUV) region. (3)P state luminescence of atomic zinc observed in the Zn/CH4 system points to the involvement of the spin triplet state in the relaxation of CH3ZnH system as it evolves into the C3v ground state. This state is not involved in the relaxation of the higher symmetry molecule ZnD2. Time dependent density functional theory (TD-DFT) calculations were conducted to predict the electronic transitions of the inserted molecular species. Comparisons with experimental data indicate the predicted transition energies are approximately 0.5 eV less than the recorded values. Possible reasons for the discrepancy are discussed. The molecular photochemistry of ZnD2 and CH3ZnH observed in the VUV was modeled successfully with a simple four-valence electron AH2 Walsh-type diagram.

  6. Vacuum-Ultraviolet Photoionization and Mass Spectrometric Characterization of Lignin Monomers Coniferyl and Sinapyl Alcohols

    Energy Technology Data Exchange (ETDEWEB)

    Takahashi, Lynelle K.; Zhou, Jia; Kostko, Oleg; Golan, Amir; Leone, Stephen R.; Ahmed, Musahid

    2011-02-09

    The fragmentation mechanisms of monolignols under various energetic processes are studied with jet-cooled thermal desorption molecular beam (TDMB) mass spectrometry (MS), 25 keV Bi3+ secondary ion MS (SIMS), synchrotron vacuum-ultraviolet secondary neutral MS (VUV-SNMS) and theoretical methods. Experimental and calculated appearance energies of fragments observed in TDMB MS indicate that the coniferyl alcohol photoionization mass spectra contain the molecular parent and several dissociative photoionization products. Similar results obtained for sinapyl alcohol are also discussed briefly. Ionization energies of 7.60 eV ? 0.05 eV for coniferyl alcohol and<7.4 eV for both sinapyl and dihydrosinapyl alcohols are determined. The positive ion SIMS spectrum of coniferyl alcohol shares few characteristic peaks (m/z = 137 and 151) with the TDMB mass spectra, shows extensive fragmentation, and does not exhibit clear molecular parent signals. VUV-SNMS spectra, on the other hand, are dominated by the parent ion and main fragments also present in the TDMB spectra. Molecular fragmentation in VUV-SNMS spectra can be reduced by increasing the extraction delay time. Some features resembling the SIMS spectra are also observed in the desorbed neutral products. The monolignol VUV-SNMS peaks shared with the TDMB mass spectra suggest that dissociative photoionization of ion-sputtered neutral molecules predominate in the VUV-SNMS mass spectra, despite the extra internal energy imparted in the initial ion impact. The potential applications of these results to imaging mass spectrometry of bio-molecules are discussed.

  7. Comparison of direct and alternating current vacuum ultraviolet lamps in atmospheric pressure photoionization.

    Science.gov (United States)

    Vaikkinen, Anu; Haapala, Markus; Kersten, Hendrik; Benter, Thorsten; Kostiainen, Risto; Kauppila, Tiina J

    2012-02-07

    A direct current induced vacuum ultraviolet (dc-VUV) krypton discharge lamp and an alternating current, radio frequency (rf) induced VUV lamp that are essentially similar to lamps in commercial atmospheric pressure photoionization (APPI) ion sources were compared. The emission distributions along the diameter of the lamp exit window were measured, and they showed that the beam of the rf lamp is much wider than that of the dc lamp. Thus, the rf lamp has larger efficient ionization area, and it also emits more photons than the dc lamp. The ionization efficiencies of the lamps were compared using identical spray geometries with both lamps in microchip APPI mass spectrometry (μAPPI-MS) and desorption atmospheric pressure photoionization-mass spectrometry (DAPPI-MS). A comprehensive view on the ionization was gained by studying six different μAPPI solvent compositions, five DAPPI spray solvents, and completely solvent-free DAPPI. The observed reactant ions for each solvent composition were very similar with both lamps except for toluene, which showed a higher amount of solvent originating oxidation products with the rf lamp than with the dc lamp in μAPPI. Moreover, the same analyte ions were detected with both lamps, and thus, the ionization mechanisms with both lamps are similar. The rf lamp showed a higher ionization efficiency than the dc lamp in all experiments. The difference between the lamp ionization efficiencies was greatest when high ionization energy (IE) solvent compositions (IEs above 10 eV), i.e., hexane, methanol, and methanol/water, (1:1 v:v) were used. The higher ionization efficiency of the rf lamp is likely due to the larger area of high intensity light emission, and the resulting larger efficient ionization area and higher amount of photons emitted. These result in higher solvent reactant ion production, which in turn enables more efficient analyte ion production. © 2012 American Chemical Society

  8. Flash vacuum-ultraviolet generator having a mercury-anode tube

    Science.gov (United States)

    Sagae, Michiaki; Sato, Eiichi; Oizumi, Teiji; Yamamoto, Mariko; Takabe, Akihito; Sakamaki, Kimio; Ojima, Hidenori; Takayama, Kazuyoshi; Tamakawa, Yoshiharu; Yanagisawa, Toru

    1995-09-01

    The fundamental studies on a flash vacuum-ultraviolet (VUV) generator for producing water- window x rays are described. this generator consisted of the following essential components: a high-voltage power supply, a polarity-inversion-type high-voltage pulser having a 15 nF condenser, a thyristor pulser as a trigger device, a turbo molecular pump, and a VUV tube. The VUV tube employed a mercury anode, and the ferrite cathode was embedded in the anode. The pressure in the tube was primarily determined by the steam pressure of mercury as a function of temperature. The condenser in the pulser was charged from -10 to -30 kV by the power supply, and the electric charges in the condenser were discharged to the radiation tube after closing a gap switch by the thyristor pulser. As the high electron flows from the cathode electrode evaporated the anode electrode, VUV rays were then produced. The maximum output voltage from the pulser was approximately -1 times the charging voltage, and both the tube voltage and current displayed damped oscillations. The maximum values of the tube voltage and current were 14 kV and 2.0 kA, respectively. Since the effective accelerating voltage was substantially decreased by the ferrite cathode, soft x rays were easily generated. The pulse durations of the VUV rays including water-window x rays were nearly equivalent to those of the damped oscillations of the voltage and current, and their values were less than 15 microsecond(s) .

  9. Vacuum ultraviolet photon-mediated production of [18 F]F2.

    Science.gov (United States)

    Krzyczmonik, Anna; Keller, Thomas; Kirjavainen, Anna K; Forsback, Sarita; Solin, Olof

    2017-04-01

    The chemistry of F2 and its derivatives are amenable to facile aliphatic or aromatic substitution, as well as electrophilic addition. The main limitation in the use of [18 F]F2 for radiopharmaceutical synthesis is the low specific activity achieved by the traditional methods of production. The highest specific activities, 55 GBq/μmol, for [18 F]F2 have been achieved so far by using electrical discharge in the post-target production of [18 F]F2 gas from [18 F]CH3 F. We demonstrate that [18 F]F2 is produced by illuminating a gas mixture of neon/F2 /[18 F]CH3 F with vacuum ultraviolet photons generated by an excimer laser. We tested several illumination chambers and production conditions. The effects of the initial amount of [18 F]F- , amount of carrier F2 , and number of 193-nm laser pulses at constant power were evaluated regarding radiochemical yield and specific activity. The specific activity attained for [18 F]F2 -derived [18 F]NFSi was 10.3 ± 0.9 GBq/μmol, and the average radiochemical yield over a wide range of conditions was 6.7% from [18 F]F- . The production can be improved by optimization of the synthesis device and procedures. The use of a commercially available excimer laser and the simplicity of the process can make this method relatively easy for adaptation in radiochemistry laboratories. Copyright © 2017 The Authors. Journal of Labelled Compounds and Radiopharmaceuticals Published by John Wiley & Sons, Ltd.

  10. Effect of axial ligand on the binding mode of M-meso-tetrakis(N-methylpyridinium-4-yl)porphyrin to DNA probed by circular and linear dichroism spectroscopies.

    Science.gov (United States)

    Gong, Lindan; Bae, Inho; Kim, Seog K

    2012-10-18

    The binding modes of cationic porphyrins, namely M-meso-tetrakis(N-methylpyridinium-4-yl)porphyrin (MTMPyP, where M = free base, Cu(II), Ni(II), Co(III), Mn(III), V(IV)═O, and Ti(IV)═O), to native DNA were systematically investigated by polarized light spectroscopies, viz. circular and linear dichroism spectroscopy (CD and LD, respectively). At low [porphyrin]/[DNA] ratio, planar porphyrins including TMPyP, CuTMPyP, and NiTMPyP exhibited a negative CD signal in the Soret region and large negative wavelength-dependent LD(r) signal which is characteristics of their intercalative binding mode. In the intercalation pocket, the molecular plane of porphyrin is skewed to a large extent as it was judged from a large wavelength-dependency of the LD(r) magnitude in the Soret region. As the mixing ratio was increased, a bisignate CD spectrum became apparent for all of the planar porphyrins, while the shape of LD(r) remained the same, indicating the coupling of the electric transition moments of the intercalated porphyrins. Thus, coupling can occur between the porphyrins when they are separated at least two DNA base-pairs according to the nearest neighboring site exclusion model. This coupling interaction was the weakest for NiTMPyP. The porphyrins with axial ligands, namely VOTMPyP, TiOTMPyP, MnTMPyP, and CoTMPyP, bind to the exterior of the DNA at a low [porphyrin]/[DNA] ratio, which is indicated by the positive CD signal in the Soret region. The absorption and LD spectra in the Soret region were treated as the sum of two transitions to calculate the angle between each of the electric transition moments of the porphyrin, i.e., the B(x) and B(y) transitions relative to the local DNA helix axis. The angle of one of the two electric transitions of the porphyrin is in the range of 56°∼59°, whereas the other is in the range of 59°∼65°. Increasing the porphyrin density resulted in the appearance of an interaction between the bound porphyrins, which was indicated by the

  11. Electronic and magnetic properties of off-stoichiometric Co{sub 2}Mn{sub β}Si/MgO interfaces studied by x-ray magnetic circular dichroism

    Energy Technology Data Exchange (ETDEWEB)

    Singh, V. R.; Verma, V. K.; Ishigami, K.; Shibata, G.; Fujimori, A., E-mail: fujimori@wyvern.phys.s.u-tokyo.ac.jp [Department of Physics, University of Tokyo, Bunkyo-ku, Tokyo 113-0033 (Japan); Koide, T. [Photon Factory, IMSS, High Energy Accelerator Research Organization, Tsukuba, Ibaraki 305-0801 (Japan); Miura, Y.; Shirai, M. [Research Institute of Electrical Communication, Tohoku University, Katahira 2-1-1, Aoba-ku, Sendai 980-8577 (Japan); Ishikawa, T.; Li, G.-F.; Yamamoto, M. [Division of Electronics for Informatics, Hokkaido University, Sapporo 060-0814 (Japan)

    2015-05-28

    We have studied the electronic and magnetic states of Co and Mn atoms at the interface of the Co{sub 2}Mn{sub β}Si (CMS)/MgO (β = 0.69, 0.99, 1.15, and 1.29) magnetic tunnel junction (MTJ) by means of x-ray magnetic circular dichroism. In particular, the Mn composition (β) dependences of the Mn and Co magnetic moments were investigated. The experimental spin magnetic moments of Mn, m{sub spin}(Mn), derived from x-ray magnetic circular dichroism weakly decreased with increasing Mn composition β in going from Mn-deficient to Mn-rich CMS films. This behavior was explained by first-principles calculations based on the antisite-based site-specific formula unit (SSFU) composition model, which assumes the formation of only antisite defect, not vacancies, to accommodate off-stoichiometry. Furthermore, the experimental spin magnetic moments of Co, m{sub spin}(Co), also weakly decreased with increasing Mn composition. This behavior was consistently explained by the antisite-based SSFU model, in particular, by the decrease in the concentration of Co{sub Mn} antisites detrimental to the half-metallicity of CMS with increasing β. This finding is consistent with the higher tunnel magnetoresistance ratios which have been observed for CMS/MgO/CMS MTJs with Mn-rich CMS electrodes.

  12. Sulfur Isotopic Fractionation During Vacuum Ultraviolet Photolysis of SO2: Implication for Meteorites and Early Earth

    Science.gov (United States)

    Chakraborty, S.; Jackson, T. L.; Rude, B.; Ahmed, M.; Thiemens, M. H.

    2016-12-01

    Several sulfur bearing gas phase species existed in the solar nebula, including H2S, SO2, SiS, OCS, CS2, CS, NS and SO as a consequence of multiple available chemical valence states (S2- to S6+). Sulfur directly condensed into refractory phases in the solar nebula under reducing conditions. Mass independent (MI) sulfur isotopic compositions have been measured in chondrules and organics from chondritic meteorites. Large 33S excesses in sulfides from achondrite meteoritic groups have also been found suggesting that refractory sulfide minerals condensed from a nebular gas with an enhanced carbon to oxygen ratio. Photochemical reactions in the early solar nebula have been inferred to be a leading process in generating MI sulfur compositions. Previously, we have reported wavelength dependent mass-independent sulfur isotopic compositions (with a varying degree in D33S and D36S) in the product elemental sulfur during vacuum ultraviolet (VUV) photodissociation of H2S. Recently we performed photodissociation of SO2 experiments in the wavelength region 98 to 200 nm at low pressures (0.5 torr) using the VUV photons from the Advanced Light Source Synchrotron in a differentially pumped reaction chamber. To our knowledge, this is the first ever experiment to determine the isotopic fractionation in VUV photodissociation of SO2. At VUV energy region, SO2 is mostly predissociative. The measured sulfur isotopic compositions in the product elemental sulfur are MI and dependent on the wavelength. These new results support the previous finding from photodissociation of other di- and tri-atomic molecules (CO, N2, H2S) that predissociative photodissociation produces MI isotopic products and is a quantum mechanically driven selective phenomenon. These new results are useful because (i) they are important in interpreting meteoritic data and decipher sulfur chemistry in the early nebula which is indicative of the redox condition of the nebula (ii) SO2 photolysis in the atmosphere of early

  13. Selective adsorption of protein on micropatterned flexible poly(ethylene terephthalate) surfaces modified by vacuum ultraviolet lithography

    Energy Technology Data Exchange (ETDEWEB)

    Li Shaoying [School of Materials Science and Engineering, Wuhan University of Technology, 122 Luoshi Rd, Wuhan 430070 (China); Wu Zhongkui, E-mail: zkwu@whut.edu.cn [School of Materials Science and Engineering, Wuhan University of Technology, 122 Luoshi Rd, Wuhan 430070 (China); Tang Hongxiao; Yang Jun [School of Materials Science and Engineering, Wuhan University of Technology, 122 Luoshi Rd, Wuhan 430070 (China)

    2012-03-01

    Protein micropattern was fabricated on the flexible poly(ethylene terephthalate) (PET) surfaces modified by vacuum ultraviolet lithography (VUV). Chemical composition and topographies changes of the modified PET surfaces were characterized and analyzed by X-ray photoelectron spectroscopy (XPS), atomic force microscope (AFM) and static water contact angle. As demonstrated in fluorescence microscope, the protein patterns were surrounded by a protein-repellant layer of poly(ethylene glycol) (PEG) that were faithful reproductions of the copper mesh. These results suggested that this technique can be extended to other polymeric materials and will be useful in fields where arrays of protein patterns are desired.

  14. Surface Emitting, High Efficiency Near-Vacuum Ultraviolet Light Source with Aluminum Nitride Nanowires Monolithically Grown on Silicon.

    Science.gov (United States)

    Zhao, S; Djavid, M; Mi, Z

    2015-10-14

    To date, it has remained challenging to realize electrically injected light sources in the vacuum ultraviolet wavelength range (∼200 nm or shorter), which are important for a broad range of applications, including sensing, surface treatment, and photochemical analysis. In this Letter, we have demonstrated such a light source with molecular beam epitaxially grown aluminum nitride (AlN) nanowires on low cost, large area Si substrate. Detailed angle dependent electroluminescence studies suggest that, albeit the light is TM polarized, the dominant light emission direction is from the nanowire top surface, that is, along the c axis, due to the strong light scattering effect. Such an efficient surface emitting device was not previously possible using conventional c-plane AlN planar structures. The AlN nanowire LEDs exhibit an extremely large electrical efficiency (>85%), which is nearly ten times higher than the previously reported AlN planar devices. Our detailed studies further suggest that the performance of AlN nanowire LEDs is predominantly limited by electron overflow. This study provides important insight on the fundamental emission characteristics of AlN nanowire LEDs and also offers a viable path to realize an efficient surface emitting near-vacuum ultraviolet light source through direct electrical injection.

  15. Stereospecific ligands and their complexes. Part XIX. Synthesis, characterization, circular dichroism and antimicrobial activity of oxalato and malonato-(S,S)-ethylenediamine-N,N‧-di-2-(3-methyl)butanoato-chromate(III) complexes

    Science.gov (United States)

    Ilić, Dragoslav; Jevtić, Verica V.; Radojević, Ivana D.; Vasić, Sava M.; Stefanović, Olgica D.; Čomić, Ljiljana R.; Vasojević, Miorad M.; Jelić, Miodrag Ž.; Koval'chuk, Tatyana V.; Loginova, Natalia V.; Trifunović, Srećko R.

    2013-10-01

    The s-cis-[Cr(S,S-eddv)L]-complexes (1,2) (S,S-eddv = (S,S)-ethylenediamine-N,N‧-di-2-(3-methyl)butanoato ion; L = oxalate or malonate ion) were prepared. The complexes were purified by ion-exchange chromatography. The geometry of the complexes has been supposed on the basis of the infrared and electronic absorption spectra, and the absolute configurations of the isolated s-cis-[Cr(S,S-eddv)L]-complexes have been predicted on the basis of their circular dichroism (CD) spectra. Also, the results of thermal decomposition have been discussed. Antimicrobial activity of the prepared complexes (1-4) was investigated against 28 species of microorganisms. Testing was performed by microdilution method and minimum inhibitory concentrations (MIC) and minimum microbicidal concentration (MMC) have been determined. Complexes demonstrated in generally low antibacterial and antifungal activity.

  16. Itinerant ferromagnetism in the As 4p conduction band of Ba_{0.6}K_{0.4}Mn_{2}As_{2} identified by X-ray magnetic circular dichroism.

    Science.gov (United States)

    Ueland, B G; Pandey, Abhishek; Lee, Y; Sapkota, A; Choi, Y; Haskel, D; Rosenberg, R A; Lang, J C; Harmon, B N; Johnston, D C; Kreyssig, A; Goldman, A I

    2015-05-29

    X-ray magnetic circular dichroism (XMCD) measurements on single-crystal and powder samples of Ba_{0.6}K_{0.4}Mn_{2}As_{2} show that the ferromagnetism below T_{C}≈100  K arises in the As 4p conduction band. No XMCD signal is observed at the Mn x-ray absorption edges. Below T_{C}, however, a clear XMCD signal is found at the As K edge which increases with decreasing temperature. The XMCD signal is absent in data taken with the beam directed parallel to the crystallographic c axis indicating that the orbital magnetic moment lies in the basal plane of the tetragonal lattice. These results show that the previously reported itinerant ferromagnetism is associated with the As 4p conduction band and that distinct local-moment antiferromagnetism and itinerant ferromagnetism with perpendicular easy axes coexist in this compound at low temperature.

  17. Intricacies of the Co3 + spin state in Sr2Co0.5Ir0.5O4 : An x-ray absorption and magnetic circular dichroism study

    Science.gov (United States)

    Agrestini, S.; Kuo, C.-Y.; Mikhailova, D.; Chen, K.; Ohresser, P.; Pi, T. W.; Guo, H.; Komarek, A. C.; Tanaka, A.; Hu, Z.; Tjeng, L. H.

    2017-06-01

    We report on a combined soft x-ray absorption and magnetic circular dichroism (XMCD) study at the Co-L3 ,2 edge on the hybrid 3 d /5 d solid state oxide Sr2Co0.5Ir0.5O4 with K2NiF4 structure. Our data indicate unambiguously a pure high spin state (S =2 ) for the Co3 + (3 d6 ) ions with a significant unquenched orbital moment Lz/2 Sz=0.25 despite the sizable elongation of the CoO6 octahedra. Using quantitative model calculations based on parameters consistent with our spectra, we have investigated the stability of this high spin state with respect to the competing low spin and intermediate spin states.

  18. Selective protein patterning based on the micro-structured organosilane self-assembled monolayer by vacuum ultraviolet light lithography.

    Science.gov (United States)

    Lim, Sung-Hyuk; Yamaguchi, Munehiro; Nishimura, Okio; Mie, Yasuhiro; Tamura, Tomohiro; Kim, Byung-Woo; Suzuki, Masaaki

    2009-12-01

    We have succeeded to immobilize fluorescent proteins selectively using a micro-structured organosilane self-assembled monolayer as a template. An organosilane layer with amino terminal group was formed on a thermally oxidized Si wafer by liquid-phase method and then was pattern-etched by vacuum ultraviolet light (VUV). The second organosilane layer with thiol terminal group was deposited on the etched area by chemical vapor surface modification method (CVSM). These micro-structured organosilane layer containing two reactive terminal groups were chemically modified using bi-functional linkers. Two kinds of fluorescent protein, Enhanced Cyan Fluorescent Protein (ECFP) and R-phycoerythrin were selectively immobilized on the chemically modified surface.

  19. The characterization of selected drugs with infrared laser desorption/tunable synchrotron vacuum ultraviolet photoionization mass spectrometry.

    Science.gov (United States)

    Pan, Yang; Yin, Hao; Zhang, Taichang; Guo, Huijun; Sheng, Liusi; Qi, Fei

    2008-08-01

    Some selected drugs including captopril, fudosteine and racecadotril have been analyzed by infrared (IR) laser desorption/tunable synchrotron vacuum ultraviolet (VUV) photoionization mass spectrometry (PIMS). The molecular ions of captopril and racecadotril are exclusively observed without any fragments at near threshold single-photon ionization (SPI). However, fudosteine easily forms fragments even at a photon energy near the ionization threshold, indicating the instability of its molecular ion. For these drugs, a number of fragments are yielded with the increase of photon energy. The structures of such fragments proposed by IR LD/VUV PIMS are supported by electron ionization time-of-flight mass spectrometry (EI-TOFMS) results. Fragmentation pathways are discussed in detail. Copyright (c) 2008 John Wiley & Sons, Ltd.

  20. Determination of the coherence length in the vacuum-ultraviolet spectral region for the BPO4 crystal

    Science.gov (United States)

    Zhang, Xin; Wang, Guiling; Zhang, Shufeng; Zhang, Erpan; Wang, Lirong; Zhu, Yong; Wu, Yicheng; Chen, Chuangtian

    2012-03-01

    An experimental system has been set up to determine the coherence lengths of nonlinear optical crystals in the vacuum-ultraviolet (VUV) spectral region by measuring the Maker fringes in the VUV region. Using this system, the Maker fringes generated by frequency conversion from 354.7 to 177.3 nm in the BPO4 crystal were obtained and the coherence length corresponding to the nonlinear optical (NLO) coefficient d36 of the BPO4 crystal was determined to be lc(d36) = (0.785 ± 0.002) μm. To the best of our knowledge, this is the first time that the coherence length of NLO crystals in VUV was determined by experiment, and the result could be an essential parameter for designing a quasi-phase-matched BPO4 device.

  1. Ultraviolet-vacuum ultraviolet photoluminescence and x ray radioluminescence of Ce3+-doped Ba3MgSi2O8

    NARCIS (Netherlands)

    Ding, X.; Liang, H.; Hou, D.; Su, Q.; Dorenbos, P.; Sun, S.; Tao, Y.

    2011-01-01

    Ce3+-doped Ba3MgSi2O8 phosphors were prepared by a solid-state reaction route. The photoluminescence properties in the vacuum ultraviolet-vis spectral range and the x ray excited radioluminescence were investigated. Ce3+ ions were found to enter three different sites in the host lattice. Five

  2. Luminescence of Ce3+ at two different sites in ?-Sr2P2O7 under vacuum ultraviolet-UV and x-ray excitation

    NARCIS (Netherlands)

    Hou, D.; Han, B.; Chen, W.; Liang, H.; Su, Q.; Dorenbos, P.; Huang, Y.; Gao, Z.; Tao, Y.

    2010-01-01

    A series of Ce3+ doped ?-Sr2?2xCexNaxP2O7 phosphor compounds has been prepared using a high-temperature solid-state reaction technique. The luminescence properties under vacuum ultraviolet-UV and x-ray excitation were studied. Luminescence spectra reveal three UV-emitting peaks at about 310, 330,

  3. The electronic states of 1,2,3-triazole studied by vacuum ultraviolet photoabsorption and ultraviolet photoelectron spectroscopy, and a comparison with ab initio configuration interaction methods

    DEFF Research Database (Denmark)

    Palmer, Michael H.; Hoffmann, Søren Vrønning; Jones, Nykola C.

    2011-01-01

    The Rydberg states in the vacuum ultraviolet photoabsorption spectrum of 1,2,3-triazole have been measured and analyzed with the aid of comparison to the UV valence photoelectron ionizations and the results of ab initio configuration interaction (CI) calculations. Calculated electronic ionization...

  4. Calculation of parity violating effects in the 6/sup 2/P/sub 1/2/-7/sup 2/P/sub 1/2/ forbidden M1 transition in thallium. [E1 amplitude, circular dichroism, parity violation, hyperfine structure

    Energy Technology Data Exchange (ETDEWEB)

    Neuffer, D.B.

    1977-05-01

    Calculations are presented of the E1 amplitude expected in forbidden M1 transitions of Tl and Cs if parity is violated in the neutral weak e-N interaction, as proposed in a number of gauge models, including that of Weinberg and Salam. Valence electron wave functions are generated as numerical solutions to the Dirac equation in a modified Tietz central potential. These wave functions are used to calculate allowed E1 transition rates, hfs splittings, and Stark E1 transition ampitudes. These results are compared with experiment and the agreement is generally good. The relativistic Tl 6/sup 2/P/sub 1/2/-7/sup 2/P/sub 1/2/ M1 transition amplitude M is also calculated, and corrections due to interconfiguration interaction, Breit interaction, and hfs mixing are included. The parity violating E1 amplitude E/sub PV/ is calculated and a value for the circular dichroism in the Weinberg model delta = -2.6 x 10/sup -3/ is obtained. Parity violating effects in other Tl transitions are discussed. Contributions to the M1 amplitude for the forbidden Cs 6/sup 2/S/sub 1/2/-7/sup 2/S/sub 1/2/ and 6/sup 2/S/sub 1/2/-8/sup 2/S/sub 1/2/ transitions and to the Cs 6/sup 2/S/sub 1/2/ g-factor anomaly from relativistic effects, Breit interaction, interconfiguration interaction, and hfs mixing are calculated, and it is found that this current theoretical description is not entirely adequate. The parity violating E1 amplitude E/sub PV/ for the 6S/sub 1/2/-7/sup 2/S/sub 1/2/ and 6S/sub 1/2/-8/sup 2/S/sub 1/2/ transitions is evaluated. With a measured value M/sub expt/ and the Weinberg value Q/sub W/ = -99, a circular dichroism delta = 1.64 x 10/sup -4/ for the 6/sup 2/S/sub 1/2/-7/sup 2/S/sub 1/2/ transition is found.

  5. Cluster model calculation for X-ray magnetic circular dichroism at rare-earth (R) L sub 2 sub , sub 3 absorption edges in R sub 2 Fe sub 1 sub 4 B

    CERN Document Server

    Asakura, K; Harada, I; Ogasawara, H; Fukui, K; Kotani, A

    2002-01-01

    X-ray magnetic circular dichroism (MCD) at the L sub 2 sub , sub 3 absorption edges for the entire series of rare-earth (RE) elements in R sub 2 Fe sub 1 sub 4 B (R=RE) is studied based on a cluster model including 10 RE and 16 Fe atoms. The cluster model takes into account band effects of RE 5d states, to which the electric dipole transition occurs from the core 2p states, as well as spin polarization of the 5d states due to the interatomic hybridization with the spin polarized Fe 3d states. We also take into account spin and orbital polarization of the 5d states due to the 5d-4f intra-atomic exchange interaction, and the 2p to 4f quadrupole transition. The calculated results are in satisfactory agreement with experimental ones, suggesting that the cluster model calculation provides a new method to calculate quantitatively MCD spectra of RE systems with complicated atomic arrangements. (author)

  6. Measurement of the transmission magnetic circular dichroism of Ga{sub 1−x}Mn{sub x}As epilayers using a built-in p-i-n photodiode

    Energy Technology Data Exchange (ETDEWEB)

    He, Z. X.; Zheng, H. Z., E-mail: hzzheng@red.semi.ac.cn; Wang, H. L.; Zhao, J. H. [State Key Laboratory of Superlattices and Microstructures, Institute of Semiconductors, Chinese Academy of Sciences, P. O. Box 912, Beijing 100083 (China)

    2014-02-28

    By constructing a GaMnAs epilayer/semi-insulating In{sub 0.2}Ga{sub 0.8}As/(001) n{sup +}-GaAs substrate layer structure as a built-in p-i-n photodiode, we developed a scheme for on-chip measurements of transmission magnetic circular dichroism (T-MCD). Both the hysteresis loops in the magnetic field sweeps and the wavelength scans at saturated magnetic fields measured using the new T-MCD scheme, illustrated the same features as those previously measured on the freestanding GaMnAs thin films by conventional T-MCD. Because a large group of epitaxially grown magnetic film/semiconductor heterostructures, such as Fe, NiFe, CoFeAl, and MnGa films on semiconductor substrates, are becoming important new building blocks for semiconductor-based spin field-effect transistor, perpendicular magnetic tunnel junction (p-MTJ) and lateral MTJ devices, the new T-MCD scheme can be applied to tests of their magnetic properties by forming either p-i-n or Schottky photodiodes.

  7. Modified spectrophotometer for multi-dimensional circular dichroism/fluorescence data acquisition in titration experiments: application to the pH and guanidine-HCI induced unfolding of apomyoglobin.

    Science.gov (United States)

    Ramsay, G; Ionescu, R; Eftink, M R

    1995-01-01

    In a previous paper (Ramsay and Eftink, Biophys. J. 66:516-523) we reported the development of a modified spectrophotometer that can make nearly simultaneous circular dichroism (CD) and fluorescence measurements. This arrangement allows multiple data sets to be collected during a single experiment, resulting in a saving of time and material, and improved correlation between the different types of measurements. The usefulness of the instrument was shown by thermal melting experiments on several different protein systems. This CD/fluorometer spectrophotometer has been further modified by interfacing with a syringe pump and a pH meter. This arrangement allows ligand, pH, and chemical denaturation titration experiments to be performed while monitoring changes in the sample's CD, absorbance, fluorescence, and light scattering properties. Our data acquisition program also has an ability to check whether the signals have approached equilibrium before the data is recorded. For performing pH titrations we have developed a procedure which uses the signal from a pH meter in a feedback circuit in order to collect data at evenly spaced pH intervals. We demonstrate the use of this instrument with studies of the unfolding of sperm whale apomyoglobin, as induced by acid pH and by the addition of guanidine-HCI. Images FIGURE 2 PMID:8527683

  8. Low Damage Reductive Patterning of Oxidized Alkyl Self-Assembled Monolayers through Vacuum Ultraviolet Light Irradiation in an Evacuated Environment.

    Science.gov (United States)

    Soliman, Ahmed I A; Tu, Yudi; Utsunomiya, Toru; Ichii, Takashi; Sugimura, Hiroyuki

    2017-10-17

    Through 172 nm vacuum ultraviolet light irradiation in a high vacuum condition (HV-VUV), well-defined micropatterns with a varied periodic friction were fabricated at the surface of self-assembled monolayers (SAMs) terminated with oxygenated groups. No apparent height contrast between the HV-VUV-irradiated and -masked areas was observed, which indicated the stability of the C-C skeleton of the assembled molecules. The trimming of oxygenated groups occurred through dissociating the C-O bonds and promoting the occurrence of α- and β-cleavages in the C═O-containing components. Hence, the HV-VUV treatment trimmed the oxygenated groups without degrading the C-C skeleton. The HV-VUV treatment influenced the order of the assembled molecules, and the step-terrace structure was distorted. The decrease in friction at the HV-VUV-irradiated domains was attributed to the dissociation of oxygenated groups. (3-Aminopropyl)trimethoxysilane (APTMS) aggregated at the masked areas of the HV-VUV-patterned SAM, where the oxygenated groups worked as anchors. APTMS aggregations did not exist at the irradiated areas, indicating the trimming of the oxygenated groups at these areas. The direct assembling of APTMS on the Si substrate at the irradiated areas was prevented by the remaining C-C skeleton.

  9. Development of a high-speed vacuum ultraviolet (VUV) imaging system for the Experimental Advanced Superconducting Tokamak

    Science.gov (United States)

    Zhou, Fan; Ming, Tingfeng; Wang, Yumin; Wang, Zhijun; Long, Feifei; Zhuang, Qing; Li, Guoqiang; Liang, Yunfeng; Gao, Xiang

    2017-07-01

    A high-speed vacuum ultraviolet (VUV) imaging system for edge plasma studies is being developed on the Experimental Advanced Superconducting Tokamak (EAST). Its key optics is composed of an inverse type of Schwarzschild telescope made of a set of Mo/Si multilayer mirrors, a micro-channel plate (MCP) equipped with a P47 phosphor screen and a high-speed camera with CMOS sensors. In order to remove the contribution from low-energy photons, a Zr filter is installed in front of the MCP detector. With this optics, VUV photons with a wavelength of 13.5 nm, which mainly come from the line emission from intrinsic carbon (C vi: n = 4-2 transition) or the Ly-α line emission from injected Li iii on the EAST, can be selectively measured two-dimensionally with both high temporal and spatial resolutions. At present, this system is installed to view the plasma from the low field side in a horizontal port in the EAST. It has been operated routinely during the 2016 EAST experiment campaign, and the first result is shown in this work. To roughly evaluate the system performance, synthetic images are created. And it indicates that this system mainly measures the edge localized emissions by comparing the synthetic images and experimental data.

  10. Impact of plasma jet vacuum ultraviolet radiation on reactive oxygen species generation in bio-relevant liquids

    Science.gov (United States)

    Jablonowski, H.; Bussiahn, R.; Hammer, M. U.; Weltmann, K.-D.; von Woedtke, Th.; Reuter, S.

    2015-12-01

    Plasma medicine utilizes the combined interaction of plasma produced reactive components. These are reactive atoms, molecules, ions, metastable species, and radiation. Here, ultraviolet (UV, 100-400 nm) and, in particular, vacuum ultraviolet (VUV, 10-200 nm) radiation generated by an atmospheric pressure argon plasma jet were investigated regarding plasma emission, absorption in a humidified atmosphere and in solutions relevant for plasma medicine. The energy absorption was obtained for simple solutions like distilled water (dH2O) or ultrapure water and sodium chloride (NaCl) solution as well as for more complex ones, for example, Rosewell Park Memorial Institute (RPMI 1640) cell culture media. As moderate stable reactive oxygen species, hydrogen peroxide (H2O2) was studied. Highly reactive oxygen radicals, namely, superoxide anion (O2•-) and hydroxyl radicals (•OH), were investigated by the use of electron paramagnetic resonance spectroscopy. All species amounts were detected for three different treatment cases: Plasma jet generated VUV and UV radiation, plasma jet generated UV radiation without VUV part, and complete plasma jet including all reactive components additionally to VUV and UV radiation. It was found that a considerable amount of radicals are generated by the plasma generated photoemission. From the experiments, estimation on the low hazard potential of plasma generated VUV radiation is discussed.

  11. Vacuum ultraviolet trimming of oxygenated functional groups from oxidized self-assembled hexadecyl monolayers in an evacuated environment

    Science.gov (United States)

    Soliman, Ahmed I. A.; Utsunomiya, Toru; Ichii, Takashi; Sugimura, Hiroyuki

    2017-09-01

    Vacuum ultraviolet light irradiation in dry air generates active oxygen species, which have powerful oxidation abilities. These active oxygen species (O) can oxidize the alkyl moieties of polymers, and generate new oxygenated groups such as OH, CHO and COOH groups. Reducing the oxygen content in the exposure environment decreases the rate of oxidation processes. In this study, we examined the influences of the 172 nm VUV irradiation in a high vacuum (HV, < 10-3 Pa) environment on the chemical constituents, surface properties and morphological structure of well-defined VUV/(O)-modified hexadecyl (HD-) self-assembled monolayer (SAM) prepared on hydrogen-terminated silicon (H-Si) substrate. After VUV light irradiation in a HV environment (HV-VUV), the chemical constituents and surface properties were changed in two distinct stages. At short irradiation time (the first stage), the Csbnd O and COO groups decreased rapidly, while the Cdbnd O groups slightly changed. The dissociation of nonderivatizable groups (such as ether (Csbnd Osbnd C) and ester (Csbnd COOsbnd C) groups) compensated the dissociated OH, CHO, Csbnd COsbnd C and COOH groups. With further irradiation (the second stage), the quantities of the oxygenated groups slightly decreased. The carbon skeleton (Csbnd C) of SAM was scarcely dissociated during the HV-VUV treatment. These chemical changes affected the surface properties, such as wettability and morphology.

  12. STUDENT AWARD FINALIST: Study of Self-Absorbed Vacuum Ultraviolet Radiation during Pulsed Atmospheric Breakdown in Air

    Science.gov (United States)

    Laity, George; Fierro, Andrew; Hatfield, Lynn; Neuber, Andreas

    2011-10-01

    This paper describes recent experiments to investigate the role of self-produced vacuum ultraviolet (VUV) radiation in the physics of pulsed atmospheric breakdown. A unique apparatus was constructed which enables the detailed exploration of VUV light in the range 115-135 nm, which is emitted from breakdown between two point-point electrodes in an air environment at atmospheric pressure. Time-resolved diagnostics include VUV sensitive photomultipliers, intensified CCD imaging, optically isolated high voltage probes, and fast rise-time Rogowski current monitors. Temporally resolved spectroscopy from air breakdowns revealed VUV emission is released during the initial streamer phase before voltage collapse, with the majority of the emission lines identified from various atmospheric gases or surface impurities. Imaging of VUV radiation was performed which conserved the spatial emission profile, and distinct differences between nitrogen and oxygen VUV emission during onset of breakdown have been observed. Specifically, the self-absorption of HI, OI, and NI lines is addressed which elucidates the role of radiation transport during the photon-dominated streamer breakdown process. Supported by AFOSR, NASA / TSGC, DEPS, and IEEE DEIS.

  13. Effects of vacuum-ultraviolet irradiation on copper penetration into low-k dielectrics under bias-temperature stress

    Energy Technology Data Exchange (ETDEWEB)

    Guo, X.; Zheng, H.; Xue, P.; Shohet, J. L. [Plasma Processing and Technology Laboratory and Department of Electrical and Computer Engineering, University of Wisconsin-Madison, Madison, Wisconsin 53706 (United States); King, S. W. [Logic Technology Development, Intel Corporation, Hillsboro, Oregon 97124 (United States); Nishi, Y. [Department of Electrical Engineering, Stanford University, Stanford, California 94305 (United States)

    2015-01-05

    The effects of vacuum-ultraviolet (VUV) irradiation on copper penetration into non-porous low-k dielectrics under bias-temperature stress (BTS) were investigated. By employing x-ray photoelectron spectroscopy depth-profile measurements on both as-deposited and VUV-irradiated SiCOH/Cu stacks, it was found that under the same BTS conditions, the diffusion depth of Cu into the VUV-irradiated SiCOH is higher than that of as-deposited SiCOH. On the other hand, under the same temperature-annealing stress (TS) without electric bias, the Cu distribution profiles in the VUV-irradiated SiCOH were same with that for the as-deposited SiCOH. The experiments suggest that in as-deposited SiCOH, the diffused Cu exists primarily in the atomic state, while in VUV-irradiated SiCOH, the diffused Cu is oxidized by the hydroxyl ions (OH{sup −}) generated from VUV irradiation and exists in the ionic state. The mechanisms for metal diffusion and ion injection in VUV irradiated low-k dielectrics are discussed.

  14. Impact of plasma jet vacuum ultraviolet radiation on reactive oxygen species generation in bio-relevant liquids

    Energy Technology Data Exchange (ETDEWEB)

    Jablonowski, H.; Hammer, M. U.; Reuter, S. [Center for Innovation Competence plasmatis, Felix-Hausdorff-Str. 2, 17489 Greifswald (Germany); Leibniz Institute for Plasma Science and Technology, INP Greifswald e.V. Felix-Hausdorff-Str. 2, 17489 Greifswald (Germany); Bussiahn, R.; Weltmann, K.-D.; Woedtke, Th. von [Leibniz Institute for Plasma Science and Technology, INP Greifswald e.V. Felix-Hausdorff-Str. 2, 17489 Greifswald (Germany)

    2015-12-15

    Plasma medicine utilizes the combined interaction of plasma produced reactive components. These are reactive atoms, molecules, ions, metastable species, and radiation. Here, ultraviolet (UV, 100–400 nm) and, in particular, vacuum ultraviolet (VUV, 10–200 nm) radiation generated by an atmospheric pressure argon plasma jet were investigated regarding plasma emission, absorption in a humidified atmosphere and in solutions relevant for plasma medicine. The energy absorption was obtained for simple solutions like distilled water (dH{sub 2}O) or ultrapure water and sodium chloride (NaCl) solution as well as for more complex ones, for example, Rosewell Park Memorial Institute (RPMI 1640) cell culture media. As moderate stable reactive oxygen species, hydrogen peroxide (H{sub 2}O{sub 2}) was studied. Highly reactive oxygen radicals, namely, superoxide anion (O{sub 2}{sup •−}) and hydroxyl radicals ({sup •}OH), were investigated by the use of electron paramagnetic resonance spectroscopy. All species amounts were detected for three different treatment cases: Plasma jet generated VUV and UV radiation, plasma jet generated UV radiation without VUV part, and complete plasma jet including all reactive components additionally to VUV and UV radiation. It was found that a considerable amount of radicals are generated by the plasma generated photoemission. From the experiments, estimation on the low hazard potential of plasma generated VUV radiation is discussed.

  15. System for time resolved spectral studies of pulsed atmospheric discharges in the visible to vacuum ultraviolet range.

    Science.gov (United States)

    Laity, G; Neuber, A; Rogers, G; Frank, K

    2010-08-01

    Vacuum ultraviolet (VUV) emission is believed to play a major role in the development of plasma streamers in pulsed atmospheric discharges, but detection of VUV light is difficult in pulsed experiments at atmospheric pressures. Since VUV light is absorbed in most standard optical materials as well, careful attention must be given to the selection of the lens and mirror optics used in these studies. Of highest interest is the VUV emission during the initial stage of pulsed atmospheric discharges, which has a typical duration in the nanosecond regime. An experiment was designed to study this fast initial stage of VUV emission coupled with fast optical imaging of streamer propagation, both with temporal resolution on the order of nanoseconds. A repetitive solid-state high voltage pulser was constructed which produces triggered flashover discharges with low jitter and consistent pulse amplitude. VUV emission is captured utilizing both photomultiplier and intensified charge-coupled device detectors during the fast stage of streamer propagation. These results are discussed in context with the streamer formation photographed in the visible wavelength regime with 3 ns exposure time.

  16. Effects of pH on photochemical decomposition of perfluorooctanoic acid in different atmospheres by 185nm vacuum ultraviolet.

    Science.gov (United States)

    Wang, Yuan; Zhang, Pengyi

    2014-11-01

    Perfluorooctanoic acid (PFOA), a persistent organic pollutant, receives increasing concerns due to its worldwide occurrence and resistance to most conventional treatment processes. The photochemical decomposition by 185nm vacuum ultraviolet (VUV) is one of the efficient methods for PFOA decomposition. The effects of pH on PFOA decomposition in nitrogen atmosphere or oxygen atmosphere were investigated. At its original pH (4.5) of PFOA aqueous solution, PFOA decomposed efficiently both in nitrogen and in oxygen atmosphere. However, when the pH increased to 12.0, PFOA decomposition was greatly inhibited in oxygen atmosphere, while it was greatly accelerated in nitrogen atmosphere with a very short half-life time (9min). Furthermore, fluorine atoms originally contained in PFOA molecules were almost completely transformed into fluoride ions. Two decomposition pathways have been proposed to explain the PFOA decomposition under different conditions. In acidic and neutral solutions, PFOA predominantly decomposes via the direct photolysis in both atmospheres; while in the alkaline solution and in the absence of oxygen, the decomposition of PFOA is mainly induced by hydrated electrons. Copyright © 2014. Published by Elsevier B.V.

  17. Real-time radiative divertor feedback control development for the NSTX-U tokamak using a vacuum ultraviolet spectrometer

    Energy Technology Data Exchange (ETDEWEB)

    Soukhanovskii, V. A., E-mail: vlad@llnl.gov [Lawrence Livermore National Laboratory, 7000 East Ave., Livermore, California 94550 (United States); Kaita, R.; Stratton, B. [Princeton Plasma Physics Laboratory, 100 Stellarator Rd., Princeton, New Jersey 08543 (United States)

    2016-11-15

    A radiative divertor technique is planned for the NSTX-U tokamak to prevent excessive erosion and thermal damage of divertor plasma-facing components in H-mode plasma discharges with auxiliary heating up to 12 MW. In the radiative (partially detached) divertor, extrinsically seeded deuterium or impurity gases are used to increase plasma volumetric power and momentum losses. A real-time feedback control of the gas seeding rate is planned for discharges of up to 5 s duration. The outer divertor leg plasma electron temperature T{sub e} estimated spectroscopically in real time will be used as a control parameter. A vacuum ultraviolet spectrometer McPherson Model 251 with a fast charged-coupled device detector is developed for temperature monitoring between 5 and 30 eV, based on the Δn = 0, 1 line intensity ratios of carbon, nitrogen, or neon ion lines in the spectral range 300–1600 Å. A collisional-radiative model-based line intensity ratio will be used for relative calibration. A real-time T{sub e}-dependent signal within a characteristic divertor detachment equilibration time of ∼10–15 ms is expected.

  18. Real-time analysis of soot emissions from bituminous coal pyrolysis and combustion with a vacuum ultraviolet photoionization aerosol time-of-flight mass spectrometer.

    Science.gov (United States)

    Gao, Shaokai; Zhang, Yang; Meng, Junwang; Shu, Jinian

    2009-01-15

    This paper reports on-line analyses of the soot emissions from the Inner Mongolia bituminous coal combustion and pyrolysis processes with a vacuum ultraviolet photoionization aerosol time-of-flight mass spectrometer (VUV-ATOFMS). The soot particles are generated by heating a small amount of screened coal powder in synthetic air and nitrogen atmosphere in a tubular oven. The vacuum ultraviolet photoionization time-of-flight (VUV-TOF) mass spectra of the soot particles emitted from combustion and pyrolysis at different oven temperatures and different stages are obtained. The VUV-TOF mass spectra are assigned with the references of the results of the off-line GC/MS analysis.

  19. Preparation and characterization of pixelated phosphor screens for high-resolution linear imaging in the vacuum ultraviolet and x-ray ranges

    Science.gov (United States)

    Rodríguez-Barquero, L.; Zurro, B.; Martin, P.; McCarthy, K. J.; Baciero, A.

    2004-10-01

    Indirect digital imaging sensors employ tailored phosphors screens to convert incident x-ray or vacuum-ultraviolet (VUV) photons to visible light quanta A convenient method to prepare pixelated phosphor screens that can be easily tailored in thickness, type, and spatial resolution is presented. The characterization and evaluation of these screens in the laboratory is addressed and their application to high-resolution VUV and x-ray cameras is discussed.

  20. Structured near-infrared Magnetic Circular Dichroism spectra of the Mn4CaO5 cluster of PSII in T. vulcanus are dominated by Mn(IV) d-d 'spin-flip' transitions.

    Science.gov (United States)

    Morton, Jennifer; Chrysina, Maria; Craig, Vincent S J; Akita, Fusamichi; Nakajima, Yoshiki; Lubitz, Wolfgang; Cox, Nicholas; Shen, Jian-Ren; Krausz, Elmars

    2018-02-01

    Photosystem II passes through four metastable S-states in catalysing light-driven water oxidation. Variable temperature variable field (VTVH) Magnetic Circular Dichroism (MCD) spectra in PSII of Thermosynochococcus (T.) vulcanus for each S-state are reported. These spectra, along with assignments, provide a new window into the electronic and magnetic structure of Mn4CaO5. VTVH MCD spectra taken in the S2 state provide a clear g=2, S=1/2 paramagnetic characteristic, which is entirely consistent with that known by EPR. The three features, seen as positive (+) at 749nm, negative (-) at 773nm and (+) at 808nm are assigned as 4A→2E spin-flips within the d3 configuration of the Mn(IV) centres present. This assignment is supported by comparison(s) to spin-flips seen in a range of Mn(IV) materials. S3 exhibits a more intense (-) MCD peak at 764nm and has a stronger MCD saturation characteristic. This S3 MCD saturation behaviour can be accurately modelled using parameters taken directly from analyses of EPR spectra. We see no evidence for Mn(III) d-d absorption in the near-IR of any S-state. We suggest that Mn(IV)-based absorption may be responsible for the well-known near-IR induced changes induced in S2 EPR spectra of T. vulcanus and not Mn(III)-based, as has been commonly assumed. Through an analysis of the nephelauxetic effect, the excitation energy of S-state dependent spin-flips seen may help identify coordination characteristics and changes at each Mn(IV). A prospectus as to what more detailed S-state dependent MCD studies promise to achieve is outlined. Copyright © 2017 Elsevier B.V. All rights reserved.

  1. Phytochemical and Bioactive Potential of in vivo and in vitro Grown Plants of Centaurea ragusina L. - Detection of DNA/RNA Active Compounds in Plant Extracts via Thermal Denaturation and Circular Dichroism.

    Science.gov (United States)

    Vujčić, Valerija; Radić Brkanac, Sandra; Radojčić Redovniković, Ivana; Ivanković, Siniša; Stojković, Ranko; Žilić, Irena; Radić Stojković, Marijana

    2017-11-01

    The phytochemical composition and biological activity of non-volatile components of Centaurea ragusina L. has not been studied previously. Our aim was to evaluate the phytochemical and bioactive potential (including interactions with polynucleotides) of C. ragusina L. depending on the origin of plant material (in vivo - leaves from natural habitats, ex vitro - leaves from plants acclimated from culture media, in vitro - leaves and calli from plants grown in culture media) and polarity of solvents used in extract preparation (80 and 96% ethanol and water combinations or single solvents). The polyphenol composition was determined by spectrophotometric and HPLC analysis. Biological activity of extracts was evaluated by following methods: 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid) (ABTS) and 1,1-diphenyl-2-picrylhydrazyl (DPPH) methods for antioxidative activity, 2,3,5-triphenyl tetrazolium chloride (TTC) microdilution method for antibacterial activity, crystal-violet test for cytotoxic activity and thermal denaturation (TD) and circular dichroism (CD) for DNA/RNA interactions. Conditions for the most efficient polyphenol extraction were determined: the 80% ethanol/water solvent system was the most suitable for callus and leaf ex vitro samples and 80 or 96% ethanol for leaf in vivo samples. Significantly higher levels of chlorogenic acid and naringenin were detected in callus tissue than in vivo plant. Ethanolic extracts exhibited the significant antibacterial activity against Staphylococcus aureus ATCC 25923. DNA/RNA active compounds in plant extracts were detected by TD and CD methods. Callus tissue and ex vitro leaves represent a valuable source of polyphenols as in vivo leaves. TD and CD can be applied for detection of DNA/RNA active compounds in extracts from natural resources. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

  2. Circular dichroism and fluorescence spectroscopy of cysteinyl-tRNA synthetase from Halobacterium salinarum ssp. NRC-1 demonstrates that group I cations are particularly effective in providing structure and stability to this halophilic protein.

    Directory of Open Access Journals (Sweden)

    Christopher J Reed

    Full Text Available Proteins from extremophiles have the ability to fold and remain stable in their extreme environment. Here, we investigate the presence of this effect in the cysteinyl-tRNA synthetase from Halobacterium salinarum ssp. NRC-1 (NRC-1, which was used as a model halophilic protein. The effects of salt on the structure and stability of NRC-1 and of E. coli CysRS were investigated through far-UV circular dichroism (CD spectroscopy, fluorescence spectroscopy, and thermal denaturation melts. The CD of NRC-1 CysRS was examined in different group I and group II chloride salts to examine the effects of the metal ions. Potassium was observed to have the strongest effect on NRC-1 CysRS structure, with the other group I salts having reduced strength. The group II salts had little effect on the protein. This suggests that the halophilic adaptations in this protein are mediated by potassium. CD and fluorescence spectra showed structural changes taking place in NRC-1 CysRS over the concentration range of 0-3 M KCl, while the structure of E. coli CysRS was relatively unaffected. Salt was also shown to increase the thermal stability of NRC-1 CysRS since the melt temperature of the CysRS from NRC-1 was increased in the presence of high salt, whereas the E. coli enzyme showed a decrease. By characterizing these interactions, this study not only explains the stability of halophilic proteins in extremes of salt, but also helps us to understand why and how group I salts stabilize proteins in general.

  3. Iron L2,3-Edge X-ray Absorption and X-ray Magnetic Circular Dichroism Studies of Molecular Iron Complexes with Relevance to the FeMoco and FeVco Active Sites of Nitrogenase

    Science.gov (United States)

    2017-01-01

    Herein, a systematic study of a series of molecular iron model complexes has been carried out using Fe L2,3-edge X-ray absorption (XAS) and X-ray magnetic circular dichroism (XMCD) spectroscopies. This series spans iron complexes of increasing complexity, starting from ferric and ferrous tetrachlorides ([FeCl4]−/2–), to ferric and ferrous tetrathiolates ([Fe(SR)4]−/2–), to diferric and mixed-valent iron–sulfur complexes [Fe2S2R4]2–/3–. This test set of compounds is used to evaluate the sensitivity of both Fe L2,3-edge XAS and XMCD spectroscopy to oxidation state and ligation changes. It is demonstrated that the energy shift and intensity of the L2,3-edge XAS spectra depends on both the oxidation state and covalency of the system; however, the quantitative information that can be extracted from these data is limited. On the other hand, analysis of the Fe XMCD shows distinct changes in the intensity at both L3 and L2 edges, depending on the oxidation state of the system. It is also demonstrated that the XMCD intensity is modulated by the covalency of the system. For mononuclear systems, the experimental data are correlated with atomic multiplet calculations in order to provide insights into the experimental observations. Finally, XMCD is applied to the tetranuclear heterometal–iron–sulfur clusters [MFe3S4]3+/2+ (M = Mo, V), which serve as structural analogues of the FeMoco and FeVco active sites of nitrogenase. It is demonstrated that the XMCD data can be utilized to obtain information on the oxidation state distribution in complex clusters that is not readily accessible for the Fe L2,3-edge XAS data alone. The advantages of XMCD relative to standard K-edge and L2,3-edge XAS are highlighted. This study provides an important foundation for future XMCD studies on complex (bio)inorganic systems. PMID:28653855

  4. Electronic structure and magnetic properties of magnetically dead layers in epitaxial CoF e2O4/A l2O3/Si (111 ) films studied by x-ray magnetic circular dichroism

    Science.gov (United States)

    Wakabayashi, Yuki K.; Nonaka, Yosuke; Takeda, Yukiharu; Sakamoto, Shoya; Ikeda, Keisuke; Chi, Zhendong; Shibata, Goro; Tanaka, Arata; Saitoh, Yuji; Yamagami, Hiroshi; Tanaka, Masaaki; Fujimori, Atsushi; Nakane, Ryosho

    2017-09-01

    Epitaxial CoF e2O4/A l2O3 bilayers are expected to be highly efficient spin injectors into Si owing to the spin filter effect of CoF e2O4 . To exploit the full potential of this system, understanding the microscopic origin of magnetically dead layers at the CoF e2O4/A l2O3 interface is necessary. In this paper, we study the cation distribution, electronic structures, and the magnetic properties of CoF e2O4(111 ) layers with various thicknesses (thickness d =1.4 , 2.3, 4, and 11 nm) in the epitaxial CoF e2O4(111 ) /A l2O3(111 ) /Si (111 ) structures using soft x-ray absorption spectroscopy (XAS) and x-ray magnetic circular dichroism (XMCD) combined with cluster-model calculation. The magnetization of CoF e2O4 measured by XMCD gradually decreases with decreasing thickness d , and finally, a magnetically dead layer is clearly detected at d =1.4 nm . The magnetically dead layer has frustration of magnetic interactions, which is revealed from comparison between the magnetizations at 300 and 6 K. From analysis using configuration-interaction cluster-model calculation, the decrease of d leads to a decrease in the inverse-to-normal spinel structure ratio and also a decrease in the average valence of Fe at the octahedral sites. These results strongly indicate that the magnetically dead layer at the CoF e2O4/A l2O3 interface originates from various complex networks of superexchange interactions through the change in the cation distribution and electronic structure. Furthermore, from comparison of the magnetic properties between d =1.4 and 2.3 nm, it is found that the ferrimagnetic order of the magnetically dead layer at the CoF e2O4/A l2O3 interface is partially restored by increasing the thickness from d =1.4 to 2.3 nm.

  5. Analysis of the major chiral compounds of Artemisia herba-alba essential oils (EOs) using reconstructed vibrational circular dichroism (VCD) spectra: En route to a VCD chiral signature of EOs.

    Science.gov (United States)

    Said, Mohammed El-Amin; Vanloot, Pierre; Bombarda, Isabelle; Naubron, Jean-Valère; Dahmane, El Montassir; Aamouche, Ahmed; Jean, Marion; Vanthuyne, Nicolas; Dupuy, Nathalie; Roussel, Christian

    2016-01-15

    An unprecedented methodology was developed to simultaneously assign the relative percentages of the major chiral compounds and their prevailing enantiomeric form in crude essential oils (EOs). In a first step the infrared (IR) and vibrational circular dichroism (VCD) spectra of the crude essential oils were recorded and in a second step they were modelized as a linear weighted combination of the IR and VCD spectra of the individual spectra of pure enantiomer of the major chiral compounds present in the EOs. The VCD spectra of enantiomer of known enantiomeric excess shall be recorded if they are not yet available in a library of VCD spectra. For IR, the spectra of pure enantiomer or racemic mixture can be used. The full spectra modelizations were performed using a well known and powerful mathematical model (least square estimation: LSE) which resulted in a weighting of each contributing compound. For VCD modelization, the absolute value of each weighting represented the percentage of the associate compound while the attached sign addressed the correctness of the enantiomeric form used to build the model. As an example, a model built with the non-prevailing enantiomer will show a negative sign of the weighting value. For IR spectra modelization, the absolute value of each weighting represented the percentage of the compounds without of course accounting for the chirality of the prevailing enantiomers. Comparison of the weighting values issuing from IR and VCD spectra modelizations is a valuable source of information: if they are identical, the EOs are composed of nearly pure enantiomers, if they are different the chiral compounds of the EOs are not in an optically pure form. The method was applied on four samples of essential oil of Artemisia herba-alba in which the three major compounds namely (-)-α-thujone, (+)-β-thujone and (-)-camphor were found in different proportions as determined by GC-MS and chiral HPLC using polarimetric detector. In order to validate the

  6. Dichroism in spinach chloroplasts

    NARCIS (Netherlands)

    Thomas, J.B.; Lierop, J.H. van; Ham, M. ten

    1967-01-01

    In spinach chloroplasts oriented at steel-water interfaces parallel to the light beam a distinct dichroism is measured at about 680 nm. This dichroism is minimal upon addition of sucrose up to a final concentration of 0.18 M to the medium, the dichroic ratio amounting to 1.02. It is concluded that

  7. Absorption spectroscopy of xenon and ethylene-noble gas mixtures at high pressure: Towards Bose-Einstein condensation of vacuum ultraviolet photons

    CERN Document Server

    Wahl, Christian; Schmitt, Julian; Vewinger, Frank; Christopoulos, Stavros; Weitz, Martin

    2016-01-01

    Bose-Einstein condensation is a phenomenon well known for material particles as cold atomic gases, and this concept has in recent years been extended to photons confined in microscopic optical cavities. Essential for the operation of such a photon condensate is a thermalization mechanism that conserves the average particle number, as in the visible spectral regime can be realized by subsequent absorption re-emission processes in dye molecules. Here we report on the status of an experimental effort aiming at the extension of the concept of Bose-Einstein condensation of photons towards the vacuum ultraviolet spectral regime, with gases at high pressure conditions serving as a thermalization medium for the photon gas. We have recorded absorption spectra of xenon gas at up to 30 bar gas pressure of the $5p^6 - 5p^56s$ transition with a wavelength close to 147 nm. Moreover, spectra of ethylene noble gas mixtures between 155 and 180 nm wavelength are reported.

  8. 3m Vacuum Ultraviolet Spectrometer with Optical Multichannel Detector; Espectrometro de ultravioleta de vacio de 3m provisto de sistema de deteccion optical multicanal

    Energy Technology Data Exchange (ETDEWEB)

    Martin, P.; Peraza, C.; Blanco, F.; Campos, J.

    1993-07-01

    This paper describes the design and the performance of a normal incidence vacuum ultraviolet spectrometer, for the 300-2400 A spectral range. It is provided with a multichannel detection system. The monochromator is original design and it has been built at CIEMAT. It is equipped with a 3 m concave holographic grating with 2400 grooves/mm. The multichannel detector consists of a windowless double microchannel plate / phosphor screen image intensifier, coupled by fiber optic to a 1024 elements self-scanning linear photodiode array. The output from the array is digitized by a 12-bit analog to digital converter and stored in a computer, for its later analysis. The necessary software to store and display data has been developed. (Author) 18 refs.

  9. Supercontinuum generation and tunable ultrafast emission in the vacuum ultraviolet using noble-gas-filled hollow-core photonic crystal fiber

    CERN Document Server

    Ermolov, Alexey; Frosz, Michael H; Travers, John C; Russell, Philip St J

    2015-01-01

    We report on the generation of a three-octave supercontinuum extending from the vacuum ultraviolet (VUV) to the near-infrared, spanning at least 113 to 1000 nm (i.e., 11 to 1.2 eV), in He-filled hollow-core kagome-style photonic crystal fiber. The same system also permits generation of narrower-band VUV radiation tunable from 113 to 200 nm with efficiencies exceeding 1% and VUV pulse energies in excess of 50 nJ. Modeling confirms that the mechanism involves soliton self-compression to sub-femtosecond pulse durations, dispersive-wave emission and the plasma-induced soliton self-frequency blue-shift. The bandwidth of the generated VUV light, which modeling shows to be coherent, is sufficient to support 500 as single-cycle pulses.

  10. Synergistic Formation of Radicals by Irradiation with Both Vacuum Ultraviolet and Atomic Hydrogen: A Real-Time In Situ Electron Spin Resonance Study

    CERN Document Server

    Ishikawa, Kenji; Kono, Akihiko; Horibe, Hideo; Takeda, Keigo; Kondo, Hiroki; Sekine, Makoto; Hori, Masaru; 10.1021/jz2002937

    2012-01-01

    We report on the surface modification of polytetrafluoroethylene (PTFE) as an example of soft- and bio-materials that occur under plasma discharge by kinetics analysis of radical formation using in situ real-time electron spin resonance (ESR) measurements. During irradiation with hydrogen plasma, simultaneous measurements of the gas-phase ESR signals of atomic hydrogen and the carbon dangling bond (C-DB) on PTFE were performed. Dynamic changes of the C-DB density were observed in real time, where the rate of density change was accelerated during initial irradiation and then became constant over time. It is noteworthy that C-DBs were formed synergistically by irradiation with both vacuum ultraviolet (VUV) and atomic hydrogen. The in situ real-time ESR technique is useful to elucidate synergistic roles during plasma surface modification.

  11. Photoluminescence performance of thulium doped Li{sub 4}SrCa(SiO{sub 4}){sub 2} under irradiation of ultraviolet and vacuum ultraviolet lights

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Zhaofeng [Department of Science Teaching, Gansu University of Traditional Chinese Medicine, Lanzhou 730000 (China); State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000 (China); Li, Yezhou, E-mail: leelienzoey@gmail.com [Department of Science Teaching, Gansu University of Traditional Chinese Medicine, Lanzhou 730000 (China); Liu, Xiong; Wei, Xingmin; Chen, Yueling; Zhou, Fei [Department of Science Teaching, Gansu University of Traditional Chinese Medicine, Lanzhou 730000 (China); Wang, Yuhua [Department of Materials Science, School of Physical Science and Technology, Lanzhou University, Lanzhou 730000 (China)

    2014-11-15

    Highlights: • A novel blue-emitting phosphor Li{sub 4}SrCa(SiO{sub 4}){sub 2}:Tm{sup 3+} was reported. • Li{sub 4}SrCa(SiO{sub 4}){sub 2}:Tm{sup 3+} exhibited excellent thermal and irradiation stability. • Li{sub 4}SrCa(SiO{sub 4}){sub 2}:Tm{sup 3+} was found to possess high color purity. - Abstract: In this work, we synthesized Tm{sup 3+} doped Li{sub 4}SrCa(SiO{sub 4}){sub 2} phosphors and investigated their photoluminescence properties under the excitation of ultraviolet and vacuum ultraviolet lights. The crystal structure analysis and variation of cell parameters confirm that Tm{sup 3+} ions have been successfully doped in the structure of Li{sub 4}SrCa(SiO{sub 4}){sub 2} host by occupying the sites of Ca{sup 2+} with the coordination number of 6. The luminescence results suggest that Li{sub 4}SrCa(SiO{sub 4}){sub 2}:Tm{sup 3+} is a good blue-emitting phosphor when excited by ultraviolet and vacuum ultraviolet irradiations. In addition, it is observed that there is nearly no degradation for Li{sub 4}SrCa(SiO{sub 4}){sub 2}:Tm{sup 3+} after undergoing thermal and irradiation treatments. Possible mechanisms for the luminescence processes are proposed on the basis of the discussion of excitation and emission spectra. In particular, the emission color of Li{sub 4}SrCa(SiO{sub 4}){sub 2}:Tm{sup 3+} by excitation of 147 and 172 nm irradiations is very close to the standard blue color, suggesting that it could be potentially applied in plasma display panels and mercury-free fluorescence lamps.

  12. The electronic states of 1,2,4-triazoles: A study of 1H- and1-methyl-1,2,4-triazole by vacuum ultraviolet photoabsorption and ultraviolet photoelectron spectroscopy and a comparison with ab initio configuration interaction computations

    DEFF Research Database (Denmark)

    Palmer, Michael H.; Camp, Philip J.; Hoffmann, Søren Vrønning

    2012-01-01

    The first vacuum ultraviolet absorption spectrum of a 1,2,4-triazole has been obtained and analyzed in detail, with assistance from both an enhanced UV photoelectron spectroscopic study and ab initio multi-reference multi-root configuration interaction procedures. For both 1H- and 1-methyl-1,2,4-...

  13. Direct surface magnetometry with photoemission magnetic x-ray dichroism

    Energy Technology Data Exchange (ETDEWEB)

    Tobin, J.G.; Goodman, K.W. [Lawrence Berkeley National Lab., CA (United States); Schumann, F.O. [Pennsylvania State Univ., University Park, PA (United States)] [and others

    1997-04-01

    Element specific surface magnetometry remains a central goal of synchrotron radiation based studies of nanomagnetic structures. One appealing possibility is the combination of x-ray absorption dichroism measurements and the theoretical framework provided by the {open_quotes}sum rules.{close_quotes} Unfortunately, sum rule analysis are hampered by several limitations including delocalization of the final state, multi-electronic phenomena and the presence of surface dipoles. An alternative experiment, Magnetic X-Ray Dichroism in Photoelectron Spectroscopy, holds out promise based upon its elemental specificity, surface sensitivity and high resolution. Computational simulations by Tamura et al. demonstrated the relationship between exchange and spin orbit splittings and experimental data of linear and circular dichroisms. Now the authors have developed an analytical framework which allows for the direct extraction of core level exchange splittings from circular and linear dichroic photoemission data. By extending a model initially proposed by Venus, it is possible to show a linear relation between normalized dichroism peaks in the experimental data and the underlying exchange splitting. Since it is reasonable to expect that exchange splittings and magnetic moments track together, this measurement thus becomes a powerful new tool for direct surface magnetometry, without recourse to time consuming and difficult spectral simulations. The theoretical derivation will be supported by high resolution linear and circular dichroism data collected at the Spectromicroscopy Facility of the Advanced Light Source.

  14. Vacuum ultraviolet spectroscopic properties of rare earth (RE=Ce,Tb,Eu,Tm,Sm)-doped hexagonal KCaGd(PO4)2 phosphate

    Science.gov (United States)

    Zhang, Z. J.; Yuan, J. L.; Duan, C. J.; Xiong, D. B.; Chen, H. H.; Zhao, J. T.; Zhang, G. B.; Shi, C. S.

    2007-11-01

    Hexagonal KCaGd(PO4)2:RE3+ (RE =Ce,Tb,Eu,Tm,Sm) were synthesized by coprecipitation method and their vacuum ultraviolet-ultraviolet (VUV-UV) spectroscopic properties were investigated. The bands at about 165nm in the VUV excitation spectra are attributed to the host lattice absorptions. For Ce3+-doped samples, the bands at 207, 256, 275, and 320nm are assigned to the 4f-5d transitions of Ce3+ in KCaGd(PO4)2. For Tb3+-doped sample, the bands at 203 and 222nm are related to the 4f-5d spin-allowed transitions. For Eu3+-doped sample, the O2--Eu3+ charge-transfer band (CTB) at 229nm is observed, and the fine emission spectrum of Eu3+ indicates that Eu3+ ions prefer to occupy Gd3+ or Ca2+ sites in the host lattice. For Tm3+- and Sm3+-doped samples, the O2--Tm3+ and O2--Sm3+ CTBs are observed to be at 176 and 186nm, respectively. From the standpoints of the absorption band, color purity, and luminescent intensity, Tb3+-doped KCaGd(PO4)2 is a potential candidate for 172nm excited green plasma display phosphors.

  15. Thermal desorption/tunable vacuum-ultraviolet time-of-flight photoionization aerosol mass spectrometry for investigating secondary organic aerosols in chamber experiments.

    Science.gov (United States)

    Fang, Wenzheng; Gong, Lei; Shan, Xiaobin; Liu, Fuyi; Wang, Zhenya; Sheng, Liusi

    2011-12-01

    This paper describes thermal desorption/tunable vacuum-ultraviolet photoionization time-of-flight aerosol mass spectrometry (TD-VUV-TOF-PIAMS) for the real-time analysis of secondary organic aerosols (SOAs) in smog chamber experiments. SOAs are sampled directly from atmospheric pressure and are focused through an aerodynamic lens assembly into the mass spectrometer. Once the particles have entered the source region, they impact on a heater and are vaporized. The nascent vapor is then softly ionized by tunable VUV synchrotron radiation. TD-VUV-TOF-PIAMS was used in conjunction with the smog chamber to study SOA formation from the photooxidation of toluene with hydroxyl radicals. The ionization energies (IEs) of these SOA products are sometimes very different with each other. As the ideal photon source is tunable, its energy can be adjusted for each molecular to be ionized. The mass spectra obtained at different photon energies are then to be useful for molecular identification. Real-time analysis of the mass spectra of SOAs is compared with previous off-line measurements. These results illustrate the potential of TD-VUV-TOF-PIAMS for direct molecular characterization of SOAs in smog chamber experiments.

  16. Effect of the methyl substitution on the combustion of two methylheptane isomers: Flame chemistry using vacuum-ultraviolet (VUV) photoionization mass spectrometry

    KAUST Repository

    Selim, Hatem

    2015-04-16

    Alkanes with one or more methyl substitutions are commonly found in liquid transportation fuels, so a fundamental investigation of their combustion chemistry is warranted. In the present work, stoichiometric low-pressure (20 Torr) burner-stabilized flat flames of 2-methylheptane and 3-methylheptane were investigated. Flame species were measured via time-of-flight molecular-beam mass spectrometry, with vacuum-ultraviolet (VUV) synchrotron radiation as the ionization source. Mole fractions of major end-products and intermediate species (e.g., alkanes, alkenes, alkynes, aldehydes, and dienes) were quantified axially above the burner surface. Mole fractions of several free radicals were also measured (e.g., CH3, HCO, C2H3, C3H3, and C3H5). Isomers of different species were identified within the reaction pool by an energy scan between 8 and 12 eV at a distance of 2.5 mm away from the burner surface. The role of methyl substitution location on the alkane chain was determined via comparisons of similar species trends obtained from both flames. The results revealed that the change in CH3 position imposed major differences on the combustion of both fuels. Comparison with numerical simulations was performed for kinetic model testing. The results provide a comprehensive set of data about the combustion of both flames, which can enhance the erudition of both fuels combustion chemistry and also improve their chemical kinetic reaction mechanisms. © 2015 American Chemical Society.

  17. Determination of ionization energies of CnN (n=4-12): Vacuum-ultraviolet (VUV) photoionization experiments and theoretical calculations

    Energy Technology Data Exchange (ETDEWEB)

    Kostko, Oleg; Zhou, Jia; Sun, Bian Jian; Lie, Jie Shiuan; Chang, Agnes H.H.; Kaiser, Ralf I.; Ahmed, Musahid

    2010-06-10

    Results from single photon vacuum ultraviolet photoionization of astrophysically relevant CnN clusters, n = 4 - 12, in the photon energy range of 8.0 eV to 12.8 eV are presented. The experimental photoionization efficiency curves, combined with electronic structure calculations, provide improved ionization energies of the CnN species. A search through numerous nitrogen-terminated CnN isomers for n=4-9 indicates that the linear isomer has the lowest energy, and therefore should be the most abundant isomer in the molecular beam. Comparison with calculated results also shed light on the energetics of the linear CnN clusters, particularly in the trends of the even-carbon and the odd-carbon series. These results can help guide the search of potential astronomical observations of these neutral molecules together with their cations in highly ionized regions or regions with a high UV/VUV photon flux (ranging from the visible to VUV with flux maxima in the Lyman- region) in the interstellar medium.

  18. Determination of ionization energies of CnN (n=4-12): Vacuum-ultraviolet (VUV) photoionization experiments and theoretical calculations

    Energy Technology Data Exchange (ETDEWEB)

    Kostko, Oleg; Zhou, Jia; Sun, Bian Jian; Lie, Jie Shiuan; Chang, Agnes H.H.; Kaiser, Ralf I.; Ahmed, Musahid

    2010-03-02

    Results from single photon vacuum ultraviolet photoionization of astrophysically relevant CnN clusters, n = 4 - 12, in the photon energy range of 8.0 eV to 12.8 eV are presented. The experimental photoionization efficiency curves, combined with electronic structure calculations, provide improved ionization energies of the CnN species. A search through numerous nitrogen-terminated CnN isomers for n=4-9 indicates that the linear isomer has the lowest energy, and therefore should be the most abundant isomer in the molecular beam. Comparison with calculated results also shed light on the energetics of the linear CnN clusters, particularly in the trends of the even-carbon and the odd-carbon series. These results can help guide the search of potential astronomical observations of these neutral molecules together with their cations in highly ionized regions or regions with a high UV/VUV photon flux (ranging from the visible to VUV with flux maxima in the Lyman-a region) in the interstellar medium.

  19. Airfoil sampling of a pulsed Laval beam with tunable vacuum ultraviolet synchrotron ionization quadrupole mass spectrometry: application to low-temperature kinetics and product detection.

    Science.gov (United States)

    Soorkia, Satchin; Liu, Chen-Lin; Savee, John D; Ferrell, Sarah J; Leone, Stephen R; Wilson, Kevin R

    2011-12-01

    A new pulsed Laval nozzle apparatus with vacuum ultraviolet (VUV) synchrotron photoionization quadrupole mass spectrometry is constructed to study low-temperature radical-neutral chemical reactions of importance for modeling the atmosphere of Titan and the outer planets. A design for the sampling geometry of a pulsed Laval nozzle expansion has been developed that operates successfully for the determination of rate coefficients by time-resolved mass spectrometry. The new concept employs airfoil sampling of the collimated expansion with excellent sampling throughput. Time-resolved profiles of the high Mach number gas flow obtained by photoionization signals show that perturbation of the collimated expansion by the airfoil is negligible. The reaction of C(2)H with C(2)H(2) is studied at 70 K as a proof-of-principle result for both low-temperature rate coefficient measurements and product identification based on the photoionization spectrum of the reaction product versus VUV photon energy. This approach can be used to provide new insights into reaction mechanisms occurring at kinetic rates close to the collision-determined limit.

  20. Comparison of surface vacuum ultraviolet emissions with resonance level number densities. II. Rare-gas plasmas and Ar-molecular gas mixtures

    Energy Technology Data Exchange (ETDEWEB)

    Boffard, John B., E-mail: jboffard@wisc.edu; Lin, Chun C. [Department of Physics, University of Wisconsin, Madison, Wisconsin 53706 (United States); Wang, Shicong; Wendt, Amy E. [Department of Electrical and Computer Engineering, University of Wisconsin, Madison, Wisconsin 53706 (United States); Culver, Cody [Materials Science Program, University of Wisconsin, Madison, Wisconsin 53706 (United States); Radovanov, Svetlana; Persing, Harold [Applied Materials Inc., Gloucester, Massachusetts 01939 (United States)

    2015-03-15

    Vacuum ultraviolet (VUV) emissions from excited plasma species can play a variety of roles in processing plasmas, including damaging the surface properties of materials used in semiconductor processing. Depending on their wavelength, VUV photons can easily transmit thin upper dielectric layers and affect the electrical characteristics of the devices. Despite their importance, measuring VUV fluxes is complicated by the fact that few materials transmit at VUV wavelengths, and both detectors and windows are easily damaged by plasma exposure. The authors have previously reported on measuring VUV fluxes in pure argon plasmas by monitoring the concentrations of Ar(3p{sup 5}4s) resonance atoms that produce the VUV emissions using noninvasive optical emission spectroscopy in the visible/near-infrared wavelength range [Boffard et al., J. Vac. Sci. Technol., A 32, 021304 (2014)]. Here, the authors extend this technique to other rare-gases (Ne, Kr, and Xe) and argon-molecular gas plasmas (Ar/H{sub 2}, Ar/O{sub 2}, and Ar/N{sub 2}). Results of a model for VUV emissions that couples radiation trapping and the measured rare-gas resonance level densities are compared to measurements made with both a calibrated VUV photodiode and a sodium salicylate fluorescence detection scheme. In these more complicated gas mixtures, VUV emissions from a variety of sources beyond the principal resonance levels of the rare gases are found to contribute to the total VUV flux.

  1. Vacuum ultraviolet emission spectrum measurement of a microwave-discharge hydrogen-flow lamp in several configurations: Application to photodesorption of CO ice

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Y.-J.; Wu, C.-Y. R. [Space Sciences Center and Department of Physics and Astronomy, University of Southern California, Los Angeles, CA 90089-1341 (United States); Chuang, K.-J.; Chu, C.-C.; Yih, T.-S. [Department of Physics, National Central University, Jhongli City, Taoyuan County 32054, Taiwan (China); Muñoz Caro, G. M. [Centro de Astrobiología, INTA-CSIC, Torrejón de Ardoz, E-28850 Madrid (Spain); Nuevo, M. [NASA Ames Research Center, Moffett Field, CA 94035 (United States); Ip, W.-H., E-mail: yujung@usc.edu [Graduate Institute of Astronomy, National Central University, Jhongli City, Taoyuan County 32049, Taiwan (China)

    2014-01-20

    We report measurements of the vacuum ultraviolet (VUV) emission spectra of a microwave-discharge hydrogen-flow lamp (MDHL), a common tool in astrochemistry laboratories working on ice VUV photoprocessing. The MDHL provides hydrogen Ly-α (121.6 nm) and H{sub 2} molecular emission in the 110-180 nm range. We show that the spectral characteristics of the VUV light emitted in this range, in particular the relative proportion of Ly-α to molecular emission bands, strongly depend on the pressure of H{sub 2} inside the lamp, the lamp geometry (F type versus T type), the gas used (pure H{sub 2} versus H{sub 2} seeded in He), and the optical properties of the window used (MgF{sub 2} versus CaF{sub 2}). These different configurations are used to study the VUV irradiation of CO ice at 14 K. In contrast to the majority of studies dedicated to the VUV irradiation of astrophysical ice analogs, which have not taken into consideration the emission spectrum of the MDHL, our results show that the processes induced by photons in CO ice from a broad energy range are different and more complex than the sum of individual processes induced by monochromatic sources spanning the same energy range, as a result of the existence of multistate electronic transitions and discrepancy in absorption cross sections between parent molecules and products in the Ly-α and H{sub 2} molecular emission ranges.

  2. Versatile high-repetition-rate phase-locked chopper system for fast timing experiments in the vacuum ultraviolet and x-ray spectral region.

    Science.gov (United States)

    Plogmaker, Stefan; Linusson, Per; Eland, John H D; Baker, Neville; Johansson, Erik M J; Rensmo, Håkan; Feifel, Raimund; Siegbahn, Hans

    2012-01-01

    A novel light chopper system for fast timing experiments in the vacuum-ultraviolet (VUV) and x-ray spectral region has been developed. It can be phase-locked and synchronized with a synchrotron radiation storage ring, accommodating repetition rates in the range of ~8 to ~120 kHz by choosing different sets of apertures and subharmonics of the ring frequency (MHz range). Also the opening time of the system can be varied from some nanoseconds to several microseconds to meet the needs of a broad range of applications. Adjusting these parameters, the device can be used either for the generation of single light pulses or pulse packages from a microwave driven, continuous He gas discharge lamp or from storage rings which are otherwise often considered as quasi-continuous light sources. This chopper can be utilized for many different kinds of experiments enabling, for example, unambiguous time-of-flight (TOF) multi-electron coincidence studies of atoms and molecules excited by a single light pulse as well as time-resolved visible laser pump x-ray probe electron spectroscopy of condensed matter in the valence and core level region.

  3. Versatile high-repetition-rate phase-locked chopper system for fast timing experiments in the vacuum ultraviolet and x-ray spectral region

    Energy Technology Data Exchange (ETDEWEB)

    Plogmaker, Stefan; Johansson, Erik M. J.; Rensmo, Haakan; Feifel, Raimund; Siegbahn, Hans [Department of Physics and Astronomy, Uppsala University, Box 516, SE-751 20 Uppsala (Sweden); Linusson, Per [Department of Physics, Stockholm University, AlbaNova University Center, SE-106 91 Stockholm (Sweden); Eland, John H. D. [Department of Physics and Astronomy, Uppsala University, Box 516, SE-751 20 Uppsala (Sweden); Department of Chemistry, Physical and Theoretical Chemistry Laboratory, Oxford University, South Parks Road, Oxford OX1 3QZ (United Kingdom); Baker, Neville [Department of Chemistry, Physical and Theoretical Chemistry Laboratory, Oxford University, South Parks Road, Oxford OX1 3QZ (United Kingdom)

    2012-01-15

    A novel light chopper system for fast timing experiments in the vacuum-ultraviolet (VUV) and x-ray spectral region has been developed. It can be phase-locked and synchronized with a synchrotron radiation storage ring, accommodating repetition rates in the range of {approx}8 to {approx}120 kHz by choosing different sets of apertures and subharmonics of the ring frequency (MHz range). Also the opening time of the system can be varied from some nanoseconds to several microseconds to meet the needs of a broad range of applications. Adjusting these parameters, the device can be used either for the generation of single light pulses or pulse packages from a microwave driven, continuous He gas discharge lamp or from storage rings which are otherwise often considered as quasi-continuous light sources. This chopper can be utilized for many different kinds of experiments enabling, for example, unambiguous time-of-flight (TOF) multi-electron coincidence studies of atoms and molecules excited by a single light pulse as well as time-resolved visible laser pump x-ray probe electron spectroscopy of condensed matter in the valence and core level region.

  4. Single photon ionization and chemical ionization combined ion source based on a vacuum ultraviolet lamp for orthogonal acceleration time-of-flight mass spectrometry.

    Science.gov (United States)

    Hua, Lei; Wu, Qinghao; Hou, Keyong; Cui, Huapeng; Chen, Ping; Wang, Weiguo; Li, Jinghua; Li, Haiyang

    2011-07-01

    A novel combined ion source based on a vacuum ultraviolet (VUV) lamp with both single photon ionization (SPI) and chemical ionization (CI) capabilities has been developed for an orthogonal acceleration time-of-flight mass spectrometer (oaTOFMS). The SPI was accomplished using a commercial 10.6 eV krypton discharge lamp with a photon flux of about 10(11) photons s(-1), while the CI was achieved through ion-molecule reactions with O(2)(+) reactant ions generated by photoelectron ionization at medium vacuum pressure (MVP). To achieve high ionization efficiency, the ion source pressure was elevated to 0.3 mbar and the photoionization length was extended to 36 mm. As a result, limits of detection (LODs) down to 3, 4, and 6 ppbv were obtained for benzene, toluene, and p-xylene in MVP-SPI mode, and values of 8 and 10 ppbv were obtained for toluene and chloroform, respectively, in SPI-CI mode. As it is feasible to switch between MVP-SPI mode and SPI-CI mode rapidly, this system is capable of monitoring complex organic mixtures with a wide range of ionization energies (IEs). The analytical capacity of this system was demonstrated by measuring dehydrogenation products of long-chain paraffins to olefins through direct capillary sampling and drinking water disinfection byproducts from chlorine through a membrane interface.

  5. A new membrane inlet interface of a vacuum ultraviolet lamp ionization miniature mass spectrometer for on-line rapid measurement of volatile organic compounds in air.

    Science.gov (United States)

    Hou, Keyong; Wang, Junde; Li, Haiyang

    2007-01-01

    A novel membrane inlet interface coupled to a single-photon ionization (SPI) miniature time-of-flight mass spectrometer has been developed for on-line rapid measurement of volatile organic compounds (VOCs). The vacuum ultraviolet (VUV) light source for SPI was a commercial krypton discharge lamp with photon energy of 10.6 eV and photon flux of 10(10) photons/s. The experimental results showed that the sensitivity was 5 times as high as obtained with the traditional membrane inlet. The enrichment efficiency could be adjusted in the range of 10 to 20 times for different VOCs when a buffer cell was added to the inlet interface, and the memory effect was effectively eliminated. A detection limit as low as 25 parts-per-billion by volume (ppbv) for benzene has been achieved, with a linear dynamic range of three orders of magnitude. The rise times were 6 s, 10 s and 15 s for benzene, toluene and p-xylene, respectively, and the fall time was only 6 s for all of these compounds. The analytical capacity of this system was demonstrated by the on-line analysis of VOCs in single puff mainstream cigarette smoke, in which more than 50 compounds were detected in 2 s. Copyright 2007 John Wiley & Sons, Ltd.

  6. A straightforward method for Vacuum-Ultraviolet flux measurements: The case of the hydrogen discharge lamp and implications for solid-phase actinometry

    Energy Technology Data Exchange (ETDEWEB)

    Fulvio, D., E-mail: daniele.fulvio@uni-jena.de, E-mail: dfu@oact.inaf.it; Brieva, A. C.; Jäger, C. [Laboratory Astrophysics Group of the Max Planck Institute for Astronomy at the Friedrich Schiller University Jena, Institute of Solid State Physics, Helmholtzweg 3, D-07743 Jena (Germany); Cuylle, S. H.; Linnartz, H. [Raymond and Beverly Sackler Laboratory for Astrophysics, Leiden Observatory, Leiden University, P.O. box 9513, 2300 RA Leiden (Netherlands); Henning, T. [Max Planck Institute for Astronomy, Königstuhl 17, D-69117 Heidelberg (Germany)

    2014-07-07

    Vacuum-Ultraviolet (VUV) radiation is responsible for the photo-processing of simple and complex molecules in several terrestrial and extraterrestrial environments. In the laboratory such radiation is commonly simulated by inexpensive and easy-to-use microwave-powered hydrogen discharge lamps. However, VUV flux measurements are not trivial and the methods/devices typically used for this purpose, mainly actinometry and calibrated VUV silicon photodiodes, are not very accurate or expensive and lack of general suitability to experimental setups. Here, we present a straightforward method for measuring the VUV photon flux based on the photoelectric effect and using a gold photodetector. This method is easily applicable to most experimental setups, bypasses the major problems of the other methods, and provides reliable flux measurements. As a case study, the method is applied to a microwave-powered hydrogen discharge lamp. In addition, the comparison of these flux measurements to those obtained by O{sub 2} actinometry experiments allow us to estimate the quantum yield (QY) values QY{sub 122} = 0.44 ± 0.16 and QY{sub 160} = 0.87 ± 0.30 for solid-phase O{sub 2} actinometry.

  7. Linear and Chiral Dichroism in the Electron Microscope

    CERN Document Server

    Schattschneider, Peter

    2012-01-01

    The growing interest in the miniaturization of magnetic storage media and the quest for novel spintronics applications rely on element specific detection of spin and orbital magnetic moments in a solid. The most sophisticated technique to reach this aim has been XMCD (X-ray magnetic circular dichroism), largely used in synchrotron beam lines. The spatial resolution limit of this technique is of the order of 20 - 50 nm. This poses a sensible limit for the study of nanostructured devices. This book describes EMCD (energy loss magnetic chiral dichroism), a phenomenon in energy loss spectroscopy d

  8. Vacuum ultraviolet excited luminescence properties of sol–gel derived GdP{sub 5}O{sub 14}:Eu{sup 3+} powders

    Energy Technology Data Exchange (ETDEWEB)

    Mbarek, Aïcha [Clermont Université, Université Blaise Pascal, Institut de Chimie de Clermont-Ferrand, BP 10448, F-63000 CLERMONT-FERRAND (France); Laboratoire de Chimie Industrielle, Ecole Nationale d' Ingénieurs de Sfax, Université de Sfax, BP W 3038, Sfax (Tunisia); Chadeyron, Geneviève, E-mail: genevieve.chadeyron@ensccf.fr [Clermont Université, ENSCCF, Institut de Chimie de Clermont-Ferrand, BP 10448, F-63000 CLERMONT-FERRAND (France); Clermont Université, Université Blaise Pascal, Institut de Chimie de Clermont-Ferrand, BP 10448, F-63000 CLERMONT-FERRAND (France); Boyer, Damien [Clermont Université, ENSCCF, Institut de Chimie de Clermont-Ferrand, BP 10448, F-63000 CLERMONT-FERRAND (France); Clermont Université, Université Blaise Pascal, Institut de Chimie de Clermont-Ferrand, BP 10448, F-63000 CLERMONT-FERRAND (France); Avignant, Daniel [Clermont Université, Université Blaise Pascal, Institut de Chimie de Clermont-Ferrand, BP 10448, F-63000 CLERMONT-FERRAND (France); Fourati, Mohieddine [Laboratoire de Chimie Industrielle, Ecole Nationale d' Ingénieurs de Sfax, Université de Sfax, BP W 3038, Sfax (Tunisia); Zambon, Daniel [Clermont Université, Université Blaise Pascal, Institut de Chimie de Clermont-Ferrand, BP 10448, F-63000 CLERMONT-FERRAND (France); and others

    2014-01-15

    Sol–gel route has successfully been used to synthesize pure and Eu{sup 3+} doped polycrystalline samples of the GdP{sub 5}O{sub 14} pentaphosphates. The as-prepared samples have structurally been characterized using X-ray diffraction. Optical properties in the vacuum ultraviolet (VUV) of Eu{sup 3+} activated GdP{sub 5}O{sub 14} samples prepared either by sol–gel process or solid-state reaction were investigated at room temperature for comparison. In this GdP{sub 5}O{sub 14} host matrix the P{sub 5}O{sub 14} ultraphosphate groups were proved to exhibit an efficient absorption in the VUV range. The excitation spectra recorded in the VUV-UV spectral region from 120 nm to 350 nm have revealed the presence of Gd{sup 3+} 4f–5d interconfiguration transitions, Gd{sup 3+}–O{sup 2−} and Eu{sup 3+}–O{sup 2−} charge transfer states(CTS)in addition to intraconfiguration transitions of Gd{sup 3+} ions.Furthermore the Gd{sup 3+}→Eu{sup 3+} energy transfer process was investigated and discussed in the framework of the multiphonon relaxation process. Besides, the GdP{sub 5}O{sub 14}:Eu{sup 3+} phosphor led to a strong red emission under 147/172 nm excitation, so that it can be considered as a promising red phosphor for mercury-free lamps and plasma display panels applications. -- Highlights: • Lanthanide pentaphosphates were synthesized by the sol–gel process. • A broad absorption was evidenced in the VUV range for GdP{sub 5}O{sub 14}:Eu{sup 3+}. • An efficient energy transfer was proved from pentaphosphate lattice to Eu{sup 3+} ions.

  9. 25 W of average power at 172 nm in the vacuum ultraviolet from flat, efficient lamps driven by interlaced arrays of microcavity plasmas

    Science.gov (United States)

    Park, S.-J.; Herring, C. M.; Mironov, A. E.; Cho, J. H.; Eden, J. G.

    2017-04-01

    More than 25 W of average power and >800 W of peak power have been generated at λ =172 nm (h ν =7.2 eV) in the vacuum ultraviolet (VUV) from the Xe2 molecule in flat, 10 × 10 cm2 lamps having an active area and volume of 80 cm2 and interlaced arrays of microplasmas generated within cavities fabricated into an interior surface of the 20 % . For a bipolar voltage waveform driving frequency of 137 kHz and a 54% Xe/Ne gas fill mixture at a 300 K pressure of 550 Torr, the lamp generates as much as 31.5 W of average power and intensities >350 mW cm-2 in 40-60 μJ, 70±10 ns FWHM pulses produced in a burst mode-four pulses of 600-850 W peak power in every cycle of the driving waveform. The lamp intensity is uniform to within ±2.5% at ≥10 mm from its surface and average power varies linearly with pulse repetition frequency throughout the 18-135 kHz interval. The spectral breadth of the Xe dimer emission is ˜9 nm FWHM and time-resolved, spatial intensity maps show improved utilization of the power pulse (VṡI) with two or more microcavity arrays that are interleaved. This photonic source technology is capable of generating unprecedented power levels in the VUV spectral region (e.g., ˜2.5 kW m-2) with tiled lamps.

  10. Production of reactive species using vacuum ultraviolet photodissociation as a tool for studying their effects in plasma medicine: simulations and measurements

    Science.gov (United States)

    Ono, Ryo; Tokumitsu, Yusuke; Zen, Shungo; Yonemori, Seiya

    2014-11-01

    We propose a method for producing OH, H, O, O3, and O2(a1Δg) using the vacuum ultraviolet photodissociation of H2O and O2 as a tool for studying the reaction processes of plasma medicine. For photodissociation, an H2O/He or O2/He mixture flowing in a quartz tube is irradiated by a Xe2 or Kr2 excimer lamp. The effluent can be applied to a target. Simulations show that the Xe2 lamp method can produce OH radicals within 0.1-1 ppm in the effluent at 5 mm from a quartz tube nozzle. This is comparable to those produced by a helium atmospheric-pressure plasma jet (He-APPJ) currently used in plasma medicine. The Xe2 lamp method also produces H atoms of, at most, 6 ppm. In contrast, the maximum O densities produced by the Xe2 and Kr2 lamp methods are 0.15 ppm and 2.5 ppm, respectively; these are much lower than those from He-APPJ (several tens of ppm). Both lamp methods can produce ozone at concentrations above 1000 ppm and O2(a1Δg) at tens of ppm. The validity of the simulations is verified by measuring the O3 and OH densities produced by the Xe2 lamp method using ultraviolet absorption and laser-induced fluorescence. The differences between the measured and simulated densities for O3 and OH are 20% and factors of 3-4, respectively.

  11. Magnetic x-ray dichroism in ultrathin epitaxial films

    Energy Technology Data Exchange (ETDEWEB)

    Tobin, J.G.; Goodman, K.W. [Lawrence Berkeley National Lab., CA (United States); Cummins, T.R. [Univ. of Missouri, Rolla, MO (United States)] [and others

    1997-04-01

    The authors have used Magnetic X-ray Linear Dichroism (MXLD) and Magnetic X-ray Circular Dichroism (MXCD) to study the magnetic properties of epitaxial overlayers in an elementally specific fashion. Both MXLD and MXCD Photoelectron Spectroscopy were performed in a high resolution mode at the Spectromicroscopy Facility of the ALS. Circular Polarization was obtained via the utilization of a novel phase retarder (soft x-ray quarter wave plate) based upon transmission through a multilayer film. The samples were low temperature Fe overlayers, magnetic alloy films of NiFe and CoNi, and Gd grown on Y. The authors results include a direct comparison of high resolution angle resolved Photoelectron Spectroscopy performed in MXLD and MXCD modes as well as structural studies with photoelectron diffraction.

  12. Vibrational autoionization of state-selective jet-cooled methanethiol (CH3SH) investigated with infrared vacuum-ultraviolet photoionization

    Energy Technology Data Exchange (ETDEWEB)

    Xie, Min; Sen, Zhitao; Pratt, S. T.; Lee, Yuan-Pern

    2017-11-21

    Vibrational autoionization of Rydberg states provides key information about nonadiabatic processes above an ionization threshold. We employed time-of-flight mass detection of CH3SH+ to record vibrational-state selective photo-ionization efficiency (PIE) spectra of jet-cooled methanethiol (CH3SH) on exciting CH3SH to a specific vibrationally excited state with an infrared (IR) laser, followed by excitation with a tunable laser in the vacuum-ultraviolet (VUV) region for ionization. Autoionizing Rydberg states assigned to the ns, np, nd and nf series are identified. When IR light at 2601 (ν3, SH stretching mode) and 2948 cm-12, CH3 symmetric stretching mode) was employed, the Rydberg series converged to the respective vibrationally excited (ν3 and ν2) states of CH3SH+. When IR light at 3014 cm-1 (overlapped ν19, CH3 antisymmetric stretching and CH2 antisymmetric stretching modes) was employed, two converging limits towards vibrationally excited states (ν1 and ν9) of CH3SH+ were observed. In contrast, when IR light at 2867 cm-1 (2ν10, overtone of CH3 deformation mode) and 2892 cm-1 (2ν4, overtone of CH2 scissoring mode) was employed, both Δν = -1 and Δν = -2 ionization transitions were observed; there is evidence for direct ionization from the initial state into the CH3SH+ (v4+ = 1) continuum. In all observed IR-VUV-PIE spectra, the ns and nd series show intensity greater than the other Rydberg series, which is consistent with the fact that the highest-occupied molecular orbital of CH3SH is a p-like lone pair orbital on the S atom. The quantum yields for autoionization of various vibrational excited states are discussed.

  13. A Fourier transform spectrometer without a beam splitter for the vacuum ultraviolet range: From the optical design to the first UV spectrum.

    Science.gov (United States)

    de Oliveira, N; Joyeux, D; Phalippou, D; Rodier, J C; Polack, F; Vervloet, M; Nahon, L

    2009-04-01

    We describe a Fourier transform (FT) spectrometer designed to operate down to 60 nm (20 eV) on a synchrotron radiation beamline for high resolution absorption spectrometry. As far as we know, such an instrument is not available below 140 nm mainly because manufacturing accurate and efficient beam splitters remains a major problem at these wavelengths, especially if a wide bandwidth operation is desired. In order to overcome this difficulty, we developed an interferometer based on wave front division instead of amplitude division. It relies on a modified Fresnel bimirror configuration that requires only flat mirrors. The instrument provides path difference scanning through the translation of one reflector. During the scanning, the moving reflector is controlled by an optical system that keeps its direction constant within a tolerable value and provides an accurate interferometric measurement of the path difference variation. Therefore, a regular interferogram sampling is obtained, producing a nominal spectral impulse response and an accurate spectral calibration. The first results presented in this paper show a measured spectral resolution of delta(sigma)=0.33 cm-1 (interval between spectral samples). This was obtained with a sampling interval of 29 nm (path difference) and 512 K samples from a one-sided interferogram using a cosine FT. Such a sampling interval should allow the recording of large bandwidth spectra down to lambda=58 nm with an ultimate resolving power of 500,000 at this wavelength. In order to check the instrument performances, we first recorded an interferogram from a He-Ne stabilized laser. This provided the actual spectral impulse function, which was found to be fully satisfactory. The determination of the impulse response distortion and of the noise on the vacuum ultraviolet (VUV) spectral range provided accurate information in the sampling error profile over a typical scan. Finally, the instrument has been moved to the SU5 undulator

  14. A complex-polarization-propagator protocol for magneto-chiral axial dichroism and birefringence dispersion.

    Science.gov (United States)

    Cukras, Janusz; Kauczor, Joanna; Norman, Patrick; Rizzo, Antonio; Rikken, Geert L J A; Coriani, Sonia

    2016-05-21

    A computational protocol for magneto-chiral dichroism and magneto-chiral birefringence dispersion is presented within the framework of damped response theory, also known as complex polarization propagator theory, at the level of time-dependent Hartree-Fock and time-dependent density functional theory. Magneto-chiral dichroism and magneto-chiral birefringence spectra in the (resonant) frequency region below the first ionization threshold of R-methyloxirane and l-alanine are presented and compared with the corresponding results obtained for both the electronic circular dichroism and the magnetic circular dichroism. The additional information content yielded by the magneto-chiral phenomena, as well as their potential experimental detectability for the selected species, is discussed.

  15. Administrative Circulars

    CERN Document Server

    Département des Ressources humaines

    2004-01-01

    Administrative Circular N° 2 (Rev. 2) - May 2004 Guidelines and procedures concerning recruitment and probation period of staff members This circular has been revised. It cancels and replaces Administrative Circular N° 2 (Rev. 1) - March 2000. Administrative Circular N° 9 (Rev. 3) - May 2004 Staff members contracts This circular has been revised. It cancels and replaces Administrative Circular N° 9 (Rev. 2) - March 2000. Administrative Circular N° 26 (Rev. 4) - May 2004 Procedure governing the career evolution of staff members This circular has also been revised. It Administrative Circulars Administrative Circular N° 26 (Rev. 3) - December 2001 and brings up to date the French version (Rev. 4) published on the HR Department Web site in January 2004. Operational Circular N° 7 - May 2004 Work from home This circular has been drawn up. Operational Circular N° 8 - May 2004 Dealing with alcohol-related problems...

  16. Communication: Fullerene resolution by the magnetic circular dichroism

    Czech Academy of Sciences Publication Activity Database

    Štěpánek, Petr; Straka, Michal; Andrushchenko, Valery; Bouř, Petr

    2013-01-01

    Roč. 138, č. 15 (2013), 151103/1-151103/4 ISSN 0021-9606 R&D Projects: GA ČR GAP208/11/0105; GA MŠk(CZ) LH11033; GA ČR GA13-03978S Grant - others:AV ČR(CZ) M200551205 Institutional support: RVO:61388963 Keywords : density-functional theory * minor isomers * B-term * C-60 * spectra Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.122, year: 2013

  17. Circular Dichroism Spectroscopy: Enhancing a Traditional Undergraduate Biochemistry Laboratory Experience

    Science.gov (United States)

    Lewis, Russell L.; Seal, Erin L.; Lorts, Aimee R.; Stewart, Amanda L.

    2017-01-01

    The undergraduate biochemistry laboratory curriculum is designed to provide students with experience in protein isolation and purification protocols as well as various data analysis techniques, which enhance the biochemistry lecture course and give students a broad range of tools upon which to build in graduate level laboratories or once they…

  18. Magnetic linear dichroism in absorption spectroscopy of EuTe

    Energy Technology Data Exchange (ETDEWEB)

    Henriques, A B; Galgano, G D [Instituto de Fisica, Universidade de Sao Paulo, Caixa Postal 66318, 05315-970 Sao Paulo (Brazil); Abramof, E [LAS-INPE, Av. dos Astronautas, 1758-Jd. Granja, 12227-010, Sao Jose dos Campos (Brazil)

    2008-06-25

    The magnetic linear dichroism (MLD) at band-edge photon energies in the Voigt geometry was calculated for EuTe. At the spin-flop transition, MLD shows a step-like increase. Above the spin-flop transition MLD slowly decreases and becomes zero when the averaged electronic charge becomes symmetric relative to the axis of light propagation. Further increase of the magnetic field causes ferromagnetic alignment of the spins along the magnetic field direction, and MLD is recovered but with an opposite sign, and reaches maximum absolute values. These results are explained by the rearrangement of the Eu{sup 2+} spin distribution in the crystal lattice as a function of magnetic field, due to the Zeeman interaction, demonstrating that MLD can be a sensitive probe of the spin order in EuTe, and provides information that is not accessible from other magneto-optical techniques, such as magnetic circular dichroism measurement studies.

  19. Valence and ionic lowest-lying electronic states of ethyl formate as studied by high-resolution vacuum ultraviolet photoabsorption, He(I) photoelectron spectroscopy, and ab initio calculations

    Energy Technology Data Exchange (ETDEWEB)

    Śmiałek, M. A., E-mail: smialek@pg.gda.pl [Department of Control and Energy Engineering, Faculty of Ocean Engineering and Ship Technology, Gdańsk University of Technology, Gabriela Narutowicza 11/12, 80-233 Gdańsk (Poland); Łabuda, M.; Guthmuller, J. [Department of Theoretical Physic and Quantum Information, Faculty of Applied Physics and Mathematics, Gdańsk University of Technology, Gabriela Narutowicza 11/12, 80-233 Gdańsk (Poland); Hubin-Franskin, M.-J.; Delwiche, J. [Département de Chimie, Université de Liège, Institut de Chimie-Bât. B6C, B-4000 Liège (Belgium); Duflot, D. [Laboratoire de Physique des Lasers, Atomes et Molécules (PhLAM), UMR CNRS 8523, Université Lille1 Sciences et Technologies, F-59655 Villeneuve d' Ascq Cedex (France); Mason, N. J. [Department of Physical Sciences, The Open University, Walton Hall, Milton Keynes MK7 6AA (United Kingdom); Hoffmann, S. V.; Jones, N. C. [ISA, Department of Physics and Astronomy, Aarhus University, Ny Munkegade 120, Building 1520, DK-8000 Aarhus C (Denmark); Limão-Vieira, P., E-mail: plimaovieira@fct.unl.pt [Laboratório de Colisões Atómicas e Moleculares, CEFITEC, Departamento de Física, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, 2829-516 Caparica (Portugal)

    2014-09-14

    The highest resolution vacuum ultraviolet photoabsorption spectrum of ethyl formate, C{sub 2}H{sub 5}OCHO, yet reported is presented over the wavelength range 115.0–275.5 nm (10.75–4.5 eV) revealing several new spectral features. Valence and Rydberg transitions and their associated vibronic series, observed in the photoabsorption spectrum, have been assigned in accordance with new ab initio calculations of the vertical excitation energies and oscillator strengths. Calculations have also been carried out to determine the ionization energies and fine structure of the lowest ionic state of ethyl formate and are compared with a newly recorded He(I) photoelectron spectrum (from 10.1 to 16.1 eV). New vibrational structure is observed in the first photoelectron band. The photoabsorption cross sections have been used to calculate the photolysis lifetime of ethyl formate in the upper stratosphere (20–50 km)

  20. MAGNETIC-X-RAY DICHROISM - GENERAL FEATURES OF DIPOLAR AND QUADRUPOLAR SPECTRA

    NARCIS (Netherlands)

    CARRA, P; KONIG, H; THOLE, BT; ALTARELLI, M

    1993-01-01

    Sum rules are derived for dipolar linear and quadrupolar circular dichroism in the X-ray region. They relate the intensity of the dichroic signal to the ground state expectation values of orbital and spin dependent effective operators, which act on the valence electrons. The results obtained are