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Sample records for absorption linear dichroism

  1. X-ray linear dichroism dependence on ferroelectric polarization.

    PubMed

    Polisetty, S; Zhou, J; Karthik, J; Damodaran, A R; Chen, D; Scholl, A; Martin, L W; Holcomb, M

    2012-06-20

    X-ray absorption spectroscopy and photoemission electron microscopy are techniques commonly used to determine the magnetic properties of thin films, crystals, and heterostructures. Recently, these methods have been used in the study of magnetoelectrics and multiferroics. The analysis of such materials has been compromised by the presence of multiple order parameters and the lack of information on how to separate these coupled properties. In this work, we shed light on the manifestation of dichroism from ferroelectric polarization and atomic structure using photoemission electron microscopy and x-ray absorption spectroscopy. Linear dichroism arising from the ferroelectric order in the PbZr0:2Ti0:8O3 thin films was studied as a function of incident x-ray polarization and geometry to unambiguously determine the angular dependence of the ferroelectric contribution to the dichroism. These measurements allow us to examine the contribution of surface charges and ferroelectric polarization as potential mechanisms for linear dichroism. The x-ray linear dichroism from ferroelectric order revealed an angular dependence based on the angle between the ferroelectric polarization direction and the x-ray polarization axis, allowing a formula for linear dichroism in ferroelectric samples to be defined.

  2. LINEAR AND CIRCULAR DICHROISM OF MEMBRANES FROM RHODOPSEUDOMONAS CAPSULATA

    SciTech Connect

    Bolt, John D.; Sauer, Kenneth; Shiozawa, Judith A.; Drews, Gerhart

    1980-10-01

    Absorption, linear dichroism and circular dichroism spectra of Rhodopseudomonas capsulate (wild-type - St. Louis strain, mutant Y5 and mutant A1a{sup +}) are particularly sensitive to the nature of the light-harvesting bacteriochlorophyll-carotenoid-protein complexes. Evidence for exciton-type interactions is seen near 855 nm in the membranes from the wild-type and from mutant Y5, as well as in an isolated B800+850 light-harvesting complex from mutant Y5. The strong circular dichroism that reflects these interactions is attenuated more than 10-fold in membranes from the A1a+ mutant, which lacks both B800+850 and colored carotenoids and contains only the B875 light-harvesting complex. These results lead to the conclusion that these two light-harvesting complexes have significantly different chromophore arrangements or local environments.

  3. Disorder influence on linear dichroism analyses of smectic phases.

    PubMed

    Manor, Joshua; Khattari, Ziad; Salditt, Tim; Arkin, Isaiah T

    2005-07-01

    Linear dichroism, the unequal absorption of parallel and perpendicular linear polarized light, is often used to determine the anisotropic ordering of rodlike polymers in a smectic phase, such as helices in a lipid bilayer. It is a measure of two properties of the sample: 1), orientation of the chromophore transition dipole moment (TDM) and 2), disorder. Since it is the orientation of the chromophore TDM that is needed for high resolution structural studies, it is imperative to either deconvolve sample disorder, or at a minimum, estimate its effect upon the calculated TDM orientation. Herein, a rigorous analysis of the effects of disorder is undertaken based on the recently developed Gaussian disorder model implemented in linear dichroism data. The calculation of both the rod tilt and rotational pitch angles as a function of the disorder and dichroism, yield the following conclusions: Disorders smaller than 5 degrees have a vanishingly small effect on the calculated polymer orientation, whereas values smaller than 10 degrees have a negligible effect on the calculated parameters. Disorders larger than 10 degrees have an appreciable effect on the calculated orientational parameters and as such must be estimated before any structural characterization. Finally the theory is tested on the HIV vpu transmembrane domain, employing experimental mosaicity measurements from x-ray reflectivity rocking scans and linear dichroism.

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

    PubMed Central

    Narushima, Tetsuya; Okamoto, Hiromi

    2016-01-01

    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. PMID:27761022

  5. Humidity-dependent dynamic infrared linear dichroism study of a poly(ester urethane).

    PubMed

    Schoonover, Jon R; Steckle, Warren P; Cox, Jonathan D; Johnston, Cliff T; Wang, Yanqia; Gillikin, Angela M; Palmer, Richard A

    2007-05-01

    Fourier transform infrared techniques, infrared difference spectroscopy and dynamic infrared linear dichroism (DIRLD), have been utilized to explore the effects of humidity and water absorption on a poly(ester urethane). An environmental infrared microbalance cell was used to measure the infrared spectra as a function of humidity and accompanying weight change for the absorption-desorption processes. The infrared difference data indicate that exposure to humidity affects the hydrogen-bonding interactions in the polymer. Dynamic infrared linear dichroism studies in tensile deformation mode as a function of humidity demonstrate how changes in water content affect the orientational response of functional groups. Complex behavior as a function of humidity for functional groups involved in hydrogen bonding indicates that water absorbed by the polymer affects the micro-environments near these functional groups.

  6. Pulsed electric linear dichroism of triphenylmethane dyes adsorbed on montmorillonite K10 in aqueous media

    SciTech Connect

    Yamaoka, Kiwamu; Sasai, Ryo

    2000-05-01

    Electric linear dichroism (ELD) spectra of two cationic triphenylmethane dyes, crystal violet (CV) and malachite green (MG), bound to sodium montmorillonite K10 (MK-10) were studied at 20 C in aqueous media at two mixing ratios, D/S, of 0.10 and 0.24 in the 700- to 400 nm wavelength region and in the applied electric field strength range between 0 and 3 kV/cm. The specific parallel and perpendicular dichroism ({Delta}A{sub {parallel}}/A and {Delta}A{sub {perpendicular}}/A) spectra of dye-adsorbed MK-10 suspension were measured at a fixed field strength with an apparatus equipped with a 512-channel photodiode array detector. By changing the field strength over a wide range, a series of the reduced dichroism values of the bound dyes were measured at a fixed wavelength. By fitting these dichroism values to theoretical orientation functions, the intrinsic reduced dichroism ({Delta}A/A){sub int} spectra at the limiting high fields (ELD spectrum) were determined for CV and MG bound to MK-10. No appreciable difference was observed at the two D/S values. The ELD spectra of these bound dyes are undulatory but never constant, throughout their absorption region; thus, the dye plane does not lie flatly either on the surface or between layers of MK-10 particle.

  7. Theoretical electronic absorption and natural circular dichroism spectra of (-)-trans-cyclooctene

    NASA Astrophysics Data System (ADS)

    Pedersen, Thomas Bondo; Koch, Henrik

    2000-02-01

    Using the random phase approximation and coupled cluster singles and doubles linear response theory in conjunction with two basis sets of augmented double-zeta quality and two nuclear geometries, we have calculated electronic absorption and natural circular dichroism spectra of (-)-trans-cyclooctene. We present a density functional theory optimized nuclear geometry whose ground state electric dipole moment and harmonic vibrational spectrum compare well with experimental data. The coupled cluster results obtained with this nuclear geometry are in good agreement with experimental electronic spectra, although the original interpretation of the most intense low-lying band as a π→π* transition is contradicted.

  8. Theoretical study of the large linear dichroism of herapathite

    NASA Astrophysics Data System (ADS)

    Liang, Lei; Rulis, Paul; Kahr, Bart; Ching, W. Y.

    2009-12-01

    The remarkable linear dichroism of herapathite (HPT), the active component of polaroid, resisted explanation for more than 150 years because the crystal structure was not solved until very recently. The crystal structure with a formula unit of (C20H24N2O2H2)4ṡC2H4O2ṡ3SO4ṡ2I3ṡ6H2O in an orthorhombic cell has a slight disorder related to the positions of the six water molecules and the acetic-acid molecule. The electronic and optical properties of this complex crystal are here calculated on the basis of the newly described x-ray structure using a density-functional theory based method with local-orbital basis. The theoretical optical spectrum of HPT shows giant optical anisotropy as observed experimentally with an anisotropy factor on the order of 385 that can be ascribed to transitions between molecular levels of the 2I3- chains that are oriented along the crystalline b axis. It is shown that the key to achieve large anisotropy is to align the iodine ions in a quasi-one-dimensional chain via confinement in a clatharate channel formed by the quinine molecules. The solvent molecules in the crystal have a minimal effect. The implications of this work on biologically relevant systems are discussed.

  9. Linear and nonlinear circular dichroism of R-(+)-3-methylcyclopentanone

    NASA Astrophysics Data System (ADS)

    Li, R.; Sullivan, R.; Al-Basheer, W.; Pagni, R. M.; Compton, R. N.

    2006-10-01

    Linear and nonlinear circular dichroism of R-(+)-3-methylcyclopentanone (R-3MCP ) is reported in the gas and liquid phases. Measurements of (2+1) resonance-enhanced multiphoton ionization circular dichroism (REMPICD) for nozzle-jet expanded molecular beams of the equatorial conformer of R-3MCP are presented. Monitoring either mass-selected cations or photoelectrons produced via (2+1) REMPI through the n →3s Rydberg transition yielded a REMPICD of +1.5±0.5% [REMPICD≡2(IL-IR)/(IL+IR)], where IL /R refers to the ion/electron signal for left/right circularly polarized light. A racemic mixture of 3-methylcyclopentanone showed no significant CD; however, the signal fluctuations were much larger than that observed for the resolved R-(+)-3-methylcyclopentanone as might be expected for the small number of ions produced from slightly unequal numbers of enantiomers in each laser shot. Gas phase, vibrationally resolved, one-photon CD for vapor phase R-(+)-3-methylcyclopentanone (i.e., admixture of five axial and equatorial forms) was measured to be ˜0 and -0.004 at photon energies corresponding to the one- (nonresonant) and two-(3s resonance) photon energy levels. The one-photon CD (of the room temperature population of conformers) at an energy corresponding to the ionization step was measured previously to be ˜+0.0011 which is of the same sign as the REMPICD. The first step is also near a positive CD region. This suggests that the (2+1) REMPICD is determined primarily by both the initial and continuum steps. The one-photon CDs for the equatorial and axial forms of 3MCP are calculated, using GAUSSIAN03, to be approximately equal but having opposite sign for the transitions of interest. The CD for 3MCP in cyclohexane is found to be strongly temperature dependent as a result of the presence of both the axial and equatorial conformers. The energy difference between the two conformers is determined from a van't Hoff plot of these data to be 3.50±0.05kJ /mole in cyclohexane

  10. Theory for magnetic linear dichroism of electronic transitions between twofold-degenerate molecular spin levels

    NASA Astrophysics Data System (ADS)

    Bominaar, Emile L.; Achim, Catalina; Peterson, Jim

    1998-07-01

    Magnetic linear dichroism (MLD) spectroscopy is a relatively new technique which previously has been almost exclusively applied to atoms. These investigations have revealed that the study of MLD, in conjunction with electronic absorption and magnetic circular dichroism (MCD) spectroscopies, provides significant additional information concerning the electronic structure of atoms. More recent measurements have indicated that MLD is also observable from transition ions in inorganic compounds and metalloproteins. While the theory for atomic MLD has been worked out in considerable detail during the last two decades, an MLD theory of practical utility for the analysis of the spectra derived from the majority of paramagnetic molecules is not available. In the present contribution, the MLD of an electric-dipole-allowed transition between twofold-degenerate molecular spin levels is analyzed, assuming nonsaturating conditions. As for atomic systems, it is found that the MLD of a single molecule is dominated by the term G0. However, this term vanishes in the powder average evaluated for a randomly oriented ensemble of molecules, leading to a drastic reduction of the MLD differential absorption for systems with spin S=1/2 compared to that observed for systems with higher ground-state spin. It is found that MLD and MCD spectroscopies on solution samples have complementary spin-state specific sensitivities which suggest that the two methods can be used to selectively probe the individual metal sites in multicenter metalloprotein assemblies.

  11. The magnitude of linear dichroism of biological tissues as a result of cancer changes

    NASA Astrophysics Data System (ADS)

    Bojchuk, T. M.; Yermolenko, S. B.; Fedonyuk, L. Y.; Petryshen, O. I.; Guminetsky, S. G.; Prydij, O. G.

    2012-01-01

    The results of studies of linear dichroism values of different types of biological tissues (human prostate, esophageal epithelial human muscle tissue in rats) both healthy and infected tumor at different stages of development are shown here. The significant differences in magnitude of linear dichroism and its spectral dependence in the spectral range λ = 330 - 750 nm both among the objects of study, and between biotissues: healthy (or affected by benign tumors) and cancer patients are established. It is researched that in all cases in biological tissues (prostate gland, esophagus, human muscle tissue in rats) with cancer the linear dichroism arises, the value of which depends on the type of tissue and time of the tumor process. As for healthy tissues linear dichroism is absent, the results may have diagnostic value for detecting and assessing the degree of development of cancer.

  12. The magnitude of linear dichroism of biological tissues as a result of cancer changes

    NASA Astrophysics Data System (ADS)

    Bojchuk, T. M.; Yermolenko, S. B.; Fedonyuk, L. Y.; Petryshen, O. I.; Guminetsky, S. G.; Prydij, O. G.

    2011-09-01

    The results of studies of linear dichroism values of different types of biological tissues (human prostate, esophageal epithelial human muscle tissue in rats) both healthy and infected tumor at different stages of development are shown here. The significant differences in magnitude of linear dichroism and its spectral dependence in the spectral range λ = 330 - 750 nm both among the objects of study, and between biotissues: healthy (or affected by benign tumors) and cancer patients are established. It is researched that in all cases in biological tissues (prostate gland, esophagus, human muscle tissue in rats) with cancer the linear dichroism arises, the value of which depends on the type of tissue and time of the tumor process. As for healthy tissues linear dichroism is absent, the results may have diagnostic value for detecting and assessing the degree of development of cancer.

  13. Electronic studies of chrysene. Linear and magnetic circular dichroism and quantum chemical calculations

    SciTech Connect

    Spanget-Larsen, J. ); Waluk, J. ); Thulstrup, E.W. )

    1990-03-08

    The electronic transitions of chrysene are investigated by linear dichroism spectroscopy in stretched polyethylene and by magnetic circular dichroism spectroscopy, leading to the assignment of seven excited singlet states below 47,000 cm{sup {minus}1}. One of these has not previously been observed. The linear dichroism data, combined with previously published fluorescence polarization results, lead to precise determination of transition moment directions for five transitions. The experimental results are compared with theoretical predictions with the PPP, LCOAO, CNDO/S, and INDO/S quantum chemical models.

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

    PubMed

    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. PMID:26756612

  15. Dual source fourier transform polarization modulation spectroscopy: an improved method for the measurement of circular and linear dichroism.

    PubMed

    Nafie, Laurence A; Buijs, Henry; Rilling, Allan; Cao, Xiaolin; Dukor, Rina K

    2004-06-01

    It is shown that the use of two sources in a four-port interferometer equipped with cube-corner mirrors leads to increased signal-to-noise ratios in Fourier transform (FT-IR) circular and linear dichroism spectra. The output beam to the sample is a superposition of two interferograms, one from each source, having opposite Fourier phases. These two interferograms cancel one another to the degree that the two sources are matched in intensity. If the radiation from each of the two sources is first polarized orthogonally with respect to the other and passed through a polarization modulator before reaching the sample, the resulting polarization-modulation interferograms are out of Fourier phase and out of polarization-modulation phase. As a result, the polarization-modulation interferograms, due to circular or linear dichroism in the sample, from the two sources combine positively rather than negatively. An improvement in signal-to-noise ratio of up to two (or a factor of four in scan-time reduction for the same signal-to-noise ratio) compared to single source operation can be realized, while at the same time, the potential for saturation of the detector signal is significantly reduced due to the reduction in magnitude of the combined ordinary infrared transmission interferogram. Absorption and circular dichroism spectra from a dual-source FT-IR spectrometer are presented and analyzed.

  16. Linear dichroism studies of tryptophanase and its quasisubstrate complexes oriented in polyacrylamide gel.

    PubMed

    Zakomirdina, L N; Sakharova, I S; Torchinsky, Y M

    1990-10-01

    Tryptophanase from Escherichia coli was oriented in a compressed slab of polyacrylamide gel and its linear dichroism (LD) and absorption spectra have been measured. The free enzyme displays four LD bands at 305, 340, 425 and 490 nm. Two bands at 340 and 425 nm belong to the internal coenzyme-lysine aldimine. The 305-nm band apparently belongs to an aromatic amino acid residue. The 490-nm band disappears after treatment with NaBH4 or after incubation with L-alanine and subsequent dialysis. It is suggested that the 490-nm band belongs to a quinonoid enzyme subform. The reaction of tryptophanase with threo-3-phenyl-DL-serine, L-threonine and D-alanine leads to formation of an external aldimine with an intense absorption band at 420-425 nm. The values of reduced LD (delta A/A) in this band strongly differ from that in the 420-nm band of the free enzyme. The LD value of the complex with D-alanine is intermediate between those of the free enzyme and the complex with 3-phenylserine. In the presence of indole the complex with D-alanine displays the same LD as that observed with 3-phenylserine. The reaction of tryptophanase with L-alanine or oxindolyl-L-alanine leads to formation of a quinonoid intermediate with an absorption band near 500 nm. The LD value in this band is close to that of an external aldimine with L-threonine. It is concluded that reorientations of the coenzyme occur in the course of the tryptophanase reaction.

  17. High-mobility transport anisotropy and linear dichroism in few-layer black phosphorus.

    PubMed

    Qiao, Jingsi; Kong, Xianghua; Hu, Zhi-Xin; Yang, Feng; Ji, Wei

    2014-07-21

    Two-dimensional crystals are emerging materials for nanoelectronics. Development of the field requires candidate systems with both a high carrier mobility and, in contrast to graphene, a sufficiently large electronic bandgap. Here we present a detailed theoretical investigation of the atomic and electronic structure of few-layer black phosphorus (BP) to predict its electrical and optical properties. This system has a direct bandgap, tunable from 1.51 eV for a monolayer to 0.59 eV for a five-layer sample. We predict that the mobilities are hole-dominated, rather high and highly anisotropic. The monolayer is exceptional in having an extremely high hole mobility (of order 10,000 cm(2) V(-1) s(-1)) and anomalous elastic properties which reverse the anisotropy. Light absorption spectra indicate linear dichroism between perpendicular in-plane directions, which allows optical determination of the crystalline orientation and optical activation of the anisotropic transport properties. These results make few-layer BP a promising candidate for future electronics.

  18. Probing Microscopic Orientation in Membranes by Linear Dichroism.

    PubMed

    Rocha, Sandra; Kogan, Maxim; Beke-Somfai, Tamás; Nordén, Bengt

    2016-03-29

    The cell membrane is an ordered environment, which anisotropically affects the structure and interactions of all of its molecules. Monitoring membrane orientation at a local level is rather challenging but could reward crucial information on protein conformation and interactions in the lipid bilayer. We monitored local lipid ordering changes upon varying the cholesterol concentration using polarized light spectroscopy and pyrene as a membrane probe. Pyrene, with a shape intermediate between a disc and a rod, can detect microscopic orientation variations at the level of its size. The global membrane orientation was determined using curcumin, a probe with nonoverlapping absorption relative to that of pyrene. While the macroscopic orientation of a liquid-phase bilayer decreases with increasing cholesterol concentration, the local orientation is improved. Pyrene is found to be sensitive to the local effects induced by cholesterol and temperature on the bilayer. Disentangling local and global orientation effects in membranes could provide new insights into functionally significant interactions of membrane proteins.

  19. Probing Microscopic Orientation in Membranes by Linear Dichroism.

    PubMed

    Rocha, Sandra; Kogan, Maxim; Beke-Somfai, Tamás; Nordén, Bengt

    2016-03-29

    The cell membrane is an ordered environment, which anisotropically affects the structure and interactions of all of its molecules. Monitoring membrane orientation at a local level is rather challenging but could reward crucial information on protein conformation and interactions in the lipid bilayer. We monitored local lipid ordering changes upon varying the cholesterol concentration using polarized light spectroscopy and pyrene as a membrane probe. Pyrene, with a shape intermediate between a disc and a rod, can detect microscopic orientation variations at the level of its size. The global membrane orientation was determined using curcumin, a probe with nonoverlapping absorption relative to that of pyrene. While the macroscopic orientation of a liquid-phase bilayer decreases with increasing cholesterol concentration, the local orientation is improved. Pyrene is found to be sensitive to the local effects induced by cholesterol and temperature on the bilayer. Disentangling local and global orientation effects in membranes could provide new insights into functionally significant interactions of membrane proteins. PMID:26974226

  20. Magnetic x-ray linear dichroism of ultrathin Fe-Ni alloy films

    SciTech Connect

    Schumann, F.O.; Willis, R.F.; Goodman, K.W.

    1997-04-01

    The authors have studied the magnetic structure of ultrathin Fe-Ni alloy films as a function of Fe concentration by measuring the linear dichroism of the 3p-core levels in angle-resolved photoemission spectroscopy. The alloy films, grown by molecular-beam epitaxy on Cu(001) surfaces, were fcc and approximately four monolayers thick. The intensity of the Fe dichroism varied with Fe concentration, with larger dichroisms at lower Fe concentrations. The implication of these results to an ultrathin film analogue of the bulk Invar effect in Fe-Ni alloys will be discussed. These measurements were performed at the Spectromicroscopy Facility (Beamline 7.0.1) of the Advanced Light Source.

  1. Micro-Volume Couette Flow Sample Orientation for Absorbance and Fluorescence Linear Dichroism

    PubMed Central

    Marrington, Rachel; Dafforn, Timothy R.; Halsall, David J.; Rodger, Alison

    2004-01-01

    Linear dichroism (LD) can be used to study the alignment of absorbing chromophores within long molecules. In particular, Couette flow LD has been used to good effect in probing ligand binding to DNA and to fibrous proteins. This technique has been previously limited by large sample requirements. Here we report the design and application of a new micro-volume Couette flow cell that significantly enhances the potential applications of flow LD spectroscopy by reducing the sample requirements for flow linear dichroism to 25 μL (with concentrations such that the absorbance maximum of the sample in a 1-cm pathlength cuvette is ∼1). The micro-volume Couette cell has also enabled the measurement of fluorescence-detected Couette flow linear dichroism. This new technique enables the orientation of fluorescent ligands to be probed even when their electronic transitions overlap with those of the macromolecule and conversely. The potential of flow-oriented fluorescence dichroism and application of the micro-volume Couette LD cell are illustrated by the collection of data for DNA with minor groove and intercalating ligands: DAPI, Hoechst, and ethidium bromide. As with conventional fluorescence, improved sensitivity compared with absorbance LD is to be expected after instrumentation optimization. PMID:15345576

  2. Time-resolved circular dichroism and absorption studies of the photolysis reaction of (carbonmonoxy)myoglobin.

    PubMed Central

    Milder, S J; Bjorling, S C; Kuntz, I D; Kliger, D S

    1988-01-01

    Time-resolved circular dichroism (TRCD) and absorption spectroscopy are used to follow the photolysis reaction of (carbonmonoxy)myoglobin (MbCO). Following the spectral changes associated with the initial loss of CO, a subtle change is observed in the visible absorption spectrum of the Mb product on a time scale of a few hundred nanoseconds. No changes are seen in the CD spectrum of Mb in the visible and near-UV regions subsequent to the loss of CO. The data suggest the existence of an intermediate found after ligand loss from MbCO that is similar in structure to the final Mb product. PMID:3390516

  3. Magnetic x-ray linear dichroism in resonant and non-resonant Gd 4f photoemission

    SciTech Connect

    Mishra, S.; Gammon, W.J.; Pappas, D.P.

    1997-04-01

    The enhancement of the magnetic linear dichroism in resonant 4f photoemission (MLDRPE) is studied from a 50 monolayer film of Gd/Y(0001). The ALS at beamline 7.0.1 provided the source of linearly polarized x-rays used in this study. The polarized light was incident at an angle of 30 degrees relative to the film plane, and the sample magnetization was perpendicular to the photon polarization. The linear dichroism of the 4f core levels is measured as the photon energy is tuned through the 4d-4f resonance. The authors find that the MLDRPE asymmetry is strongest at the resonance. Near the threshold the asymmetry has several features which are out of phase with the fine structure of the total yield.

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

    PubMed

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

    2016-06-14

    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

  5. Development and experimental verification of a theory for high-field, ultralow-temperature magnetic linear dichroism of glasses containing molecular chromophores with spin doublet ground states

    NASA Astrophysics Data System (ADS)

    Bominaar, Emile L.; Peterson, Jim

    1999-10-01

    The first observation of magnetic linear dichroism in a metalloprotein Kramers system is reported, namely, that exhibited by the porphyrin moiety in ferricytochrome c (spin S=1/2). The measurements were conducted at low temperatures and in strong magnetic fields to maximize the signal intensity, which is intrinsicly weak in this case. The theory used in the interpretation of the wavelength dependence of this magneto-optical effect is based on the rigid-shift approximation in which the dichroic spectra are expressed as a sum of zeroth, first, and second derivatives of the underlying electronic absorption band. Similar to the case for magnetic circular dichroism, magnetic linear dichroism is caused by the Zeeman interactions of the molecular-chromophore electrons with an applied magnetic field. Two kinds of Zeeman interaction are considered, termed "inner state" and "outer state" depending on, respectively, whether or not they act between the components of a single Kramers doublet of the chromophore. It is formally demonstrated that the zeroth-derivative term for an electric-dipole transition between Kramers doublets arising from inner-state Zeeman interactions (nominally the strongest effect) completely cancels in the powder average over a randomly oriented ensemble of chromophores for all values of temperature and field. This cancellation has a profound effect on the magnetic linear dichroism of molecular chromophores suspended in glasses, as the effect now entirely relies on a set of weaker residual terms, each one having its own spectroscopic characteristics. The residual contributions have been estimated on the basis of electronic-term-energy differences and bandwidths in ferricytochrome c, resulting in the identification of the inner- and outer-state terms C1 and F0 as the dominant signatures. This prediction is in agreement with the experimental data for the shape and dependence on applied field and temperature of the magneto-dichroic spectrum for this

  6. Linear dichroism and optical anisotropy of silver nanoprisms in polymer films

    NASA Astrophysics Data System (ADS)

    Requena, S.; Doan, H.; Raut, S.; D'Achille, A.; Gryczynski, Z.; Gryczynski, I.; Strzhemechny, Y. M.

    2016-08-01

    We present optical studies of two different size distributions of silver triangular nanoprisms, one with a dipole resonance at 520 nm and the other with a dipole resonance at 650 nm, placed in different media. Significant wavelength-dependent depolarization of scattered light from the silver nanoprisms suspended in water indicates strong interference of multiple surface plasmon resonant modes in the same particle. We use this depolarization as a probe of light scattering by the nanoprisms in a lipid solution due to the rejection of a polarized background scattering. Also, the silver nanoprisms were embedded in a polyvinyl alcohol polymer matrix and oriented by stretching the polymer/nanoprism nanocomposite films. We observe significantly increased linear dichroism in the region associated with the plasmonic in-plane dipole mode upon stretching. Additionally, there is a weaker linear dichroism in the region associated with out-of-plane modes, which vanish in the extinction spectrum of the stretched nanocomposite film.

  7. Quantitation of protein orientation in flow-oriented unilamellar liposomes by linear dichroism

    NASA Astrophysics Data System (ADS)

    Rajendra, Jascindra; Damianoglou, Angeliki; Hicks, Matthew; Booth, Paula; Rodger, P. Mark; Rodger, Alison

    2006-07-01

    The linear dichroism of the visible wavelength transitions of retinal have been used to analyse linear dichroism spectra to determine the orientation of aromatic and peptide structural motifs of Bacteriorhodopsin incorporated into unilamellar soy bean liposomes. The results are consistent with the available X-ray data. This proves that visible light absorbing chromophores can be used to analyse linear dichroism data to give the orientation of membrane proteins in membrane mimicking environments. The work has been extended by screening a wide range of hydrophobic molecules with high extinction coefficients in transitions above 300 nm to find molecules that could be used as independent probes of liposome orientation for experiments involving proteins incorporated into liposomes. Three probes were found to have potential for future work: bis-(1,3-dibutylbarbituric acid)pentamethine oxonol (DiBAC 4), retinol and rhodamine B. All three can be used to determine the orientation of the porphyrin of cytochrome c, the aromatic residues of gramicidin and the helices of both proteins. The orientation parameter, S, for the liposomes varied from batch to batch of unilamellar liposomes prepared by extruding through a 100 nm membrane. The value and variation in S was 0.030 ± 0.010. Repeat experiments with the same batch of liposomes showed less variation. Film LD data were measured for DiBAC 4 and rhodamine B to determine the polarisations of their long wavelength transitions.

  8. Experimental test of absorption flattening correction for circular dichroism of particle suspensions.

    PubMed

    Gerdova, Anna; Kelly, Sharon M; Halling, Peter

    2011-08-01

    There are well established theoretical models for correction for absorption flattening of circular dichroism (CD) measurements on particle suspensions. However, these have not been directly tested experimentally. We describe a test system with the chiral tris(ethylenediamine)Co(III) complex dissolved in water trapped inside sephadex particles, suspended in 1-butanol. Independent measurements of particle size distribution, volume fraction, and the absorbance of the suspension are used to calculate the required CD correction. The corrected CD signal is found to agree rather well with that for the same amount of Co-complex dispersed uniformly throughout the sample cell. This holds for different particle volume fractions and Co-complex concentrations inside the particles. The correction seems to work despite a substantial scattering contribution to the absorbance, which is not considered in the theoretical models.

  9. Magnetic linear dichroism of photoemission from ultrathin manganese films on silicon

    NASA Astrophysics Data System (ADS)

    Gomoyunova, M. V.; Grebenyuk, G. S.; Pronin, I. I.; Senkovskiy, B. V.

    2015-09-01

    The magnetic linear dichroism (MLD) effect in photoemission of Mn 3 p electrons was used to study magnetic properties of Mn films (to 2.5 nm thick) grown on the Si(111)-(7 × 7) surface at room temperature and manganese silicide films grown by solid-phase epitaxy. The experiments were performed using linearly polarized light with a photon energy of 130 eV, incident at an angle of 30° to the sample surface. Photoelectron spectra were measured in a narrow solid angle focused along the normal to the surface for two opposite sample magnetization directions in the surface plane, perpendicular to the polarization vector of the light wave. It was shown that the MLD effect characteristic of films with high-temperature ferromagnetism appears after depositing ˜2 nm Mn. The formation of manganese silicides upon annealings of the sample with deposited 2.5 nm Mn results in the disappearance of the MLD effect.

  10. Linear birefringence and dichroism in citric acid coated Fe3O4 magnetic nanoparticles

    NASA Astrophysics Data System (ADS)

    Lin, Jing-Fung; Tsai, Chun-Chin; Lee, Meng-Zhe

    2014-12-01

    To prepare highly dispersed water-based Fe3O4 magnetic nanoparticles (MNPs), we adopted the co-precipitation method and used citric acid (CA) as the surfactant. Via transmission electronic microscopy, dynamic light scattering, and X-ray diffractometry, we characterized the dispersibility and size of the products. Through two single-parameter experiments, including the pH value of suspension and the action of double centrifugations, the appropriate parameters' values were determined. Further, to produce CA coated MNPs with good magneto-optical properties as high retardance and low dichroism, the orthogonal design method was used to find the optimal parameters' values, including pH value of suspension after coating was 5, molar ratio of CA to Fe3O4 MNPs was 0.06, volume of CA was 40 ml, and coating temperature was 70 °C. Above all, the linear birefringence and dichroism of the best CA coated ferrofluid we produced were measured by a Stokes polarimeter as 23.6294° and 0.3411 under 64.5 mT, respectively. Thus, the biomedical applications could be performed hereafter.

  11. Linear birefringence and dichroism measurement in oil-based Fe3O4 magnetic nanoparticles

    NASA Astrophysics Data System (ADS)

    Lin, Jing-Fung; Wang, Chia-Hung; Lee, Meng-Zhe

    2013-04-01

    To prepare dispersed Fe3O4 magnetic nanoparticles (MNPs), we adopt a co-precipitation method and consider surfactant amount, stirring speed, dispersion mode, and molar ratio of Fe3+/Fe2+. Via transmission electronic microscopy and X-ray diffractometry, we characterize the dispersibility and size of the products and determine the appropriate values of experimental parameters. The stirring speed is 1000 rpm in titration. There is simultaneous ultrasonic vibration and mechanical stirring in the titration and surface coating processes. The surfactant amount of oleic acid is 1.2 ml for molar ratios of Fe3+/Fe2+ as 1.7:1, 1.8:1, and 1.9:1. The average diameters of these Fe3O4 MNPs are 11 nm, and the ratios of saturation magnetization for these MNPs to that of bulk magnetite range from 45% to 65%, with remanent magnetization close to zero and low coercivity. Above all, the linear birefringence and dichroism measurements of the kerosene-based ferrofluid (FF) samples are investigated by a Stokes polarimeter. The influences of particle size distribution and magnetization in the birefringence and dichroism measurements of FFs are discussed.

  12. Analyses of optical absorption and circular dichroism spectra of spinach ferredoxin at alkaline pH.

    PubMed

    Hasumi, H

    1982-10-01

    The whole protein structure and the microenvironments of the iron-sulfur cluster and of the side chains of amino acid residues of spinach ferredoxin were studied by optical absorption and circular dichroism (CD) spectroscopy in the alkaline pH range. From the pH-dependence of the optical absorption changes at 245 nm, the four tyrosyl residues of ferredoxin were classified into three groups: one exposed residue with a normal apparent pK value of 10.1, two exposed residues with abnormal apparent pK values of 12.0, and one buried residue showing time-dependent ionization. The absorption in the visible region disappeared gradually with the ionization of the buried residue rather than that of the three exposed residues. The apparent pK value of 10.0 was obtained from the rapid CD changes at 258 nm caused by pH elevation from neutral to alkaline pH. The structural alteration associated with the CD change had no effect on the secondary structure of the protein moiety other than the iron-sulfur cluster and the microenvironment of the cluster. The rate constants obtained from the time courses of the CD changes in the near-ultraviolet and visible regions were in good agreement with those obtained from the time courses of the optical absorption changes. These results lead to the conclusions that (1) the native ferredoxin structure is maintained through the interaction with the iron-sulfur cluster and (2) the protein structure in the neighborhood of the cluster, important for the physiological activity, is not perturbed even though the exposed tyrosyl residues are ionized.

  13. Binding of anti-prion agents to glycosaminoglycans: Evidence from electronic absorption and circular dichroism spectroscopy

    SciTech Connect

    Zsila, Ferenc . E-mail: zsferi@chemres.hu; Gedeon, Gabor

    2006-08-11

    The polyanionic glycosaminoglycans (GAGs) are intimately involved in the pathogenesis of protein conformational disorders such as amyloidosis and prion diseases. Several cationic agents are known to exhibit anti-prion activity but their mechanism of action is poorly understood. In this study, UV absorption and circular dichroism (CD) spectroscopic techniques were used to investigate the interaction between heparin and chondroitin-6-sulfate and anti-prion drugs including acridine, quinoline, and phenothiazine derivatives. UV band hypochromism of ({+-})-quinacrine, ({+-})-primaquine, tacrine, quinidine, chlorpromazine, and induced CD spectra of ({+-})-quinacrine upon addition of GAGs provided evidence for the GAG binding of these compounds. The association constants ({approx}10{sup 6}-10{sup 7} M{sup -1}) estimated from the UV titration curves show high-affinity drug-heparin interactions. Ionic strength-dependence of the absorption spectra suggested that the interaction between GAGs and the cationic drugs is principally electrostatic in nature. Drug binding differences of heparin and chondroitin-6-sulfate were attributed to their different negative charge density. These results call the attention to the alteration of GAG-prion/GAG-amyloid interactions by which these compounds might exert their anti-prion/anti-amyloidogenic activities.

  14. Linear dichroism amplification: Adapting a long-known technique for ultrasensitive femtosecond IR spectroscopy

    SciTech Connect

    Rehault, Julien; Helbing, Jan; Zanirato, Vinicio; Olivucci, Massimo

    2011-03-28

    We demonstrate strong amplification of polarization-sensitive transient IR signals using a pseudo-null crossed polarizer technique first proposed by Keston and Lospalluto [Fed. Proc. 10, 207 (1951)] and applied for nanosecond flash photolysis in the visible by Che et al. [Chem. Phys. Lett. 224, 145 (1994)]. We adapted the technique to ultrafast pulsed laser spectroscopy in the infrared using photoelastic modulators, which allow us to measure amplified linear dichroism at kilohertz repetition rates. The method was applied to a photoswitch of the N-alkylated Schiff base family in order to demonstrate its potential of strongly enhancing sensitivity and signal to noise in ultrafast transient IR experiments, to simplify spectra and to determine intramolecular transition dipole orientations.

  15. In situ azimuthal rotation device for linear dichroism measurements in scanning transmission x-ray microscopy

    NASA Astrophysics Data System (ADS)

    Hernández-Cruz, D.; Hitchcock, A. P.; Tyliszczak, T.; Rousseau, M.-E.; Pézolet, M.

    2007-03-01

    A novel miniature rotation device used in conjunction with a scanning transmission x-ray microscope is described. It provides convenient in situ sample rotation to enable measurements of linear dichroism at high spatial resolution. The design, fabrication, and mechanical characterization are presented. This device has been used to generate quantitative maps of the spatial distribution of the orientation of proteins in several different spider and silkworm silks. Specifically, quantitative maps of the dichroic signal at the C 1s→π*amide transition in longitudinal sections of the silk fibers give information about the spatial orientation, degree of alignment, and spatial distribution of protein peptide bonds. A new approach for analyzing the dichroic signal to extract orientation distributions, in addition to magnitudes of aligned components, is presented and illustrated with results from Nephila clavipes dragline spider silk measured using the in situ rotation device.

  16. Experimental study of linear magnetic dichroism in photoionization satellite transitions of atomic rubidium

    SciTech Connect

    Jaenkaelae, K.; Alagia, M.; Feyer, V.; Richter, R.; Prince, K. C.

    2011-11-15

    Laser orientation in the initial state has been used to study the properties of satellite transitions in inner-shell photoionization of rubidium atoms. The linear magnetic dichroism in the angular distribution (LMDAD) has been utilized to probe the continuum waves of orbital angular momentum conserving monopole, and angular momentum changing conjugate satellites, accompanying the 4p ionization of atomic Rb. We show experimentally that LMDAD of both types of satellite transitions is nonzero and that LMDAD of monopole satellites, measured as a function of photon energy, mimics the LMDAD of direct photoionization, whereas the LMDAD of conjugate transitions deviates drastically from that trend. The results indicate that conjugate transitions cannot be described theoretically without explicit inclusion of electron-electron interaction. The present data can thus be used as a very precise test of current models for photoionization.

  17. Probing the structure of long DNA molecules in solution using synchrotron radiation linear dichroism.

    PubMed

    Rittman, Martyn; Hoffmann, Søren V; Gilroy, Emma; Hicks, Matthew R; Finkenstadt, Bärbel; Rodger, Alison

    2012-01-01

    Linear dichroism (LD), a spectroscopic method for aligned samples, has been used with a synchrotron radiation source to reveal insights into the structure and stability of DNA with increasing salt concentrations (thus stabilizing the base pairing) and increasing temperature while remaining below the melting point (thus destabilizing the base pairing). Measurements have been made from 350 nm to 182 nm, and the spectral changes observed quantified using a Bayesian Markov chain Monte Carlo (MCMC) algorithm, which uses statistical methods to fit to experimental data. Based on literature H-D exchange experiments, we surmise that the cause of the spectral variations is the induction of transient single stranding of tracts in the DNA polymer, particularly those with significant content of the weaker AT base pairs. More detailed analysis of the LD data will require better nucleotide transition polarization assignments.

  18. Probing Magnetic Susceptibility Anisotropy of Large-Diameter Armchair Carbon Nanotubes via Magnetic Linear Dichroism Spectroscopy

    NASA Astrophysics Data System (ADS)

    Haroz, Erik; Kono, Junichiro; Searles, Thomas; Tu, Xiaomin; Zheng, Ming; Fagan, Jeffrey; McGill, Stephen; Smirnov, Dmitry

    2012-02-01

    We studied magnetic susceptibility anisotropy, via magnetic linear dichroism spectroscopy, of aqueous suspensions of single-walled carbon nanotubes in high magnetic fields up to 22T using a unique magnet system (Split-Florida Helix magnet). Specifically, we measured magnetic susceptibility anisotropies, δχ, of several armchair species ranging from (5,5)-(13,13) at room temperature over an excitation wavelength range of 400-900 nm. For large diameter armchairs such as (12,12) and (13,13), we have observed some of the strongest alignment in a static magnetic field due to their large diameters. Results will be discussed in comparison with detailed calculations involving the Aharonov-Bohm effect.

  19. Absorption dichroism of monolayer 1T‧-MoTe2 in visible range

    NASA Astrophysics Data System (ADS)

    Han, Gang Hee; Keum, Dong Hoon; Zhao, Jiong; Shin, Bong Gyu; Song, Seunghyun; Bae, Jung Jun; Lee, Jubok; Kim, Jung Ho; Kim, Hyun; Moon, Byoung Hee; Lee, Young Hee

    2016-09-01

    Among various transition metal dichalcogenides, MoTe2 has drawn attention due to its capability of robust phase engineering between semiconducting (2H) and semi-metallic distorted octahedral (1T‧) phase. In particular, 1T‧-MoTe2 has been predicted to have intriguing physics such as quantum spin Hall insulator, large magnetoresistance, and superconductivity. Recent progress showed weak antilocalization behavior in 1T‧-MoTe2 which is the one of representative characteristics in topological insulator. Here, we grow centimeter-scale monolayer 1T‧-MoTe2 on SiO2/Si substrate via chemical vapordeposition and demonstrate dichroism in visible range. Ribbon-like 1T‧-MoTe2 flakes were initially nucleated randomly on SiO2 substrate and at a later stage merged to form a continuous monolayer film over the entire substrate. Each flake revealed one dimensional Mo-Mo dimerization feature and anisotropic absorption behavior in visible range (400-600 nm). This allowed us to detect the grain boundary due to stark contrast difference among flakes in different orientations.

  20. Absorption dichroism of monolayer 1T‧-MoTe2 in visible range

    NASA Astrophysics Data System (ADS)

    Han, Gang Hee; Keum, Dong Hoon; Zhao, Jiong; Shin, Bong Gyu; Song, Seunghyun; Bae, Jung Jun; Lee, Jubok; Kim, Jung Ho; Kim, Hyun; Moon, Byoung Hee; Lee, Young Hee

    2016-09-01

    Among various transition metal dichalcogenides, MoTe2 has drawn attention due to its capability of robust phase engineering between semiconducting (2H) and semi-metallic distorted octahedral (1T‧) phase. In particular, 1T‧-MoTe2 has been predicted to have intriguing physics such as quantum spin Hall insulator, large magnetoresistance, and superconductivity. Recent progress showed weak antilocalization behavior in 1T‧-MoTe2 which is the one of representative characteristics in topological insulator. Here, we grow centimeter-scale monolayer 1T‧-MoTe2 on SiO2/Si substrate via chemical vapordeposition and demonstrate dichroism in visible range. Ribbon-like 1T‧-MoTe2 flakes were initially nucleated randomly on SiO2 substrate and at a later stage merged to form a continuous monolayer film over the entire substrate. Each flake revealed one dimensional Mo–Mo dimerization feature and anisotropic absorption behavior in visible range (400–600 nm). This allowed us to detect the grain boundary due to stark contrast difference among flakes in different orientations.

  1. Calculated x-ray linear dichroism spectra for Gd-doped GaN

    NASA Astrophysics Data System (ADS)

    Cheiwchanchamnangij, Tawinan; Lambrecht, Walter

    2013-03-01

    Gd doped GaN has been claimed to be a dilute magnetic semiconductor with colossal magnetic moments. However, the origin of huge magnetic moments is still controversial. The x-ray linear dichroism (XLD) spectrum of the Gd L3 edge and the multiple scattering calculations from Ney et al. (J. Magn. Magn. Mater. 322, 1162 (2010)) suggested that about 15% of Gd atoms should be on antisites. In contrast, our first principle calculations indicate that once the Gd is put on the N site, it will move to the interstitial site and cause large structure relaxation. The formation energy of the system is, therefore, in the order of 10 eV per Gd atom which is extremely large. We show that XLD spectra for L-edges can be analyzed in terms of suitable linear combinations of the partial densities of states of the Gd d-electrons. Core-hole effects are also included. The XLD spectra extracted from our calculations of Gd on the Ga site is shown to fit the experimental spectrum and no Gd on the N site is needed.

  2. Linear Dichroism of Cyanine Dyes in Stretched Polyvinyl Alcohol Films: A Physical Chemistry Laboratory Experiment.

    ERIC Educational Resources Information Center

    Natarajan, L. V.; And Others

    1983-01-01

    Provides background information, procedures, and results of an undergraduate physical chemistry experiment on the polarization of absorption spectra of cyanine dyes in stretched polyvinyl alcohol films. The experiment gives a simple demonstration of the concept of linear dichromism and the validity of the TEM method used in the analyses. (JN)

  3. Infrared linear dichroism investigations of deoxyribonucleic complexes with histones H2B and H3.

    PubMed

    Liquier, J; Taboury, J; Taillandier, E; Brahms, J

    1977-07-12

    Complexes between DNA and histones H2B and H3 were studies by means of infrared linear dichroism in a wide range of histone to DNA ratios and of different relative humidities. The measurement of the dichroic ratios allows one to determine the secondary structure of DNA in the complexes. It is shown that the progressive addition of histone H2B or H3 to DNA inhibits the structural B leads to A transition and DNA remains in a B-type form at low relative humidity. A new simple method is proposed to evaluate the amount of A or B forms of DNA when both structures are present. It is found that the B leads to A transition is fully inhibited when only one molecule of H2B or H3 histone is bound per about three or four turns of DNA helix, respectively. It is proposed that about four to three turns of DNA helix represent the "critical length of DNA" (minimum "cooperative unit") for the B leads to A transition.

  4. Symmetry of valence states of Heusler compounds explored by linear dichroism in hard-x-ray photoelectron spectroscopy.

    PubMed

    Ouardi, Siham; Fecher, Gerhard H; Kozina, Xeniya; Stryganyuk, Gregory; Balke, Benjamin; Felser, Claudia; Ikenaga, Eiji; Sugiyama, Takeharu; Kawamura, Naomi; Suzuki, Motohiro; Kobayashi, Keisuke

    2011-07-15

    This study reports on the linear dichroism in angular-resolved photoemission from the valence band of the Heusler compounds NiTi0.9Sc0.1Sn and NiMnSb. High-resolution photoelectron spectroscopy was performed with an excitation energy of hν = 7.938  keV. The linear polarization of the photons was changed using an in-vacuum diamond phase retarder. The valence band spectra exhibit the typical structure expected from first-principles calculations of the electronic structure of these compounds. Noticeable linear dichroism is found in the valence band of both materials, and this allows for a symmetry analysis of the contributing states. The differences in the spectra are found to be caused by symmetry-dependent angular asymmetry parameters, and these occur even in polycrystalline samples without preferential crystallographic orientation.

  5. Synchrotron radiation linear dichroism spectroscopy of the antibiotic peptide gramicidin in lipid membranes.

    PubMed

    Hicks, Matthew R; Dafforn, Timothy R; Damianoglou, Angeliki; Wormell, Paul; Rodger, Alison; Hoffmann, Søren V

    2009-08-01

    We have developed synchrotron radiation linear dichroism (SRLD) to measure the insertion of peptides into lipid bilayers, significantly improving both signal-to-noise and wavelength range over existing methods. Our wavelength cut-off is currently determined by the quality of quartz in the cell, rather than the light source, with signal quality still high at the cut-off. We demonstrate the use of a lipid probe to measure the orientation of the lipid bilayers under flow and describe the way in which this can be used to further interpret SRLD data. The antibiotic peptide gramicidin is shown to exhibit drastically different kinetic and equilibrium behaviour when interacting with lipid membranes with different properties. The charge on the membrane is of interest because of differences in charge between human and bacterial membranes. For this reason we increased the negative charge on the membrane by changing the lipid composition. Increasing negative charge in the gel phase stabilises the liposomes but changes the kinetics of peptide folding. In a gel phase with no negatively charged lipids, gramicidin does not fold well and gives a small signal that indicates a change in orientation of the tryptophan side chains over time. In the fluid phase with no negatively charged lipids, there is initially >10-fold greater peptide signal relative to the gel phase indicating a highly folded and ordered gramicidin backbone. This is followed by liposome disruption. In the gel phase with negatively charged lipids the liposomes are resistant to disruption by gramicidin and exhibit different folding kinetics depending on membrane composition. In the fluid phase with negatively charged lipids there is little signal from either the peptide or the lipid probe indicating that the liposomes have been disrupted by the gramicidin in the time it takes to make the first measurement.

  6. Flexible bent rod model with a saturating induced dipole moment to study the electric linear dichroism of DNA fragments

    NASA Astrophysics Data System (ADS)

    Bertolotto, Jorge A.; Umazano, Juan P.

    2016-06-01

    In the present work we make a theoretical study of the steady state electric linear dichroism of DNA fragments in aqueous solution. The here developed theoretical approach considers a flexible bent rod model with a saturating induced dipole moment. The electric polarizability tensor of bent DNA fragments is calculated considering a phenomenological model which theoretical and experimental backgroung is presented here. The model has into account the electric polarizability longitudinal and transversal to the macroion. Molecular flexibility is described using an elastic potential. We consider DNA fragments originally bent with bending fluctuations around an average bending angle. The induced dipole moment is supposed constant once the electric field strength grows up at critical value. To calculate the reduced electric linear dichroism we determine the optical factor considering the basis of the bent DNA perpendicular to the molecular axis. The orientational distribution function has into account the anisotropic electric properties and the molecule flexibility. We applied the present theoretical background to fit electric dichroism experimental data of DNA fragments reported in the bibliography in a wide range of molecular weight and electric field. From these fits, values of DNA physical properties are estimated. We compare and discuss the results here obtained with the theoretical and experimental data presented by other authors. The original contributions of this work are: the inclusion of the transversal electric polarizability saturating with the electric field, the description of the electric properties with an electric polarizability tensor dependant on the bending angle and the use of an arc model originally bent.

  7. Electronic states of benzo[a]pyrene. Linear and magnetic circular dichroism, polarized fluorescence, and quantum chemical calculations

    SciTech Connect

    Spanget-Larsen, J.; Waluk, J.; Erikksson, S.

    1992-03-11

    The carcinogen benzo[a]pyrene is investigated by UV and IR linear dichroism (LD) spectroscopy in stretched polyethylene, by UV magnetic circular dichroism (MCD) spectroscopy, and by fluorescence polarization spectroscopy. The combined results lead to detailed experimental characterization of transitions in the near-UV region, with determination of polarization directions for five electronic transitions. The experimental results are compared with theoretical predictions using the PPP, CNDO/S, CNDO-SDCI, and LCOAO quantum chemical models. Excellent agreement with observed values in the low-energy region, including transition transition moment directions and MCD signs, is obtained within the LCOAO model. The theoretical analysis reveals a strong breakdown of the alternant pairing symmetry for benzo[a]pyrene, compared with those observed in the related hydrocarbons benz[a]anthracene and chrysene. 44 refs., 7 figs., 4 tabs.

  8. Domain imaging on multiferroic BiFeO{sub 3}(001) by linear and circular dichroism in threshold photoemission

    SciTech Connect

    Sander, Anke; Christl, Maik; Chiang, Cheng-Tien; Alexe, Marin; Widdra, Wolf

    2015-12-14

    We demonstrate ferroelectric domain imaging at BiFeO{sub 3}(001) single crystal surfaces with laser-based threshold photoemission electron microscopy (PEEM). Work function differences and linear dichroism allow for the identification of the eight independent ferroelectric domain configurations in the PEEM images. There, the determined domain structure is consistent with piezoresponse force microscopy of the sample surface and can also be related to the circular dichroic PEEM images. Our results provide a method for efficient mapping of complex ferroelectric domains with laser-excited PEEM and may allow lab-based time-resolved studies of the domain dynamics in the future.

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

    SciTech Connect

    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.

  10. Observation of x-ray absorption magnetic circular dichroism in well-characterized iron-cobalt-platinum multilayers

    SciTech Connect

    Jankowski, A.F.; Waddill, G.D.; Tobin, J.G.

    1993-04-01

    Magnetic circular dichroism in the Fe 2p x-ray absorption is observed in multilayers of(Fe9.5{Angstrom}/Pt9.5{Angstrom}){sub 92}. The magnetization and helicity are both in the plane of this multilayer which is prepared by magnetron sputter deposition. This sample is part of a study to examine magnetization in the ternary multilayer system of FeCo/Pt. Lattice and layer pair spacings are measured using x-ray scattering. The atomic concentration profiles of the multilayer films are characterized using Auger electron spectroscopy coupled with depth profiling. Conventional and high resolution transmission electron microscopy are used to examine the thin film, growth morphology and atomic structure.

  11. Optical and structural properties of plasma-treated Cordyceps bassiana spores as studied by circular dichroism, absorption, and fluorescence spectroscopy

    NASA Astrophysics Data System (ADS)

    Lee, Geon Joon; Sim, Geon Bo; Choi, Eun Ha; Kwon, Young-Wan; Kim, Jun Young; Jang, Siun; Kim, Seong Hwan

    2015-01-01

    To understand the killing mechanism of fungal spores by plasma treatment, the optical, structural, and biological properties of the insect pathogenic fungus Cordyceps bassiana spores were studied. A nonthermal atmospheric-pressure plasma jet (APPJ) was used to treat the spores in aqueous solution. Optical emission spectra of the APPJ acquired in air indicated emission peaks corresponding to hydroxyl radicals and atomic oxygen. When the APPJ entered the aqueous solution, additional reactive species were derived from the interaction of plasma radicals with the aqueous solution. Fluorescence and absorption spectroscopy confirmed the generation of hydroxyl radicals and hydrogen peroxide in the plasma-activated water (PAW). Spore counting showed that plasma treatment significantly reduced spore viability. Absorption spectroscopy, circular dichroism (CD) spectroscopy, and agarose gel electrophoresis of the DNA extracted from plasma-treated spores showed a reduction in spore DNA content. The magnitude of the dip in the CD spectrum was lower in the plasma-treated spores than in the control, indicating that plasma treatment causes structural modifications and/or damage to cellular components. Tryptophan fluorescence intensity was lower in the plasma-treated spores than in the control, suggesting that plasma treatment modified cell wall proteins. Changes in spore viability and DNA content were attributed to structural modification of the cell wall by reactive species coming from the APPJ and the PAW. Our results provided evidence that the plasma radicals and the derived reactive species play critical roles in fungal spore inactivation.

  12. Optical and structural properties of plasma-treated Cordyceps bassiana spores as studied by circular dichroism, absorption, and fluorescence spectroscopy

    SciTech Connect

    Lee, Geon Joon Sim, Geon Bo; Choi, Eun Ha; Kim, Jun Young; Jang, Siun; Kim, Seong Hwan

    2015-01-14

    To understand the killing mechanism of fungal spores by plasma treatment, the optical, structural, and biological properties of the insect pathogenic fungus Cordyceps bassiana spores were studied. A nonthermal atmospheric-pressure plasma jet (APPJ) was used to treat the spores in aqueous solution. Optical emission spectra of the APPJ acquired in air indicated emission peaks corresponding to hydroxyl radicals and atomic oxygen. When the APPJ entered the aqueous solution, additional reactive species were derived from the interaction of plasma radicals with the aqueous solution. Fluorescence and absorption spectroscopy confirmed the generation of hydroxyl radicals and hydrogen peroxide in the plasma-activated water (PAW). Spore counting showed that plasma treatment significantly reduced spore viability. Absorption spectroscopy, circular dichroism (CD) spectroscopy, and agarose gel electrophoresis of the DNA extracted from plasma-treated spores showed a reduction in spore DNA content. The magnitude of the dip in the CD spectrum was lower in the plasma-treated spores than in the control, indicating that plasma treatment causes structural modifications and/or damage to cellular components. Tryptophan fluorescence intensity was lower in the plasma-treated spores than in the control, suggesting that plasma treatment modified cell wall proteins. Changes in spore viability and DNA content were attributed to structural modification of the cell wall by reactive species coming from the APPJ and the PAW. Our results provided evidence that the plasma radicals and the derived reactive species play critical roles in fungal spore inactivation.

  13. X-ray absorption spectroscopy and magnetic circular dichroism studies of L1{sub 0}-Mn-Ga thin films

    SciTech Connect

    Glas, M. Sterwerf, C.; Schmalhorst, J. M.; Reiss, G.; Ebke, D.; Jenkins, C.; Arenholz, E.

    2013-11-14

    Tetragonally distorted Mn{sub 3−x}Ga{sub x} thin films with 0.1absorption spectroscopy (XAS) and magnetic circular dichroism (XMCD). A highly textured L1{sub 0} crystal structure of the Mn-Ga films was verified by X-ray diffraction measurements. For samples with e-beam evaporated MgO barrier no evidence for Mn-O was found whereas in samples with magnetron sputtered MgO, Mn-O was detected, even for the thickest interlayer thickness. Both XAS and XMCD measurements showed an increasing interfacial Mn-O amount with decreasing CoFeB interlayer thickness. Additional element specific full hysteresis loops determined an out-of-plane magnetization axis for the Mn and Co, respectively.

  14. Angular dependence in infrared linear dichroism: a reevaluation of the theory.

    PubMed

    Gregoriou, Vasilis G; Tzavalas, Spiros; Bollas, Stavros T

    2004-06-01

    Parameters such as the viewing angle and the extinction ratio (the ratio of the transmitted light over the total light intensity that reaches the sample) are very important in the design of novel optical devices such as new types of polarizers, liquid crystal displays, etc. The initial aim of this work was the comparison of experimentally obtained results to the currently accepted theoretical model that is based on Zbinden's theory of intensity ellipsoid. Due to observed discrepancies between the above theory and experimental data, a new mathematical model was generated in order to adequately explain the experimental results. This new theory allows the calculation of light absorbance at every combination of azimuthal and tilt angles in complete agreement with the experimentally determined values. In addition, in this paper we settle, once and for all, the confusion that exists in the spectroscopic literature with regard to the dependence of absorption and transmission values vis-à-vis the angle of incidence of the incoming light. We conclusively show that it is absorptance (alpha) and not absorption or absorbance (A) which shows a cos(2) dependence on the angle formed by the electric vector and the dipole.

  15. Photo-physics study of an hydroxy-quinoline derivative as inhibitor of Pim-1 kinase: ultraviolet-visible linear dichroism spectroscopy and quantum chemical calculations.

    PubMed

    Lamhasni, T; Ait Lyazidi, S; Hnach, M; Haddad, M; Desmaële, D; Spanget-Larsen, J; Nguyen, D D; Ducasse, L

    2013-09-01

    The photophysical properties of the antiviral 7-nicotinoyl-styrylquinoline (MB96) were investigated by means of UV-Vis linear dichroism (LD) spectroscopy on molecular samples aligned in stretched polyvinylalcohol (PVA), supported by time dependent density functional theory (TD-DFT) calculations. Experimentally, the directions of the transitions moments with respect to the long axis of the molecule were deduced from the orientation K factors, determined by means of "trial-and-error" procedure. The absorption spectrum presents two parts. The main transition in the lowest energy part, observed around 365 nm and showing the highest K value 0.8, is longitudinally in-plane polarized. The highest energy part which is extended between 230 and 320 nm, large, diffuse, and of weak intensity, shows estimated K values between 0.2 and 0.5. This complex structure is transversally polarized with some contamination by the longitudinal character of the first strong band. The TD-DFT results agree fairly well with the LD measurements.

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

    PubMed

    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. PMID:27036761

  17. An analysis of the x-ray linear dichroism spectrum for NiO thin films grown on vicinal Ag(001)

    SciTech Connect

    Wu, Y.Z.; Zhao, Y.; Arenholz, E.; Young, A.T.; Sinkovic, B.; Qiu, Z.Q.

    2008-05-10

    Antiferromagnetic (AFM) NiO thin films are grown epitaxially on vicinal Ag(118) substrate and investigated by x-ray linear dichroism (XLD). We find that the NiO AFM spin exhibits an in-plane spin reorientation transition from parallel to perpendicular to the step edges with increasing the NiO film thickness. In addition to the conventional L{sub 2} adsorption edge, x-ray linear dichroism (XLD) effect at the Ni L{sub 3} adsorption edge is also measured and analyzed. The result identifies a small energy shift of the L{sub 3} peak. Temperature-dependent measurement confirms that the observed XLD effect in this system at the normal incidence of the x-rays originates entirely from the NiO magnetic ordering.

  18. Circular dichroism and optical absorption spectra of mononuclear and trinuclear chiral Cu(II) amino-alcohol coordinated compounds: A combined theoretical and experimental study

    NASA Astrophysics Data System (ADS)

    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.

  19. Circular dichroism in magnesium sulfite hexahydrate doped with cobalt

    NASA Astrophysics Data System (ADS)

    Bunzarov, Zh.; Iliev, I.; Dimov, T.; Petkova, P.; Kovachev, Tz.; Lyutov, L.; Tzoukrovski, Y.

    2009-10-01

    The new nonlinear crystal of magnesium sulfite hexahydrate (MgSO3.6H2O) belongs to the rare crystallographic class C3 (without a symmetry centre), the other known only representative being sodium periodate (NaIO4). There are some scarce data in the scientific papers about magnesium sulfite hexahydrate's physical properties. Single crystals of significant sizes (up to 40-50 mm) of MgSO3.6H2O as well as such, doped with Ni, Co, and Zn, for the time being are grown only by our own method developed in the Laboratory for Crystal growth at the Faculty of Physics of Sofia University. Recently we have observed the supposed presence of optical activity. Circular dichroism is not observed in pure MgSO3.6H2O. The results of the first ever investigations are presented, which demonstrate the presence of circular dichroism in MgSO3.6H2O doped with Co. The circular dichroism appears in the spectral range from 420 nm to 580 nm. The spectrum of circular dichroism demonstrates a well expressed structure - an isolated maximum at 470 nm and a combination of two overlapped maxima at ~ 495 nm and 520 nm respectively. The spectrum of the circular dichroism is compared with the absorption spectrum of MgSO3.6H2O:Co, along the direction (0001) and with the linear dichroism spectrum measured in direction(1210). It is shown in this way that the circular dichroism appears only in the spectral range of the optical absorption structure due to Co dopant. In the same spectral range can be observed also the linear dichroism determined by Co presence in MgSO3.6H2O.

  20. Direct surface magnetometry with photoemission magnetic x-ray dichroism

    SciTech Connect

    Tobin, J.G.; Goodman, K.W.; Schumann, F.O.

    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.

  1. Interaction between adenovirus DNA-binding protein and single-stranded polynucleotides studied by circular dichroism and ultraviolet absorption.

    PubMed

    van Amerongen, H; van Grondelle, R; van der Vliet, P C

    1987-07-28

    The adenovirus DNA-binding protein (AdDBP) is a multifunctional protein required for viral DNA replication and control of transcription. We have studied the binding of AdDBP to single-stranded M13 DNA and to the homopolynucleotides poly(rA), poly(dA), and poly(dT) by means of circular dichroism (CD) and optical density (OD) measurements. The binding to all these polynucleotides was strong and nearly stoichiometric. Titration experiments showed that the size of the binding site is 9-11 nucleotides long for M13 DNA, poly(dA), and poly(rA). A higher value (15.0 +/- 0.8) was found for poly(dT). Pronounced changes in the circular dichroism and optical density spectra were observed upon binding of AdDBP. In general, both the positive peak around 260-270 nm and the negative peak around 240-250 nm in the CD spectra decreased in intensity, and a shift of the crossover point to longer wavelengths was found. The OD spectra observed upon binding of AdDBP are remarkably similar to those obtained with prokaryotic helix-destabilizing proteins like bacteriophage T4 gene 32 protein and fd gene 5 protein. The data can best be interpreted by assuming that the AdDBP-polynucleotide complex has a regular, rigid, and extended configuration that satifies two criteria: (1) a considerable tilt of the bases in combination with (2) a small rotation per base and/or a shift of the bases closer to the helix axis.

  2. Magnetic and structural properties of Fe/Pd multilayers studied by magnetic x-ray dichroism and x-ray absorption spectroscopy

    SciTech Connect

    Mini, S.M. |; Fullerton, E.E.; Sowers, C.H.; Fontaine, A.; Pizzini, S.; Bommannavar, A.S.; Traverse, A.; Baudelet, F.

    1994-12-01

    The results of magnetic circular x-ray dichroism (MCXD) measurements and extended x-ray absorption fine structure measurements (EXAFS) of the Fe K-edges of textured Fe(110)/Pd(111) multilayers are reported. The EXAFS results indicates that the iron in the system goes from bcc to a more densely packed system as the thickness of the iron layer is decreased. The magnetic properties were measured by SQUID magnetometry from 5-350 K. For all the samples, the saturation magnetization was significantly enhanced over the bulk values indicating the interface Pd atoms are polarized by the Fe layer. The enhancement corresponds to a moment of {approx}2.5{mu}{sub B} per interface Pd atom.

  3. Investigation of the electronic absorption spectra and the circular dichroism spectra of binuclear tetra-. mu. -mandelato complexes of Mo/sub 2//sup 4 +/

    SciTech Connect

    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.

  4. Absorption mode Fourier transform electrostatic linear ion trap mass spectrometry.

    PubMed

    Hilger, Ryan T; Wyss, Phillip J; Santini, Robert E; McLuckey, Scott A

    2013-09-01

    In Fourier transform mass spectrometry, it is well-known that plotting the spectrum in absorption mode rather than magnitude mode has several advantages. However, magnitude spectra remain commonplace due to difficulties associated with determining the phase of each frequency at the onset of data acquisition, which is required for generating absorption spectra. The phasing problem for electrostatic traps is much simpler than for Fourier transform ion cyclotron resonance (FTICR) instruments, which greatly simplifies the generation of absorption spectra. Here, we present a simple method for generating absorption spectra from a Fourier transform electrostatic linear ion trap mass spectrometer. The method involves time shifting the data prior to Fourier transformation in order to synchronize the onset of data acquisition with the moment of ion acceleration into the electrostatic trap. Under these conditions, the initial phase of each frequency at the onset of data acquisition is zero. We demonstrate that absorption mode provides a 1.7-fold increase in resolution (full width at half maximum, fwhm) as well as reduced peak tailing. We also discuss methodology that may be applied to unsynchronized data in order to determine the time shift required to generate an absorption spectrum.

  5. Retinoic acid binding properties of the lipocalin member beta-lactoglobulin studied by circular dichroism, electronic absorption spectroscopy and molecular modeling methods.

    PubMed

    Zsila, Ferenc; Bikádi, Zsolt; Simonyi, Miklós

    2002-12-01

    Interaction between the Vitamin A derivative all-trans retinoic acid and the lipocalin member bovine beta-lactoglobulin (BLG) was studied by circular dichroism (CD) and electronic absorption spectroscopy at different pH values. In neutral and alkaline solutions achiral retinoic acid forms a non-covalent complex with the protein as indicated by the appearance of a negative Cotton effect around 347 nm associated to the narrowed and red shifted pi-pi(*) absorption band of the ligand. The induced optical activity is attributed to the helical distortion of the conjugated chain caused by the chiral protein binding environment. As the disappearing CD activity showed in the course of CD-pH titration experiment, retinoic acid molecules dissociate from BLG upon acidification but this release is completely reversible as proved by the reconstitution of the CD and absorption spectra after setting the pH back to neutral. This unique behavior of the complex is explained by the conformational change of BLG (Tanford transition) which involves a movement of the EF loop at the entrance of the central cavity from open to closed conformation in the course of pH lowering. From these results it was inferred that retinoic acid binds within the hydrophobic calyx of the beta-barrel. PMID:12429354

  6. X-ray magnetic circular dichroism and x-ray absorption spectroscopy of novel magnetic thin films

    SciTech Connect

    Brewer, M.A.; Ju, H.L.; Krishnan, K.M.

    1997-04-01

    The optimization of the magnetic properties of materials for a wide range of applications requires a dynamic iteration between synthesis, property measurements and characterization at appropriate length scales. The authors interest arises both from the increased appreciation of the degree to which magnetic properties can be influenced by tailored microstructures and the ability to characterize them by x-ray scattering/dichroism techniques. Preliminary results of this work at the ALS on `giant` moment in {alpha}{double_prime}-Fe{sub 16}N{sub 2} and `colossal` magnetoresistance in manganite perovskites is presented here. It has recently been claimed that {alpha}{double_prime}-Fe{sub 16}N{sub 2} possesses a giant magnetization of 2.9 T ({approximately}2300 emu/cc) when grown on lattice-matched In{sub 0.2}Ga{sub 0.8}As(001) and Fe/GaAs(001). However, attempts at growth on simpler substrates have resulted in only a modest enhancement in moment and often in multiphase mixtures. Theoretical calculations based on the band structure of Fe{sub 16}N{sub 2} predict values for the magnetization around 2.3 T ({approximately}1780 emu/cc), well below Sugita`s claims, but consistent with the magnetization reported by several other workers. Using appropriate sum rules applied to the integrated MCD spectrum, they hope to determine the magnetic moment of the iron species in the {alpha}{double_prime}-Fe{sub 16}N{sub 2} films and other phases and resolve the orbital and spin contributions to the moment. There is also rapidly growing interest in the `colossal magnetoresistance` effect observed in manganese oxides for both fundamental and commercial applications. To address some of these issues the authors have measured the electron energy loss spectra (EELS) of manganese perovskites at room temperature.

  7. Study of the Effect of the Pulse Width of the Excitation Source on the Two-Photon Absorption and Two-Photon Circular Dichroism Spectra of Biaryl Derivatives.

    PubMed

    Vesga, Yuly; Hernandez, Florencio E

    2016-09-01

    Herein we report on the expanded theoretical calculations and the experimental measurements of the two-photon absorption (TPA) and two-photon circular dichroism (TPCD) spectra of a series of optically active biaryl derivatives (R-BINOL, R-VANOL, and R-VAPOL) using femtosecond pulses. The comparative analysis of the experimental TPCD spectra obtained with our tunable amplified femtosecond system with those previously measured in our group on the same series of compounds in the picosecond regime reveals a decrease in the amplitude of the signal and an improvement in matching with the theory in the former. These results can be explained based on the negligible contribution of excited state absorption (ESA) using femtosecond pulses compared to the picosecond regime. We show how ESA affects both the strength of the signal and the shape of the TPA and TPCD spectra. TPA and TPCD spectra were obtained using the double L-scan technique over a broad spectral range (450-750 nm) using 90 fs pulses at 50 Hz repetition rate produced by an amplified femtosecond system. The theoretical calculations were performed using modern analytical response theory within the time-dependent density functional theory (TD-DFT) approach using CAM-B3LYP and 6-311++G(d,p) basis sets. PMID:27525702

  8. X-ray natural linear dichroism of graphitic materials across the carbon K-edge: Correction for perturbing high-order harmonics

    NASA Astrophysics Data System (ADS)

    Jansing, C.; Mertins, H. C.; Gaupp, A.; Sokolov, A.; Gilbert, M. C.; Wahab, H.; Timmers, H.

    2016-05-01

    Reflectivity measurements on graphitic materials such as graphene at energies across the carbon K-edge are frustrated by significant intensity loss due to adventitious carbon on beamline mirrors. Such intensity reduction enhances effects due to perturbing high-order harmonics in the beam. These effects distort the actual structure of the reflectance curve. In order to overcome this limitation, a correction technique has been developed and demonstrated first with measurements for highly ordered pyrolytic graphite. The same approach may be applied to other graphitic materials such as graphene and it may be used with other synchrotron beamlines. The fraction of high-order harmonics was determined by passing the incident beam through a 87 nm thin silicon nitride absorber that can be well modeled. Using the corrected measurements the x-ray natural linear dichroism of the sample has been determined.

  9. The magnetic circular dichroism spectra of the linear trinuclear clusters [Fe 3S 4(SR) 4] 3- in purple aconitase and in a synthetic model

    NASA Astrophysics Data System (ADS)

    Richards, A. J. M.; Thomson, A. J.; Holm, R. H.; Hagen, K. S.

    The low-temperature magnetic circular dichroism (MCD) spectra and MCD magnetization properties of the linear three-iron cluster [Fe(μ 2-S) 2Fe(μ 2-S) 2Fe] + have been compared in a solution of the model compound (Et 4N) 3[Fe 3S 4(SEt) 4] and in the "purple" form of beef heart aconitase. The similarity between the spectra confirms the close equivalence of the structures in the model and the protein. Analysis of the MCD magnetization curves has been carried out in terms of a ground state spin S = 5/2 and E / D values of 0.33 (model) and 0.31 (aconitase) established from the electron paramagnetic resonance (EPR) spectra. This gives estimates of the axial zero-field splitting parameters D = +0.7 ± 0.2 cm -1 and +1.5 ± 0.2 cm -1 for the model and protein, respectively.

  10. Tryptophan orientations in membrane-bound gramicidin and melittin-a comparative linear dichroism study on transmembrane and surface-bound peptides.

    PubMed

    Svensson, Frida R; Lincoln, Per; Nordén, Bengt; Esbjörner, Elin K

    2011-01-01

    In the search for methods to study structure and function of membrane-associated proteins and peptides flow linear dichroism, LD, spectroscopy has emerged as a promising technique. Using shear-aligned lipid vesicles, conformations and binding geometries of membrane-bound bio-macromolecules can be assessed. Here we investigate anchoring properties and specific orientations of tryptophan relative to the peptide backbone and to the membrane normal for the model peptides gramicidin and melittin. We have monitored the conformational change associated with the refolding of non-channel gramicidin into its channel form, and quantitatively determined the average orientations of its tryptophan transition moments, suggesting that these residues adopt a well-defined orientation at the membrane interface. An important conclusion regards the structural variation of gramicidin between these two distinct transmembrane forms. Whilst circular dichroism (CD) spectra, as has been reported before, vary strongly between the two forms suggesting their structures might be quite different, the LD results clearly evidence both the peptide backbone orientation and tryptophan side-chain positioning to be very similar. The latter are oriented in accord with what is expected from their role to anchor peptide termini to the membrane surface. The variations in CD could be due to, the in LD observed, minor shifts in mutual orientation and distance between neighbouring tryptophans sensitively determining their exciton interactions. Our data dispute that the non-channel form of membrane-bound gramicidin would be any of the intertwined forms often observed in crystal as the positioning of tryptophans along the peptide axis would not be compatible with the strong interfacial positioning observed here. The general role of tryptophans as interfacial anchors is further assessed for melittin whose conformation shows considerable angular spread, consistent with a carpet model of its mechanism for induced

  11. Disentanglement of magnetic contributions in multi-component systems by using X-ray magnetic circular dichroism at a single absorption edge.

    PubMed

    Chaboy, Jesús; Laguna-Marco, María Angeles; Piquer, Cristina; Boada, Roberto; Maruyama, Hiroshi; Kawamura, Naomi

    2008-09-01

    X-ray magnetic circular dichroism (XMCD) has become in recent years an outstanding tool for studying magnetism. Its element specificity, inherent to core-level spectroscopy, combined with the application of magneto-optical sum rules allows quantitative magnetic measurements at the atomic level. These capabilities are now incorporated as a standard tool for studying the localized magnetism in many systems. However, the application of XMCD to the study of the conduction-band magnetism is not so straightforward. Here, it is shown that the atomic selectivity is not lost when XMCD probes the delocalized states. On the contrary, it provides a direct way of disentangling the magnetic contributions to the conduction band coming from the different elements in the material. This is demonstrated by monitoring the temperature dependence of the XMCD spectra recorded at the rare-earth L(2)-edge in the case of RT(2) (R = rare-earth, T = 3d transition metal) materials. These results open the possibility of performing element-specific magnetometry by using a single X-ray absorption edge.

  12. Local electronic states of Fe{sub 4}N films revealed by x-ray absorption spectroscopy and x-ray magnetic circular dichroism

    SciTech Connect

    Ito, Keita; Toko, Kaoru; Suemasu, Takashi; Takeda, Yukiharu; Saitoh, Yuji; Oguchi, Tamio; Kimura, Akio

    2015-05-21

    We performed x-ray absorption spectroscopy (XAS) and x-ray magnetic circular dichroism (XMCD) measurements at Fe L{sub 2,3} and N K-edges for Fe{sub 4}N epitaxial films grown by molecular beam epitaxy. In order to clarify the element specific local electronic structure of Fe{sub 4}N, we compared experimentally obtained XAS and XMCD spectra with those simulated by a combination of a first-principles calculation and Fermi's golden rule. We revealed that the shoulders observed at Fe L{sub 2,3}-edges in the XAS and XMCD spectra were due to the electric dipole transition from the Fe 2p core-level to the hybridization state generated by σ* anti-bonding between the orbitals of N 2p at the body-centered site and Fe 3d on the face-centered (II) sites. Thus, the observed shoulders were attributed to the local electronic structure of Fe atoms at II sites. As to the N K-edge, the line shape of the obtained spectra was explained by the dipole transition from the N 1s core-level to the hybridization state formed by π* and σ* anti-bondings between the Fe 3d and N 2p orbitals. This hybridization plays an important role in featuring the electronic structures and physical properties of Fe{sub 4}N.

  13. Comparative study of optical absorption and circular dichroism of bacteriochlorophyll oligomers in Triton X-100, the antenna pigment B850, and the primary donor P-860 of photosynthetic bacteria indicates that all are similar dimers of bacteriochlorophyll a

    PubMed Central

    Scherz, A.; Rosenbach-Belkin, V.

    1989-01-01

    Dimers of bacteriochlorophyll a (Bchla) with optical absorption maximum at 853 nm and a nonconservative circular dichroism spectrum are formed in a solution of formamide/water that contains micelles of Triton X-100. The apparent equilibrium constant and the corresponding Gibbs energy change for the Bchl self-organization are 4.9 × 106 M-1 and -9.2 kcal/mol, respectively. The experimental absorption and circular dichroism spectra of the in vitro Bchl dimer (termed Bchl-853) are similar to the spectra of the bacterial light-harvesting complex B850 and the primary electron donor P-860 and probably point to a common structural motif. Indeed, simulation of the dimers' spectra (optical absorption and circular dichroism), achieved by using an extended version of the exciton theory, suggests the same geometry as recently elucidated for P-860 by x-ray diffraction crystallography. The proposed geometry is predicted to have the minimum energy in the gas phase. In conclusion, the spectral properties of the bathochromically shifted forms of Bchla are likely a result of strong dipolar interactions in self-organized structures of Bchls. PMID:16578840

  14. Vibrational absorption and vibrational circular dichroism spectra of leucine in water under different pH conditions: Hydrogen-bonding interactions with water

    NASA Astrophysics Data System (ADS)

    Poopari, Mohammad Reza; Zhu, Peiyan; Dezhahang, Zahra; Xu, Yunjie

    2012-11-01

    Vibrational absorption (VA) and vibrational circular dichroism (VCD) spectroscopy have been used to study leucine, a flexible branched-chain amino acid, in aqueous solution. The VA spectra in the range of 1800-1250 cm-1 of leucine in D2O under three representative pHs from strongly acidic (pH = 1), near neutral (pH = 6), to strongly basic (pH = 13), have been measured. The related VCD spectrum has been obtained under near neutral condition. Searches have been carried out to identify the most stable conformers of the Zwitterionic, protonated, and deprotonated forms of leucine in water. The geometry optimization, harmonic frequency calculations, and VA and VCD intensities have been computed at the B3LYP/6-311++G(d,p) level with the implicit polarizable continuum solvation model. While the observed VA spectra under three pHs can be well interpreted with the inclusion of the implicit solvation model, both implicit and explicit solvation models have been found to be crucial for the adequate interpretation of the complex VCD features observed. Molecular dynamics simulations and radial distribution functions have been used to aid the modeling of the leucine-(water)N clusters. It has been recognized that the insertion of a water molecule between the COO- and NH3+ functional groups in the explicit solvated clusters is critical to reproduce the VCD signatures observed. Furthermore, the inclusion of the implicit bulk water environment has been found to be essential to lock water molecules, which are directly hydrogen bonded to leucine, into the positions expected in solution. The application of the explicit and implicit solvation models simultaneously allows new insights into the hydrogen bonding network surrounding leucine in aqueous solution and the role of the surrounding bulk water in stabilizing such hydrogen-bonding network.

  15. Infrared linear dichroism studies of DNA-drug complexes: quantitative determination of the drug-induced restriction of the B-A transition.

    PubMed Central

    Fritzsche, H

    1994-01-01

    The B-A transition of films or fibers of NaDNA occurs at a relative humidity of 75-85%. The fraction of DNA that changed the conformation from B to A form can be determined quantitatively by infrared linear dichroism. DNA-binding drugs can 'freeze' a fraction of DNA in the B form. This fraction of DNA is in the B form and cannot be converted to A-DNA even at a reduced relative humidity of 54%. The 'freezing' potentiality of various drugs can be described by the 'freezing' index, FI, expressed in base pairs per added drug. Drugs with a high value of FI (more than eight base pairs per drug) were observed among both intercalating and groove-binding drugs. High values of FI imply restriction of the conformational flexibility of DNA significantly going beyond the binding site of the drug. This long-range effect of drugs on the conformational flexibility of DNA may be connected with the molecular mechanism of drug action. The freezing index FI is a new quantitative parameter of drug-DNA interaction that should be considered as a valuable tool for drug design. PMID:8139919

  16. Impact of energy-related pollutants on chromosome structure. Progress report, January 1-December 31, 1980. IQUID COLUMN CHROMATOGRAPHY; ABSORPTION SPECTRA; COMPUTER CODES; DICHROISM; EQUIPMENT INTERFACES; MICROPROCESSORS; SPECTROPHOTOMETERS; ; CARBON 13; COMPLEXES; NUCLEAR MAGNETIC RESONANCE

    SciTech Connect

    Not Available

    1980-01-01

    Methods for rapidly analyzing methylated and ethylated nucleosides and bases by high pressure liquid chromatography were investigated. Deoxyribonucleotides were alkylated with alkyl iodides and dialkyl sulfates. Several unreported products of the reactions of methyl and ethyl iodide in dimethylsulfoxide were found and are being characterized. The Cary 219 UV-Vis spectrophotometer was interfaced to a microcomputer and several utility programs were written. Preliminary absorption and circular dichroism studies of the binding of ethidium to DNA and nucleosome cores showed binding to cores to be quite different from binding to DNA. Free radical and additional reactions of bisulfite with DNA in chromatin were examined. Free radical attack was minimal. Some conversion of cytosine to uracil was noted, but protein crosslinking to DNA was not detected. The first valid natural abundance /sup 13/C nmr spectra of double-stranded DNA and double-stranded DNA complexed with ethidium were obtained. These spectra suggested that DNA undergoes considerable internal motion. The data show that 13-C nmr studies of the conformational and motional properties of native DNA and of complexes of native DNA with small molecules are practical and promising. Studies of subnucleosomes derived from nucleosomes were completed. Based on these studies, a model of the linear arrangement of histone C-terminal and N-terminal chain regions along nucleosome DNA was proposed. The use of staphylococcal protease to probe histone conformations in nucleosomes was explored. Preliminary data indicate that H3 is much more susceptible to protease than other core histones, and is cleaved in its hydrophobic domain. A procedure for fractionating chromatin was alos developed. (ERB)

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

    SciTech Connect

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

  19. Hydration of the dienic lipid dioctadecadienoylphosphatidylcholine in the lamellar phase--an infrared linear dichroism and x-ray study on headgroup orientation, water ordering, and bilayer dimensions.

    PubMed Central

    Binder, H; Gutberlet, T; Anikin, A; Klose, G

    1998-01-01

    In the phospholipid 1,2-bis(2,4-octadecadienoyl)-sn-glycero-3-phosphorylcholine (DODPC) in each of the fatty acid chains, a rigid diene group is inserted in a position near the polar/apolar boundary that is exceptionally sensitive for membrane stability. DODPC transforms upon gradual dehydration from the liquid-crystalline to a metastable gel state, which rearranges into two subgel phases at low and intermediate degrees of hydration. The molecular dimensions of the respective bilayers were determined by means of x-ray diffraction. Infrared linear dichroism of selected vibrations of the phosphate and trimethylammonium groups and of the nu13(OH) band of water adsorbed onto the lipid was used to study the molecular order in the polar part of the bilayers in macroscopically oriented samples. The dense packing of the tilted acyl chains in the subgel causes the in-plane orientation of the phosphatidylcholine headgroups with direct interactions between the phosphate and trimethylammonium groups, and a strong orientation of adsorbed water molecules. In the more disordered gel, the thickness of the polar part of the bilayer increases and the lateral interactions between the lipid headgroups weaken. The higher order in the headgroup region of the subgels correlates with shorter decay lengths of the repulsive forces acting between opposite membrane surfaces. This result can be understood if the work to dehydrate the lipid is determined to a certain degree by the work to break up the lipid-water interactions without compensation by adequate lipid-lipid contacts. Almost similar area compressibility moduli are found in the liquid-crystalline and solid phases. Obviously, the lipid avoids lateral stress by the structural rearrangement. PMID:9545052

  20. Simulation of magnetic circular dichroism in the electron microscope

    NASA Astrophysics Data System (ADS)

    Rubino, Stefano; Schattschneider, Peter; Rusz, Jan; Verbeeck, Johan; Leifer, Klaus

    2010-12-01

    As electron energy-loss spectroscopy (EELS) and x-ray absorption spectroscopy (XAS) probe the same transitions from core-shell states to unoccupied states above the Fermi energy, it should always be possible to apply the two techniques to the same physical phenomena, such as magnetic dichroism, and obtain the same information. Indeed, the similarity in the expression of the electron and x-ray cross-sections had been already exploited to prove the equivalence of x-ray magnetic linear dichroism and anisotropy in EELS, by noting that the polarization vector of a photon plays the same role as the momentum transfer in electron scattering. Recently, the same was proven true for x-ray magnetic circular dichroism (XMCD) by establishing a new TEM technique called EMCD (electron energy-loss magnetic chiral dichroism) (Schattschneider P et al 2006 Nature 441 486-8), which makes use of special electron scattering conditions to force the absorption of a circularly polarized virtual photon. The intrinsic advantage of EMCD over XMCD is the high spatial resolution of electron microscopes, which are readily available. Among the particular obstacles in EMCD that do not exist for synchrotron radiation, is the notoriously low signal and the very particular scattering conditions necessary to observe a chiral dichroic signal. In spite of that, impressive progress has been made in recent years. The signal strength could be considerably increased, and some innovations such as using a convergent beam have been introduced. EMCD has evolved into several techniques, which make full use of the versatility of the TEM and energy filtering, spectroscopy or STEM conditions (Rubino S 2007 Magnetic circular dichroism in the transmission electron microscope PhD Thesis Vienna University of Technology, Vienna, Austria).

  1. N-Acetyl-L-alanine N'-methylamide: a density functional analysis of the vibrational absorption and vibrational circular dichroism spectra

    NASA Astrophysics Data System (ADS)

    Jalkanen, K. J.; Suhai, S.

    1996-07-01

    Ab initio 6-31G ∗ Becke 3LYP DFT optimized geometries, vibrational frequencies, vibrational absorption (VA) intensities and vibrational circular dichroism (VCD) intensities have been calculated for the eight low energy conformers of N-acetyl-L-alanine N'-methylamide (L-AANMA) in the gas phase and one conformer stabilized by the addition of four water molecules. The VA and VCD spectra are calculated with the 6-31G ∗ Becke 3LYP force fields (Hessians) and atomic polar tensors (APT); 6-31G ∗∗ RHF atomic axial tensors (AAT) for the eight gas phase structures and 6-31G ∗/6-31G RHF AAT for the L-AANMA-water complex. The VA and VCD spectra are also calculated using the 6-31G ∗ Becke 3LYP Hessians; 6-31G ∗∗ RHF APT and AAT for the eight gas phase structures and 6-31G ∗/6-31G RHF APT and AAT for the L-AANMA-water complex. The rotational strengths of the amide A, I, II, III, IV, V and VI modes found in proteins as a function of φ and ψ (for various secondary structures) are for the first time reported for an inherently optically active molecule (non-glycine model) using the 6-31G ∗∗ and 6-31G ∗/6-31G RHF DOG AAT and 6-31G ∗ Becke 3LYP Hessians and APT. This is also the first reported VCD calculation of a molecule with the solvent present. The molecule is not completely solvated, but the important hydrogen-bonded interactions are present and the feasibility of the calculation of the Hessian, APT and AAT with solvent molecules present is demonstrated. The VA and VCD spectra are compared to the experimental VA and VCD spectra in the literature and the conformational analysis (CA) and vibrational assignment of L-AANMA are reinvestigated. The rotational strengths of the amide modes for the various conformers are also compared to peptide and protein VCD spectra of molecules with known secondary structures. The agreement between the calculated rotational strengths of the various amide modes for which experimental measurements have been made is very good

  2. Zero-field dichroism in the solar chromosphere.

    PubMed

    Sainz, R Manso; Bueno, J Trujillo

    2003-09-12

    We explain the linear polarization of the Ca ii infrared triplet observed close to the edge of the solar disk. In particular, we demonstrate that the physical origin of the enigmatic polarizations of the 866.2 and 854.2 nm lines lies in the existence of atomic polarization in their metastable (2)D(3)(/2, 5/2) lower levels, which produces differential absorption of polarization components (dichroism). To this end, we have solved the problem of the generation and transfer of polarized radiation by taking fully into account all the relevant optical pumping mechanisms in multilevel atomic models. We argue that "zero-field" dichroism may be of great diagnostic value in astrophysics. PMID:14525412

  3. Dichroism in Helicoidal Crystals.

    PubMed

    Cui, Xiaoyan; Nichols, Shane M; Arteaga, Oriol; Freudenthal, John; Paula, Froilanny; Shtukenberg, Alexander G; Kahr, Bart

    2016-09-21

    Accounting for the interactions of light with heterogeneous, anisotropic, absorbing, optically active media is part of the characterization of complex, transparent materials. Stained biological structures in thin tissue sections share many of these features, but systematic optical analyses beyond the employ of the simple petrographic microscopes have not be established. Here, this accounting is made for polycrystalline, spherulitic bundles of twisted d-mannitol lamellae grown from melts containing light-absorbing molecules. It has long been known that a significant percentage of molecular crystals readily grow as helicoidal ribbons with mesoscale pitches, but a general appreciation of the commonality of these non-classical crystal forms has been lost. Helicoidal crystal twisting was typically assayed by analyzing refractivity modulation in the petrographic microscope. However, by growing twisted crystals from melts in the presence of dissolved, light-absorbing molecules, crystal twisting can be assayed by analyzing the dichroism, both linear and circular. The term "helicoidal dichroism" is used here to describe the optical consequences of anisotropic absorbers precessing around radii of twisted crystalline fibrils or lamellae. d-Mannitol twists in two polymorphic forms, α and δ. The two polymorphs, when grown from supercooled melts in the presence of a variety of histochemical stains and textile dyes, are strongly dichroic in linearly polarized white light. The bis-azo dye Chicago sky blue is modeled because it is most absorbing when parallel and perpendicular to the radial axes in the respective spherulitic polymorphs. Optical properties were measured using Mueller matrix imaging polarimetry and simulated by taking into account the microstructure of the lamellae. The optical analysis of the dyed, patterned polycrystals clarifies aspects of the mesostructure that can be difficult to extract from bundles of tightly packed fibrils. PMID:27617640

  4. Dichroism in Helicoidal Crystals.

    PubMed

    Cui, Xiaoyan; Nichols, Shane M; Arteaga, Oriol; Freudenthal, John; Paula, Froilanny; Shtukenberg, Alexander G; Kahr, Bart

    2016-09-21

    Accounting for the interactions of light with heterogeneous, anisotropic, absorbing, optically active media is part of the characterization of complex, transparent materials. Stained biological structures in thin tissue sections share many of these features, but systematic optical analyses beyond the employ of the simple petrographic microscopes have not be established. Here, this accounting is made for polycrystalline, spherulitic bundles of twisted d-mannitol lamellae grown from melts containing light-absorbing molecules. It has long been known that a significant percentage of molecular crystals readily grow as helicoidal ribbons with mesoscale pitches, but a general appreciation of the commonality of these non-classical crystal forms has been lost. Helicoidal crystal twisting was typically assayed by analyzing refractivity modulation in the petrographic microscope. However, by growing twisted crystals from melts in the presence of dissolved, light-absorbing molecules, crystal twisting can be assayed by analyzing the dichroism, both linear and circular. The term "helicoidal dichroism" is used here to describe the optical consequences of anisotropic absorbers precessing around radii of twisted crystalline fibrils or lamellae. d-Mannitol twists in two polymorphic forms, α and δ. The two polymorphs, when grown from supercooled melts in the presence of a variety of histochemical stains and textile dyes, are strongly dichroic in linearly polarized white light. The bis-azo dye Chicago sky blue is modeled because it is most absorbing when parallel and perpendicular to the radial axes in the respective spherulitic polymorphs. Optical properties were measured using Mueller matrix imaging polarimetry and simulated by taking into account the microstructure of the lamellae. The optical analysis of the dyed, patterned polycrystals clarifies aspects of the mesostructure that can be difficult to extract from bundles of tightly packed fibrils.

  5. Itinerant and localized magnetic moments in ferrimagnetic Mn{sub 2}CoGa thin films probed by x-ray magnetic linear dichroism: Experiment and ab initio theory

    SciTech Connect

    Meinert, Markus; Schmalhorst, Jan-Michael; Klewe, Christoph; Reiss, Guenter; Arenholz, Elke; Boehnert, Tim; Nielsch, Kornelius

    2011-10-01

    Epitaxial thin films of the half-metallic X{sub a} compound Mn{sub 2}CoGa (Hg{sub 2}CuTi prototype) were prepared by dc magnetron co-sputtering with different heat treatments on MgO (001) substrates. High-quality films with a bulk magnetization of 1.95(5) {mu}{sub B} per unit cell were obtained. The L{sub 3,2} x-ray magnetic circular dichroism spectra agree with calculations based on density functional theory (DFT) and reveal the antiparallel alignment of the two inequivalent Mn moments. X-ray magnetic linear dichroism, in good agreement with theory as well, allows us to distinguish between itinerant and local Mn moments. Based on noncollinear spin DFT, it is shown that one of the two Mn moments has local character, whereas the other Mn moment and the Co moment are itinerant.

  6. Itinerant and localized magnetic moments in ferrimagnetic Mn{sub 2}CoGa thin films identified with x-ray magnetic linear dichroism: experiment and ab initio theory

    SciTech Connect

    Meinert, M.; Schmalhorst, J; Klewe, C.; Reiss, G.; Arenholz, E.; Bohnert, T.; Nielsch, K.

    2011-08-08

    Epitaxial thin films of the half-metallic X{sub a}-compound Mn{sub 2}CoGa (Hg{sub 2}CuTi prototype) were prepared by dc magnetron co-sputtering with different heat treatments on MgO (001) substrates. High-quality lms with a bulk magnetization of 1.95(5) {mu}{sub }B per unit cell were obtained. The average Mn magnetic moment and the Co moment are parallel, in agreement with theory. The x-ray magnetic circular dichroism spectra agree with calculations based on density functional theory and reveal the antiparallel alignment of the two inequivalent Mn moments. X-ray magnetic linear dichroism allows to distinguish between itinerant and localized Mn moments. It is shown that one of the two Mn moments has localized character, whereas the other Mn moment and the Co moment are itinerant.

  7. Absorption and Circular Dichroism Spectra of La{sub 3}Ga{sub 5}SiO{sub 14} Crystals Doped with Pr{sup 3+}, Ho{sup 3+}, and Er{sup 3+} Ions

    SciTech Connect

    Burkov, V. I.; Lysenko, O. A.; Mill, B. V.

    2010-11-15

    The absorption and circular dichroism (CD) spectra of La{sub 3}Ga{sub 5}SiO{sub 14} langasite crystals doped with Pr{sup 3+}, Ho{sup 3+}, and Er{sup 3+} ions have been studied in the wavelength range of 350-700 nm. The electronic transitions of these ions, which replace La3+ ions in the 3e position with the symmetry 2, are observed in the spectra. All transitions are active in both the absorption and CD spectra. The dipole strengths D{sub om}, rotational strengths R{sub om}, and anisotropy factors g have been calculated for well-resolved bands. Some features are noted for the spectra that were obtained, and their relationship with the structure disorder is considered.

  8. Toroidal circular dichroism

    NASA Astrophysics Data System (ADS)

    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.

  9. Characterization of the coral allene oxide synthase active site with UV-visible absorption, magnetic circular dichroism, and electron paramagnetic resonance spectroscopy: evidence for tyrosinate ligation to the ferric enzyme heme iron.

    PubMed

    Abraham, B D; Sono, M; Boutaud, O; Shriner, A; Dawson, J H; Brash, A R; Gaffney, B J

    2001-02-20

    Coral allene oxide synthase (AOS), a hemoprotein with weak sequence homology to catalase, is the N-terminal domain of a naturally occurring fusion protein with an 8R-lipoxygenase. AOS converts 8R-hydroperoxyeicosatetraenoic acid to the corresponding allene oxide. The UV--visible absorption and magnetic circular dichroism spectra of ferric AOS and of its cyanide and azide complexes, and the electron paramagnetic resonance spectra of native AOS (high-spin, g = 6.56, 5.22, 2.00) and of its cyanide adduct (low-spin, g = 2.86, 2.24, 1.60) closely resemble the corresponding spectra of bovine liver catalase (BLC). These results provide strong evidence for tyrosinate ligation to the heme iron of AOS as has been established for catalases. On the other hand, the positive circular dichroism bands in the Soret region for all three derivatives of ferric AOS are almost the mirror image of those in catalase. In addition, the cyanide affinity of native AOS (K(d) = 10 mM at pH 7) is about 3 orders of magnitude lower than that of BLC. Thus, while these results conclusively support a common tyrosinate-ligated heme in AOS as in catalase, significant differences exist in the interaction between their respective heme prosthetic groups and protein environments, and in the access of small molecules to the heme iron. PMID:11329294

  10. Nuclear spin circular dichroism

    SciTech Connect

    Vaara, Juha; Rizzo, Antonio; Kauczor, Joanna; Norman, Patrick; Coriani, Sonia

    2014-04-07

    Recent years have witnessed a growing interest in magneto-optic spectroscopy techniques that use nuclear magnetization as the source of the magnetic field. Here we present a formulation of magnetic circular dichroism (CD) due to magnetically polarized nuclei, nuclear spin-induced CD (NSCD), in molecules. The NSCD ellipticity and nuclear spin-induced optical rotation (NSOR) angle correspond to the real and imaginary parts, respectively, of (complex) quadratic response functions involving the dynamic second-order interaction of the electron system with the linearly polarized light beam, as well as the static magnetic hyperfine interaction. Using the complex polarization propagator framework, NSCD and NSOR signals are obtained at frequencies in the vicinity of optical excitations. Hartree-Fock and density-functional theory calculations on relatively small model systems, ethene, benzene, and 1,4-benzoquinone, demonstrate the feasibility of the method for obtaining relatively strong nuclear spin-induced ellipticity and optical rotation signals. Comparison of the proton and carbon-13 signals of ethanol reveals that these resonant phenomena facilitate chemical resolution between non-equivalent nuclei in magneto-optic spectra.

  11. Linear and nonlinear light scattering and absorption in free-electron nanoclusters with diffuse surface: General considerations and linear response

    SciTech Connect

    Fomichev, S. V.; Becker, W.

    2010-06-15

    Both linear and nonlinear scattering and absorption of a laser pulse by spherical nanoclusters with free electrons and with a diffuse surface are considered in the collisionless hydrodynamics approximation. The developed model of forced collective motion of electrons confined to a cluster permits one consistently to introduce into the theory all the sources of nonlinearity, as well as the inhomogeneity of the cluster near its boundary. Two different perturbation theories corresponding to different laser intensity ranges are developed in this context, and both cold metal clusters and hot laser-heated or -ionized clusters are considered within the same approach. In the present article, after developing the full nonlinear model, the linear response to the laser field of the free-electron cluster with diffuse surface is investigated in detail, especially the properties of the linear Mie resonance (width and position). Under certain conditions, depending on the various cluster parameters secondary resonances are found. The properties of resonance-enhanced third-order harmonic generation and nonlinear laser absorption and their dependence on the shape of the diffuse surface will be presented separately.

  12. DEIMOS: A beamline dedicated to dichroism measurements in the 350–2500 eV energy range

    SciTech Connect

    Ohresser, P. Otero, E.; Choueikani, F.; Chen, K.; Stanescu, S.; Deschamps, F.; Moreno, T.; Polack, F.; Lagarde, B.; Daguerre, J.-P.; Marteau, F.; Scheurer, F.; Joly, L.; Muller, B.; Kappler, J.-P.; Bunau, O.; Sainctavit, Ph.

    2014-01-15

    The DEIMOS (Dichroism Experimental Installation for Magneto-Optical Spectroscopy) beamline was part of the second phase of the beamline development at French Synchrotron SOLEIL (Source Optimisée de Lumière à Energie Intermédiaire du LURE) and opened to users in March 2011. It delivers polarized soft x-rays to perform x-ray absorption spectroscopy, x-ray magnetic circular dichroism, and x-ray linear dichroism in the energy range 350–2500 eV. The beamline has been optimized for stability and reproducibility in terms of photon flux and photon energy. The main end-station consists in a cryo-magnet with 2 split coils providing a 7 T magnetic field along the beam or 2 T perpendicular to the beam with a controllable temperature on the sample from 370 K down to 1.5 K.

  13. DEIMOS: a beamline dedicated to dichroism measurements in the 350-2500 eV energy range.

    PubMed

    Ohresser, P; Otero, E; Choueikani, F; Chen, K; Stanescu, S; Deschamps, F; Moreno, T; Polack, F; Lagarde, B; Daguerre, J-P; Marteau, F; Scheurer, F; Joly, L; Kappler, J-P; Muller, B; Bunau, O; Sainctavit, Ph

    2014-01-01

    The DEIMOS (Dichroism Experimental Installation for Magneto-Optical Spectroscopy) beamline was part of the second phase of the beamline development at French Synchrotron SOLEIL (Source Optimisée de Lumière à Energie Intermédiaire du LURE) and opened to users in March 2011. It delivers polarized soft x-rays to perform x-ray absorption spectroscopy, x-ray magnetic circular dichroism, and x-ray linear dichroism in the energy range 350-2500 eV. The beamline has been optimized for stability and reproducibility in terms of photon flux and photon energy. The main end-station consists in a cryo-magnet with 2 split coils providing a 7 T magnetic field along the beam or 2 T perpendicular to the beam with a controllable temperature on the sample from 370 K down to 1.5 K.

  14. Towards an exact theory of linear absorbance and circular dichroism of pigment-protein complexes: Importance of non-secular contributions

    NASA Astrophysics Data System (ADS)

    Dinh, Thanh-Chung; Renger, Thomas

    2015-01-01

    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.

  15. Towards an exact theory of linear absorbance and circular dichroism of pigment-protein complexes: Importance of non-secular contributions

    SciTech Connect

    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 Q{sub y} transition dipole moments in Chl b homodimers is larger by about 9{sup ∘} 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.

  16. Efficient Algorithms for Estimating the Absorption Spectrum within Linear Response TDDFT

    SciTech Connect

    Brabec, Jiri; Lin, Lin; Shao, Meiyue; Govind, Niranjan; Yang, Chao; Saad, Yousef; Ng, Esmond

    2015-10-06

    We present two iterative algorithms for approximating the absorption spectrum of molecules within linear response of time-dependent density functional theory (TDDFT) framework. These methods do not attempt to compute eigenvalues or eigenvectors of the linear response matrix. They are designed to approximate the absorption spectrum as a function directly. They take advantage of the special structure of the linear response matrix. Neither method requires the linear response matrix to be constructed explicitly. They only require a procedure that performs the multiplication of the linear response matrix with a vector. These methods can also be easily modified to efficiently estimate the density of states (DOS) of the linear response matrix without computing the eigenvalues of this matrix. We show by computational experiments that the methods proposed in this paper can be much more efficient than methods that are based on the exact diagonalization of the linear response matrix. We show that they can also be more efficient than real-time TDDFT simulations. We compare the pros and cons of these methods in terms of their accuracy as well as their computational and storage cost.

  17. Theoretical analysis of X-ray magnetic circular dichroism at the Yb L2, 3 absorption edges of YbInCu4 in high magnetic fields around the field-induced valence transition

    NASA Astrophysics Data System (ADS)

    Kotani, A.

    2012-01-01

    High-magnetic-field X-ray absorption spectra (XAS) and its X-ray magnetic circular dichroism (XMCD) at the Yb L2, 3 edges of YbInCu4 are calculated around the field-induced valence transition at about 30 T. The calculations are made by using a new theoretical framework with an extended single impurity Anderson model (SIAM) developed recently by the present author. Two parameters in SIAM, the 4 f level and the hybridization strength, are taken as different values in low- and high-magnetic-field phases of the field-induced valence transition. The calculated results are compared with recent experimental data measured by Matsuda et al. by utilizing a miniature pulsed magnet up to 40 T. The field-dependence of the calculated XMCD spectra is explained in detail on the basis of the field-dependence of the Yb 4 f wavefunctions in the ground state. Some possibilities are discussed on the negative XMCD signal observed experimentally at the L2 edge.

  18. Electronic absorption spectra of linear and cyclic Cn+ n=7-9 in a neon matrix

    NASA Astrophysics Data System (ADS)

    Fulara, Jan; Shnitko, Ivan; Batalov, Anton; Maier, John P.

    2005-07-01

    The Cn+n=7-9 cations were produced by electron-impact ionization of perchloronaphthalene, mass selected, and their electronic absorption spectra in 6K neon matrices recorded. The linear and cyclic isomers of C7+ and C8+ are detected. Three systems of linear C7+ are observed with origin bands near 770, 332, and 309nm. The cyclic C7+ shows two transitions near 676 and 448nm. One system of linear C9+ is observed commencing at 371nm. Linear C8+ shows five dipole-allowed electronic transitions from the X˜Πg2 ground state, and the strongest ones have the origin bands at 890.8 and 308.1nm. Five electronic transitions of cyclic C8+ are also discernible.

  19. An absorption detection approach for multiplexed capillary electrophoresis using a linear photodiode array.

    PubMed

    Gong, X; Yeung, E S

    1999-11-01

    A novel absorption detection method for highly multiplexed capillary electrophoresis is presented for zone electrophoresis and for micellar electrokinetic chromatography. The approach involves the use of a linear photodiode array on which a capillary array is imaged by a camera lens. Either a tungsten lamp or a mercury lamp can be used as the light source such that all common wavelengths for absorption detection are accessible by simply interchanging narrow-band filters. Each capillary spans several diodes in the photodiode array for absorption measurements. Over 100 densely packed capillaries can be monitored by a single photodiode array element with 1024 diodes. The detection limit for rhodamine 6G for each capillary in the multiplexed array is ∼1.8 × 10(-)(8) M injected (S/N = 2). The cross-talk between adjacent capillaries is less than 0.2%. Simultaneous analysis of 96 samples is demonstrated. PMID:21662842

  20. Absorption cross-section and decay rate of rotating linear dilaton black holes

    NASA Astrophysics Data System (ADS)

    Sakalli, I.; Aslan, O. A.

    2016-02-01

    We analytically study the scalar perturbation of non-asymptotically flat (NAF) rotating linear dilaton black holes (RLDBHs) in 4-dimensions. We show that both radial and angular wave equations can be solved in terms of the hypergeometric functions. The exact greybody factor (GF), the absorption cross-section (ACS), and the decay rate (DR) for the massless scalar waves are computed for these black holes (BHs). The results obtained for ACS and DR are discussed through graphs.

  1. Some new progress on the light absorption properties of linear alkyl benzene solvent

    NASA Astrophysics Data System (ADS)

    Yu, Guang-You; Cao, De-Wen; Huang, Ai-Zhong; Yu, Lei; Loh, Chang-Wei; Wang, Wen-Wen; Qian, Zhi-Qiang; Yang, Hai-Bo; Huang, Huang; Xu, Zong-Qiang; Zhu, Xue-Yuan; Xu, Bin; Qi, Ming

    2016-01-01

    Linear alkyl benzene (LAB) will be used as the solvent in a liquid scintillator mixture for the JUNO antineutrino experiment. Its light absorption properties should therefore be understood prior to its effective use in the experiment. Attenuation length measurements at a light wavelength of 430 nm have been performed on samples of LAB prepared for the JUNO experiment. Inorganic impurities in LAB have also been studied for their possibilities of light absorption in our wavelength of interest. In view of a tentative plan by the JUNO collaboration to utilize neutron capture with hydrogen in the detector, we also present in this work a preliminary study on the carbon-hydrogen ratio and the attenuation length of the samples. Supported by China Ministry of Science and Technology(2013CB834300)

  2. On the Theory of the Ballistic Linear Photovoltaic Effect in Semiconductors of Tetrahedral Symmetry Under Two-Photon Absorption

    NASA Astrophysics Data System (ADS)

    Rasulov, R. Ya.; Rasulov, V. R.; Eshboltaev, I.

    2016-07-01

    The ballistic contribution to the current of linear photovoltaic effect under two-photon absorption of light is calculated and theoretically analyzed for the semiconductors of a tetrahedral symmetry with a complex band structure consisting of two closely spaced subbands. The transitions between the branches of one band in cases of the simultaneous absorption of two photons and successive absorption of two single photons are taken into account.

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

    SciTech Connect

    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.

  4. Specific absorption rate calculations of magnetite, using a modified linear response model for applications in magnetic hyperthermia

    SciTech Connect

    Hernández S, A. E-mail: meduardo2001@hotmail.com; Cano, M. E. E-mail: meduardo2001@hotmail.com; Torres-Arenas, J.

    2014-11-07

    Currently the absorption of electromagnetic radiation by magnetic nanoparticles is studied for biomedical applications of cancer thermotherapy. Several experiments are conduced following the framework of the Rosensweig model, in order to estimate their specific absorption rate. Nevertheless, this linear approximation involves strong simplifications which constrain their accuracy and validity range. The main aim of this work is to incorporate the deviation of the sphericity assumption in particles shapes, to improve the determination of their specific absorption rate. The correction to the effective particles volume is computed as a measure of the apparent amount of magnetic material, interacting with the external AC magnetic field. Preliminary results using the physical properties of Fe3O4 nanoparticles, exhibit an important correction in their estimated specific absorption rate, as a function of the apparent mean particles radius. Indeed, we have observed using a small deviation (6% of the apparent radius), up to 40% of the predicted specific absorption rate by the Rosensweig linear approximation.

  5. Off-resonance energy absorption in a linear Paul trap due to mass selective resonant quenching.

    PubMed

    Sivarajah, I; Goodman, D S; Wells, J E; Narducci, F A; Smith, W W

    2013-11-01

    Linear Paul traps (LPT) are used in many experimental studies such as mass spectrometry, atom-ion collisions, and ion-molecule reactions. Mass selective resonant quenching (MSRQ) is implemented in LPT either to identify a charged particle's mass or to remove unwanted ions from a controlled experimental environment. In the latter case, MSRQ can introduce undesired heating to co-trapped ions of different mass, whose secular motion is off resonance with the quenching ac field, which we call off-resonance energy absorption (OREA). We present simulations and experimental evidence that show that the OREA increases exponentially with the number of ions loaded into the trap and with the amplitude of the off-resonance external ac field. PMID:24289382

  6. Microscopic Modeling of Intersubband Optical Processes in Type II Semiconductor Quantum Wells: Linear Absorption

    NASA Technical Reports Server (NTRS)

    Li, Jian-Zhong; Kolokolov, Kanstantin I.; Ning, Cun-Zheng

    2003-01-01

    Linear absorption spectra arising from intersubband transitions in semiconductor quantum well heterostructures are analyzed using quantum kinetic theory by treating correlations to the first order within Hartree-Fock approximation. The resulting intersubband semiconductor Bloch equations take into account extrinsic dephasing contributions, carrier-longitudinal optical phonon interaction and carrier-interface roughness interaction which is considered with Ando s theory. As input for resonance lineshape calculation, a spurious-states-free 8-band kp Hamiltonian is used, in conjunction with the envelop function approximation, to compute self-consistently the energy subband structure of electrons in type II InAs/AlSb single quantum well structures. We demonstrate the interplay of nonparabolicity and many-body effects in the mid-infrared frequency range for such heterostructures.

  7. Self-Focusing/Defocusing of Chirped Gaussian Laser Beam in Collisional Plasma with Linear Absorption

    NASA Astrophysics Data System (ADS)

    Wani, Manzoor Ahmad; Kant, Niti

    2016-09-01

    This paper presents an investigation on the self-focusing/defocusing of chirped Gaussian laser beam in collisional plasma with linear absorption. We have derived the differential equation for the beam width parameter by using WKB and paraxial approximations and solved it numerically. The effect of chirp and other laser plasma parameters is seen on the behavior of beam width parameter with dimensionless distance of propagation. The results are discussed and presented graphically. Our simulation results show that the amplitude of oscillations decreases with the distance of propagation. Due to collisional frequency, the laser beam shows fast divergence which can be minimized by the introduction of chirp parameter. The chirp decreases the effect of defocusing and increases the ability of self-focusing of laser beam in collisional plasma. Supported by a financial grant from CSIR, New Delhi, India, under Project No. 03(1277)/13/EMR-II

  8. X-Ray Dichroism in Photoelectron Spectroscopy for Direct Element Specific Surface Magnetometry of Nanomagnetic Structures

    NASA Astrophysics Data System (ADS)

    Tobin, James G.

    1997-03-01

    Element specific surface magnetometry remains a central goal of synchrotron radiation based studies of nanomagnetic structures. One appealing possibility is the combination of xray absorption dichroism measurements and the theoretical framework provided by the "sum rules."[1] Unfortunately, sum rule analyses are hampered by several limitations [2], including delocalization of the final state, multi-electronic phenomena and the presence of surface dipoles. An alternative experiment, Magnetic Xray Dichroism in Photoelectron Spectroscopy, holds out promise based upon its elemental specificity, surface sensitivity and high resolution. Computational simulations by Tamura et al [3] demonstrated the relationship between exchange and spin orbit splittings and experimental data of linear and circular dichroisms. Now we [4] 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 [5], 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 [6], 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. [7,8] This work was performed under the auspices of the U.S. Department of Energy by LLNL under contract No. W-7405-ENG-48. 1. B.T. Thole et al, Phys. Rev. Lett. 68,1943 (1992); P. Carra et al. Phys. Rev. Lett. 70, 694 (1993). 2. J.G. Tobin et al Phys. Rev. B 52, 6530 (1995). 3. E. Tamura et al, Phys. Rev. Lett 73, 1533 (1994) 4. J.G. Tobin, K.W. Goodman, F.O. Schumann, R.F. Willis, J

  9. Maintenance of the slope of linearized calibration curves in Zeeman graphite furnace atomic absorption spectrometry

    NASA Astrophysics Data System (ADS)

    Yuzefovsky, Alexander I.; Lonardo, Robert F.; Zhou, Jack X.; Michel, Robert G.; Koltracht, Israel

    1996-06-01

    L'vov and co-workers developed a theoretical model and computational procedure (B.V. L'vov, L.K. Polzik and N.V. Kocharova, Spectrochim. Acta Part B, 47 (1992) 889 and B.V. L'vov, L.K. Polzik, N.V. Kocharova, Yu.A. Nemets and A.V. Novichikhin, Spectrochim. Acta Part B, 47 (1992) 1187) that linearized calibration curves in Zeeman graphite furnace atomic absorption spectrometry by taking into account the presence of stray light. The calculations of L'vov and co-workers were based on three parameters: the rollover absorbance Ar, Zeeman sensitivity ratio R, and the original background corrected peak absorbance values Az. In order to simplify the calculations, R was assumed to be unity. In the studies reported here, this simplification is shown to be unsatisfactory because the slope obtained in the upper portion of the calibration curve, after linearization, is found to be different from the slope obtained in the normal linear region. Deviations between these slopes were found to be as high as 30%. The present work also shows that the theoretical model of L'vov and co-workers does not have a mathematical solution at high values of Az. This failure of the model prevents its use at high Az values. The physical nature of this failure is still unclear, which points to the necessity for further work to understand the inadequacies of the present theory. In the present studies, calculations based on the Newton method of successive approximations (A.I. Yuzefovsky, E.G. Su, R.G. Michel, W. Slavin and J.T. McCaffrey, Spectrochim. Acta Part B, 49 (1994) 1643), allow incorporation of the experimental value of R at the rollover point R', which better linearizes the calibration curves. By use of this approach, a satisfactory result is obtained for lead ( R' = 0.67) up to the point of failure of the model at high values of Az.

  10. Appraisal of Surface Hopping as a Tool for Modeling Condensed Phase Linear Absorption Spectra.

    PubMed

    Petit, Andrew S; Subotnik, Joseph E

    2015-09-01

    Whereas surface hopping is usually used to study populations and mean-field dynamics to study coherences, in two recent papers, we described a procedure for calculating dipole-dipole correlation functions (and therefore absorption spectra) directly from ensembles of surface hopping trajectories. We previously applied this method to a handful of one-dimensional model problems intended to mimic the gas phase. In this article, we now benchmark this new procedure on a set of multidimensional model problems intended to mimic the condensed phase and compare our results against other standard semiclassical methods. By comparison, we demonstrate that methods that include only dynamical information from one PES (the standard Kubo approaches) exhibit large discrepancies with the results of exact quantum dynamics. Furthermore, for model problems with nonadiabatic excited state dynamics but no quantized vibrational structure in the spectra, our surface hopping approach performs comparably to using Ehrenfest dynamics to calculate the electronic coherences. That being said, however, when quantized vibrational structures are present in the spectra but the electronic states are uncoupled, performing the dynamics on the mean PES still outperforms our present method. These benchmark results should influence future studies that use ensembles of independent semiclassical trajectories to model linear as well as multidimensional spectra in the condensed phase.

  11. Linear absorption coefficient of beryllium in the 50-300-A wavelength range. [bandpass filter materials for ultraviolet astronomy instrumentation

    NASA Technical Reports Server (NTRS)

    Barstow, M. A.; Lewis, M.; Petre, R.

    1983-01-01

    Transmittances of thin-film filters fabricated for an extreme-UV astronomy sounding-rocket experiment yield values for the linear absorption coefficient of beryllium in the 50-300-A wavelength range, in which previous measurements are sparse. The inferred values are consistent with the lowest data previously published and may have important consequences for extreme-UV astronomers.

  12. Density Transition Based Self-Focusing of cosh-Gaussian Laser Beam in Plasma with Linear Absorption

    NASA Astrophysics Data System (ADS)

    Niti, Kant; Manzoor, Ahmad Wani

    2015-07-01

    Density transition based self-focusing of cosh-Gaussian laser beam in plasma with linear absorption has been studied. The field distribution in the plasma is expressed in terms of beam width parameter, decentered parameter, and linear absorption coefficient. The differential equation for the beam width parameter is solved by following Wentzel-Kramers-Brillouin (WKB) and paraxial approximation through parabolic wave equation approach. The behaviour of beam width parameter with dimensionless distance of propagation is studied at optimum values of plasma density, decentered parameter and with different absorption levels in the medium. The results reveal that these parameters can affect the self-focusing significantly. Supported by a Financial Grant from CSIR, New Delhi, India, under Project No. 03(1277)/13/EMR-II

  13. High-resolution continuum source electrothermal atomic absorption spectrometry: Linearization of the calibration curves within a broad concentration range

    NASA Astrophysics Data System (ADS)

    Katskov, Dmitri; Hlongwane, Miranda; Heitmann, Uwe; Florek, Stefan

    2012-05-01

    The calculation algorithm suggested provides linearization of the calibration curves in high-resolution continuum source electrothermal atomic absorption spectrometry. The algorithm is based on the modification of the function wavelength-integrated absorbance vs. concentration of analyte vapor in the absorption volume. According to the suggested approach, the absorption line is represented by a triangle for low and trapezium for high analyte vapor concentration in the absorption volume. The respective semi-empirical formulas include two linearization parameters, which depend on properties of the absorption line and characteristics of the atomizer and spectrometer. The parameters can be approximately evaluated from the theory and determined in practice from the original broad-range calibration curve. The parameters were found and the proposed calculation algorithm verified in the experiments on direct determination of Ag, Cd, Cu, Fe, Mn and Pb in the solutions within a concentration ranges from 0.15 to 625 μg·L- 1 using tube, platform tube and filter furnace atomizers. The use of various atomizers, lines, elements and atomization temperatures made possible the simulation of various practical analytical conditions. It was found that the algorithm and optimal linearization parameters made it possible to obtain for each line and atomizer linear approximations of the calibration curves within 3-4 orders of magnitude with correlation coefficients close to 0.999. The algorithm makes possible to employ a single line for the direct element determination over a broad concentration range. The sources of errors and the possibility of a priori theoretical evaluation of the linearization parameters are discussed.

  14. Compact characterization of liquid absorption and emission spectra using linear variable filters integrated with a CMOS imaging camera

    PubMed Central

    Wan, Yuhang; Carlson, John A.; Kesler, Benjamin A.; Peng, Wang; Su, Patrick; Al-Mulla, Saoud A.; Lim, Sung Jun; Smith, Andrew M.; Dallesasse, John M.; Cunningham, Brian T.

    2016-01-01

    A compact analysis platform for detecting liquid absorption and emission spectra using a set of optical linear variable filters atop a CMOS image sensor is presented. The working spectral range of the analysis platform can be extended without a reduction in spectral resolution by utilizing multiple linear variable filters with different wavelength ranges on the same CMOS sensor. With optical setup reconfiguration, its capability to measure both absorption and fluorescence emission is demonstrated. Quantitative detection of fluorescence emission down to 0.28 nM for quantum dot dispersions and 32 ng/mL for near-infrared dyes has been demonstrated on a single platform over a wide spectral range, as well as an absorption-based water quality test, showing the versatility of the system across liquid solutions for different emission and absorption bands. Comparison with a commercially available portable spectrometer and an optical spectrum analyzer shows our system has an improved signal-to-noise ratio and acceptable spectral resolution for discrimination of emission spectra, and characterization of colored liquid’s absorption characteristics generated by common biomolecular assays. This simple, compact, and versatile analysis platform demonstrates a path towards an integrated optical device that can be utilized for a wide variety of applications in point-of-use testing and point-of-care diagnostics. PMID:27389070

  15. Compact characterization of liquid absorption and emission spectra using linear variable filters integrated with a CMOS imaging camera.

    PubMed

    Wan, Yuhang; Carlson, John A; Kesler, Benjamin A; Peng, Wang; Su, Patrick; Al-Mulla, Saoud A; Lim, Sung Jun; Smith, Andrew M; Dallesasse, John M; Cunningham, Brian T

    2016-01-01

    A compact analysis platform for detecting liquid absorption and emission spectra using a set of optical linear variable filters atop a CMOS image sensor is presented. The working spectral range of the analysis platform can be extended without a reduction in spectral resolution by utilizing multiple linear variable filters with different wavelength ranges on the same CMOS sensor. With optical setup reconfiguration, its capability to measure both absorption and fluorescence emission is demonstrated. Quantitative detection of fluorescence emission down to 0.28 nM for quantum dot dispersions and 32 ng/mL for near-infrared dyes has been demonstrated on a single platform over a wide spectral range, as well as an absorption-based water quality test, showing the versatility of the system across liquid solutions for different emission and absorption bands. Comparison with a commercially available portable spectrometer and an optical spectrum analyzer shows our system has an improved signal-to-noise ratio and acceptable spectral resolution for discrimination of emission spectra, and characterization of colored liquid's absorption characteristics generated by common biomolecular assays. This simple, compact, and versatile analysis platform demonstrates a path towards an integrated optical device that can be utilized for a wide variety of applications in point-of-use testing and point-of-care diagnostics. PMID:27389070

  16. Compact characterization of liquid absorption and emission spectra using linear variable filters integrated with a CMOS imaging camera

    NASA Astrophysics Data System (ADS)

    Wan, Yuhang; Carlson, John A.; Kesler, Benjamin A.; Peng, Wang; Su, Patrick; Al-Mulla, Saoud A.; Lim, Sung Jun; Smith, Andrew M.; Dallesasse, John M.; Cunningham, Brian T.

    2016-07-01

    A compact analysis platform for detecting liquid absorption and emission spectra using a set of optical linear variable filters atop a CMOS image sensor is presented. The working spectral range of the analysis platform can be extended without a reduction in spectral resolution by utilizing multiple linear variable filters with different wavelength ranges on the same CMOS sensor. With optical setup reconfiguration, its capability to measure both absorption and fluorescence emission is demonstrated. Quantitative detection of fluorescence emission down to 0.28 nM for quantum dot dispersions and 32 ng/mL for near-infrared dyes has been demonstrated on a single platform over a wide spectral range, as well as an absorption-based water quality test, showing the versatility of the system across liquid solutions for different emission and absorption bands. Comparison with a commercially available portable spectrometer and an optical spectrum analyzer shows our system has an improved signal-to-noise ratio and acceptable spectral resolution for discrimination of emission spectra, and characterization of colored liquid’s absorption characteristics generated by common biomolecular assays. This simple, compact, and versatile analysis platform demonstrates a path towards an integrated optical device that can be utilized for a wide variety of applications in point-of-use testing and point-of-care diagnostics.

  17. Magnetic x-ray circular dichroism in Fe Co Pt multilayers

    SciTech Connect

    Tobin, J.G.; Jankowski, A.F.; Waddill, G.D.; Sterne, P.A.

    1994-04-01

    Magnetic x-ray circular dichroism in x-ray absorption has been used to investigate the ternary multilayer system, Fe Co Pt. Samples were prepared by planar magnetron sputter deposition and carefully characterized, using a variety of techniques such as grazing-incidence and high-angle x-ray scattering, Auger depth profiling and cross-section transmission electron microscopy. As previously reported, the Fe9.5{Angstrom} Pt9.5{Angstrom} exhibits a large dichroism in the Fe 2p absorption. Interestingly while the Co9.5{Angstrom} Pt9.5{Angstrom} has no measurable dichroism, the Fe4.7{Angstrom} Co4.7{Angstrom} Pt9.5{Angstrom} sample has a dichroism at both the Fe 2p and Co 2p absorption edges. These and other results are compared to slab calculation predictions. Possible explanations are discussed.

  18. Magnetic circular dichroism in EELS (abstract)

    SciTech Connect

    Harp, G.R.; Farrow, R.F.; Marks, R.F.

    1996-04-01

    We evaluate the possibility of using dichroic electron energy loss spectroscopy (DEELS) as an alternative to x-ray magnetic circular dichroism (XMCD). It is well known that electron energy loss spectroscopy and x-ray absorption spectroscopy are highly analogous, providing similar information. A simple semiclassical model suggests that DEELS might have a magnetic sensitivity similar to that of XMCD. This sensitivity will be reduced, however, by multiple scattering of the probe electron before and after the energy loss event. Thus it is difficult to predict the magnitude of the DEELS effect. Experiments were performed at the {ital L}-edge of polycrystalline Fe, Co, and Ni thin film samples with uniaxial in-plane magnetic anisotropy, prepared {ital in} {ital situ} with a magnetic bias field. Even in those most favorable cases, the DEELS effect is seen to be at least 10 times smaller than similar effects in XMCD. {copyright} {ital 1996 American Institute of Physics.}

  19. Electromagnetic particle simulation of the effect of toroidicity on linear mode conversion and absorption of lower hybrid waves

    NASA Astrophysics Data System (ADS)

    Bao, J.; Lin, Z.; Kuley, A.; Wang, Z. X.

    2016-06-01

    Effects of toroidicity on linear mode conversion and absorption of lower hybrid (LH) waves in fusion plasmas have been studied using electromagnetic particle simulation. The simulation confirms that the toroidicity induces an upshift of parallel refractive index when LH waves propagate from the tokamak edge toward the core, which affects the radial position for the mode conversion between slow and fast LH waves. Furthermore, moving LH antenna launch position from low field side toward high field side leads to a larger upshift of the parallel refractive index, which helps the slow LH wave penetration into the tokamak core. The broadening of the poloidal spectrum of the wave-packet due to wave diffraction is also verified in the simulation. Both the upshift and broadening effects of the parallel spectrum of the wave-packet modify the parallel phase velocity and thus the linear absorption of LH waves by electron Landau resonance.

  20. Characterization of Photon-Counting Detector Responsivity for Non-Linear Two-Photon Absorption Process

    NASA Technical Reports Server (NTRS)

    Sburlan, S. E.; Farr, W. H.

    2011-01-01

    Sub-band absorption at 1550 nm has been demonstrated and characterized on silicon Geiger mode detectors which normally would be expected to have no response at this wavelength. We compare responsivity measurements to singlephoton absorption for wavelengths slightly above the bandgap wavelength of silicon (approx. 1100 microns). One application for this low efficiency sub-band absorption is in deep space optical communication systems where it is desirable to track a 1030 nm uplink beacon on the same flight terminal detector array that monitors a 1550 nm downlink signal for pointingcontrol. The currently observed absorption at 1550 nm provides 60-70 dB of isolation compared to the response at 1064 nm, which is desirable to avoid saturation of the detector by scattered light from the downlink laser.

  1. Dichroism and birefringence of natural violet diamond crystals

    SciTech Connect

    Konstantinova, A. F. Titkov, S. V.; Imangazieva, K. B.; Evdishchenko, E. A.; Sergeev, A. M.; Zudin, N. G.; Orekhova, V. P.

    2006-05-15

    Investigation of the optical properties of natural violet diamonds from the Yakutian kimberlites is performed. A red shift of the absorption edge is revealed in the absorption spectra of these crystals. This shift is indicative of the presence of a high concentration of nitrogen in the diamonds studied. Along with the strong band at 0.550 {mu}m, weaker bands at 0.390, 0.456 and 0.496 {mu}m are revealed. It is shown that violet diamond crystals have birefringence and dichroism of about 10{sup -5} and 10{sup -6}, respectively. When a light beam propagates perpendicularly to colored lamellas, the dichroism is much larger and the birefringence is smaller than in the case where the beam direction is parallel to lamellas.

  2. Quantum-cascade laser-based vibrational circular dichroism.

    PubMed

    Lüdeke, Steffen; Pfeifer, Marcel; Fischer, Peer

    2011-04-20

    Vibrational circular dichroism (VCD) spectra were recorded with a tunable external-cavity quantum-cascade laser (QCL). In comparison with standard thermal light sources in the IR, QCLs provide orders of magnitude more power and are therefore promising for VCD studies in strongly absorbing solvents. The brightness of this novel light source is demonstrated with VCD and IR absorption measurements of a number of compounds, including proline in water.

  3. Communication: Broadband and ultrasensitive femtosecond time-resolved circular dichroism spectroscopy.

    PubMed

    Hiramatsu, Kotaro; Nagata, Takashi

    2015-09-28

    We report the development of broadband and sensitive time-resolved circular dichroism (TRCD) spectroscopy by exploiting optical heterodyne detection. Using this method, transient CD signals of submillidegree level can be detected over the spectral range of 415-730 nm. We also demonstrate that the broadband measurement with the aid of singular value decomposition enables the discrimination of genuine TRCD signals from artificial optical-anisotropy, such as linear birefringence and linear dichroism, induced by photoexcitation. PMID:26428989

  4. Characterization of the Cu(Π) and Zn(Π) binding to the Amyloid-β short peptides by both the Extended X-ray Absorption Fine Structure and the Synchrotron Radiation Circular Dichroism spectroscopy

    NASA Astrophysics Data System (ADS)

    Zhang, Zhiyin; Sun, Shuaishuai; Xu, Jianhua; Zhang, Jing; Huang, Yan; Zhang, Bingbing; Tao, Ye

    2013-04-01

    Alzheimer's disease (AD) is a progressive and devastating neurodegenerative pathology, clinically characterized by dementia, cognitive impairment, personality disorders and memory loss. It is generally accepted that, misfolding of Aβ peptides is the key element in pathogenesis and the secondary structure of Aβ can be changed to major β-strand with reasons unknown yet. Many studies have shown that the misfolding may be linked with some biometals, mainly copper and zinc ions. To characterize interactions of Aβ and metal ions, we utilized both the extended X-ray fine structure spectroscopy (EXAFS) and the synchrotron radiation circular dichroism spectroscopy (SRCD). Aβ (13-22), Aβ (13-21), Aβ (E22G) and Aβ(HH-AA) were selected to study the mechanism of copper and zinc binding to Aβ. We found that Cu interaction with H13 and H14 residues led to the disappearance of the PPΠ, while the Cu binding E22 residue caused a remarkable conformation change to β-sheet enrichment. The Zn ion, in contrast, made little effect on the conformation and it coordinated to only one histidine (H residue) or not.

  5. Investigation of linear optical absorption coefficients in core-shell quantum dot (QD) luminescent solar concentrators (LSCs)

    NASA Astrophysics Data System (ADS)

    Ebrahimipour, Bahareh Alsadat; Askari, Hassan Ranjbar; Ramezani, Ali Behjat

    2016-09-01

    The interlevel absorption coefficient of CdSe/ZnS and ZnS/CdSe core-shell Quantum Dot (QD) in luminescent solar concentrators (LSCs) is reported. By considering the quantum confinement effects, the wave functions and eigenenergies of electrons in the nonperturebative system consists of a core-shell QD have been numerically calculated under the frame work of effective-mass approximation by solving a three-dimensional Schrӧdinger equation. And then the absorption coefficient is obtained under density matrix approximation considering in the polymer sheets of the concentrator including the core-shell QDs. The effect of the hetero-structure geometry upon the energy spectrum and absorption coefficient associated to interlevel transitions was also considered. The results show that the core-shell QDs can absorb the photons with higher energy in solar spectrum as compared to the inverted core-shell. And with a small shell layer diameter, the core-shell QDs produce larger linear absorption coefficients and consequently higher efficiency values, however it is inversed for inverted core-shell QDs. The work described here gives a detailed insight into the promise of QD-based LSCs and the optoelectronic devices applications.

  6. Sub-bandgap linear-absorption-based photodetectors in avalanche mode in PN-diode-integrated silicon microring resonators.

    PubMed

    Li, Yu; Feng, Shaoqi; Zhang, Yu; Poon, Andrew W

    2013-12-01

    We report a sub-bandgap linear-absorption-based photodetector in avalanche mode at 1550 nm in a PN-diode-integrated silicon microring resonator. The photocurrent is primarily generated by the defect-state absorption introduced by the boron and phosphorous ion implantation during the PN diode formation. The responsivity is enhanced by both the cavity effect and the avalanche multiplication. We measure a responsivity of ~72.8 mA/W upon 8 V at cavity resonances in avalanche mode, corresponding to a gain of ~72 relative to the responsivity of ~1.0 mA/W upon 3 V at cavity resonances in normal mode. Our device exhibits a 3 dB bandwidth of ~7 GHz and an open eye diagram at 15 Gbit/s upon 8 V.

  7. Influence of the light propagation models on a linearized photoacoustic image reconstruction of the light absorption coefficient

    NASA Astrophysics Data System (ADS)

    Okawa, Shinpei; Hirasawa, Takeshi; Kushibiki, Toshihiro; Ishihara, Miya

    2015-03-01

    Quantification of the optical properties of the tissues and blood by noninvasive photoacoustic (PA) imaging may provide useful information for screening and early diagnosis of diseases. Linearized 2D image reconstruction algorithm based on PA wave equation and the photon diffusion equation (PDE) can reconstruct the image with computational cost smaller than a method based on 3D radiative transfer equation. However, the reconstructed image is affected by the differences between the actual and assumed light propagations. A quantitative capability of a linearized 2D image reconstruction was investigated and discussed by the numerical simulations and the phantom experiment in this study. The numerical simulations with the 3D Monte Carlo (MC) simulation and the 2D finite element calculation of the PDE were carried out. The phantom experiment was also conducted. In the phantom experiment, the PA pressures were acquired by a probe which had an optical fiber for illumination and the ring shaped P(VDF-TrFE) ultrasound transducer. The measured object was made of Intralipid and Indocyanine green. In the numerical simulations, it was shown that the linearized image reconstruction method recovered the absorption coefficients with alleviating the dependency of the PA amplitude on the depth of the photon absorber. The linearized image reconstruction method worked effectively under the light propagation calculated by 3D MC simulation, although some errors occurred. The phantom experiments validated the result of the numerical simulations.

  8. Rotation and dichroism associated with microwave propagation in chiral composite samples

    SciTech Connect

    Umari, M.H.; Varadan, V.V.; Varadan, V.K. )

    1991-10-01

    Experimental results are presented on the angle of rotation and the axial ratio (dichroism) associated with the propagation of microwave waves in chiral composite samples (a phenomenon akin to optical rotation and optical dichroism). In the experiments the chiral composite samples tested were made in the form of planar slabs and consisted of low loss dielectric matrix materials in which miniature copper springs of left only, right only, or an equal mixture of left and right handedness were randomly distributed and oriented. The normally incident wave was linearly polarized. In the chiral sample the linearly polarized wave decomposes into left and right circularly polarized waves which propagate with different speeds and different attenuations leading to an elliptically polarized transmitted wave whose orientation (electromagnetic rotation) and axial ratio (dichroism) are proportional to the concentration of springs. Rotation and dichroism are shown to be zero in the equichiral samples. 10 refs.

  9. Quantification and parametrization of non-linearity effects by higher-order sensitivity terms in scattered light differential optical absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Puķīte, Jānis; Wagner, Thomas

    2016-05-01

    We address the application of differential optical absorption spectroscopy (DOAS) of scattered light observations in the presence of strong absorbers (in particular ozone), for which the absorption optical depth is a non-linear function of the trace gas concentration. This is the case because Beer-Lambert law generally does not hold for scattered light measurements due to many light paths contributing to the measurement. While in many cases linear approximation can be made, for scenarios with strong absorptions non-linear effects cannot always be neglected. This is especially the case for observation geometries, for which the light contributing to the measurement is crossing the atmosphere under spatially well-separated paths differing strongly in length and location, like in limb geometry. In these cases, often full retrieval algorithms are applied to address the non-linearities, requiring iterative forward modelling of absorption spectra involving time-consuming wavelength-by-wavelength radiative transfer modelling. In this study, we propose to describe the non-linear effects by additional sensitivity parameters that can be used e.g. to build up a lookup table. Together with widely used box air mass factors (effective light paths) describing the linear response to the increase in the trace gas amount, the higher-order sensitivity parameters eliminate the need for repeating the radiative transfer modelling when modifying the absorption scenario even in the presence of a strong absorption background. While the higher-order absorption structures can be described as separate fit parameters in the spectral analysis (so-called DOAS fit), in practice their quantitative evaluation requires good measurement quality (typically better than that available from current measurements). Therefore, we introduce an iterative retrieval algorithm correcting for the higher-order absorption structures not yet considered in the DOAS fit as well as the absorption dependence on

  10. Effect of the concentration of magnetic grains on the linear-optical-absorption coefficient of ferrofluid-doped lyotropic mesophases: deviation from the Beer-Lambert law.

    PubMed

    Cuppo, F L S; Gómez, S L; Figueiredo Neto, A M

    2004-04-01

    In this paper is reported a systematic experimental study of the linear-optical-absorption coefficient of ferrofluid-doped isotropic lyotropic mixtures as a function of the magnetic-grains concentration. The linear optical absorption of ferrolyomesophases increases in a nonlinear manner with the concentration of magnetic grains, deviating from the usual Beer-Lambert law. This behavior is associated to the presence of correlated micelles in the mixture which favors the formation of small-scale aggregates of magnetic grains (dimers), which have a higher absorption coefficient with respect to that of isolated grains. We propose that the indirect heating of the micelles via the ferrofluid grains (hyperthermia) could account for this nonlinear increase of the linear-optical-absorption coefficient as a function of the grains concentration.

  11. Absorption spectra of adenocarcinoma and squamous cell carcinoma cervical tissues

    NASA Astrophysics Data System (ADS)

    Ivashko, Pavlo; Peresunko, Olexander; Zelinska, Natalia; Alonova, Marina

    2014-08-01

    We studied a methods of assessment of a connective tissue of cervix in terms of specific volume of fibrous component and an optical density of staining of connective tissue fibers in the stroma of squamous cancer and cervix adenocarcinoma. An absorption spectra of blood plasma of the patients suffering from squamous cancer and cervix adenocarcinoma both before the surgery and in postsurgical periods were obtained. Linear dichroism measurements transmittance in polarized light at different orientations of the polarization plane relative to the direction of the dominant orientation in the structure of the sample of biotissues of stroma of squamous cancer and cervix adenocarcinoma were carried. Results of the investigation of the tumor tissues showed that the magnitude of the linear dichroism Δ is insignificant in the researched spectral range λ=280-840 nm and specific regularities in its change observed short-wave ranges.

  12. Gauge-Invariant Formulation of Circular Dichroism.

    PubMed

    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. PMID:27295541

  13. Spectroscopic determination of leaf biochemistry using band-depth analysis of absorption features and stepwise multiple linear regression

    USGS Publications Warehouse

    Kokaly, R.F.; Clark, R.N.

    1999-01-01

    We develop a new method for estimating the biochemistry of plant material using spectroscopy. Normalized band depths calculated from the continuum-removed reflectance spectra of dried and ground leaves were used to estimate their concentrations of nitrogen, lignin, and cellulose. Stepwise multiple linear regression was used to select wavelengths in the broad absorption features centered at 1.73 ??m, 2.10 ??m, and 2.30 ??m that were highly correlated with the chemistry of samples from eastern U.S. forests. Band depths of absorption features at these wavelengths were found to also be highly correlated with the chemistry of four other sites. A subset of data from the eastern U.S. forest sites was used to derive linear equations that were applied to the remaining data to successfully estimate their nitrogen, lignin, and cellulose concentrations. Correlations were highest for nitrogen (R2 from 0.75 to 0.94). The consistent results indicate the possibility of establishing a single equation capable of estimating the chemical concentrations in a wide variety of species from the reflectance spectra of dried leaves. The extension of this method to remote sensing was investigated. The effects of leaf water content, sensor signal-to-noise and bandpass, atmospheric effects, and background soil exposure were examined. Leaf water was found to be the greatest challenge to extending this empirical method to the analysis of fresh whole leaves and complete vegetation canopies. The influence of leaf water on reflectance spectra must be removed to within 10%. Other effects were reduced by continuum removal and normalization of band depths. If the effects of leaf water can be compensated for, it might be possible to extend this method to remote sensing data acquired by imaging spectrometers to give estimates of nitrogen, lignin, and cellulose concentrations over large areas for use in ecosystem studies.We develop a new method for estimating the biochemistry of plant material using

  14. Magnetic x-ray dichroism in ultrathin epitaxial films

    SciTech Connect

    Tobin, J.G.; Goodman, K.W.; Cummins, T.R.

    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.

  15. Circular dichroism of chiral photonic crystal liquid layers with enclosed defect inside

    NASA Astrophysics Data System (ADS)

    Gevorgyan, Ashot; Kocharian, Armen; Vardanyan, Gagik

    2015-03-01

    The photonic crystals of artificial and self-organizing structures with spatial periodic changes in dielectric and magnetic properties have attracted considerable interest recently due to unusual physical properties and wide practical applications. The chiral periodic structure in the scale of optical wavelength gives rise to strong and characteristic circular dichroism responses at visible wavelengths. Here we investigate photonic density, circular dichroism and peculiarities of absorption and emission spectra at various eigen polarizations in multilayered one-dimensional chiral soft matter with two layers of CLCs and an isotropic defect layer inside. The circular dichroism is defined by differences in light energy absorption A=1-(R + T) by the system (R and T are the reflection and transmission coefficients, respectively) and A s , r are the light absorptions, if the incident light has left and right circular polarizations, respectively. This problem can be solved by the modified Ambartsumian's layer addition method. The influence of absorption and gain on the circular dichroism, absorption and emission spectra is established in cholesteric liquid crystal (CLC) cell with an isotropic defect layer inside.

  16. Magnetic circular dichroism of chlorofullerenes: Experimental and computational study

    NASA Astrophysics Data System (ADS)

    Štěpánek, Petr; Straka, Michal; Šebestík, Jaroslav; Bouř, Petr

    2016-03-01

    Magnetic circular dichroism (MCD) spectra of C60Cl6, C70Cl10 and C60Cl24 were measured and interpreted using a sum-over-state (SOS) protocol exploiting time dependent density functional theory (TDDFT). Unlike for plain absorption, the MCD spectra exhibited easily recognizable features specific for each chlorinated molecule and appear as a useful tool for chlorofullerene identification. MCD spectrum of C60Cl24 was below 400 nm partially obscured due to scattering and low solubility. In all cases a finer vibrational structure of the electronic bands was observed at longer wavelengths. The TDDFT simulations provided a reasonable basis for interpretation of the most prominent spectral features.

  17. Fast inversion scheme for the linearized problem in optical absorption tomography on objects with radially symmetric boundaries

    NASA Astrophysics Data System (ADS)

    Hampel, Uwe; Freyer, Richard

    1996-12-01

    We present a reconstruction scheme which solves the inverse linear problem in optical absorption tomography for radially symmetric objects. This is a relevant geometry for optical diagnosis in soft tissues, e.g. breast, testis and even head. The algorithm utilizes an invariance property of the linear imaging operator in homogeneously scattering media. The inverse problem is solved in the Fourier space of the angular component leading to a considerable dimension reduction which allows to compute the inverse in a direct way using singular value decomposition. There are two major advantages of this approach. First the inverse operator can be stored in computer memory and the computation of the inverse problem comprises only a few matrix multiplications. This makes the algorithm very fast and suitable for parallel execution. On the other hand we obtain the spectrum of the imaging operator that allows conclusions about reconstruction limits in the presence of noise and gives a termination criterion for image synthesis. To demonstrate the capabilities of this scheme reconstruction results from synthetic and phantom data are presented.

  18. Scaling of the L{sub 2,3} circular magnetic x-ray dichroism of Fe nitrides

    SciTech Connect

    Alouani, M. |; Wills, J.M.; Wilkins, J.W.

    1998-04-01

    We have implemented the calculation of the x-ray-absorption cross section for left- and right-circularly polarized x-ray beams within the local-density approximation by means of our all-electron full-relativistic and spin-polarized full-potential linear muffin-tin orbital method. We show that the L{sub 2,3} circular magnetic x-ray dichroism of Fe, Fe{sub 3}N, and Fe{sub 4}N compounds scales to a single curve when divided by the local magnetic moment. Sum rules determine the spin and orbital magnetic moment of iron atoms in these ordered iron nitrides. {copyright} {ital 1998} {ital The American Physical Society}

  19. Effect of size and indium-composition on linear and nonlinear optical absorption of InGaN/GaN lens-shaped quantum dot

    NASA Astrophysics Data System (ADS)

    Ahmed, S. Jbara; Zulkafli, Othaman; M, A. Saeed

    2016-05-01

    Based on the Schrödinger equation for envelope function in the effective mass approximation, linear and nonlinear optical absorption coefficients in a multi-subband lens quantum dot are investigated. The effects of quantum dot size on the interband and intraband transitions energy are also analyzed. The finite element method is used to calculate the eigenvalues and eigenfunctions. Strain and In-mole-fraction effects are also studied, and the results reveal that with the decrease of the In-mole fraction, the amplitudes of linear and nonlinear absorption coefficients increase. The present computed results show that the absorption coefficients of transitions between the first excited states are stronger than those of the ground states. In addition, it has been found that the quantum dot size affects the amplitudes and peak positions of linear and nonlinear absorption coefficients while the incident optical intensity strongly affects the nonlinear absorption coefficients. Project supported by the Ministry of Higher Education and Scientific Research in Iraq, Ibnu Sina Institute and Physics Department of Universiti Teknologi Malaysia (UTM RUG Vote No. 06-H14).

  20. Configuration of singular optical cones in gyrotropic crystals with dichroism

    SciTech Connect

    Merkulov, V. S.

    2015-02-15

    Optical conic singularities in crystals with linear dichroism and natural optical activity at the point of intersection of dispersion curves for the main refractive indices are considered. The possible existence of singularities like a nodal point, tangency point, triple point, and cusps of the first and second order is demonstrated. Forty-nine different types of irreducible fourth-order optical cones obtained by sequential bifurcations of eight main singular cones are established. The classification is based on the concept of roughness of systems depending on parameters.

  1. Implications of dose-dependent target tissue absorption for linear and non-linear/threshold approaches in development of a cancer-based oral toxicity factor for hexavalent chromium.

    PubMed

    Haney, J

    2015-07-01

    Dose-dependent changes in target tissue absorption have important implications for determining the most defensible approach for developing a cancer-based oral toxicity factor for hexavalent chromium (CrVI). For example, mouse target tissue absorption per unit dose is an estimated 10-fold lower at the CrVI dose corresponding to the federal maximum contaminant level (MCL) than at the USEPA draft oral slope factor (SFo) point of departure dose. This decreasing target tissue absorption as doses decrease to lower, more environmentally-relevant doses is inconsistent with linear low-dose extrapolation. The shape of the dose-response curve accounting for this toxicokinetic phenomenon would clearly be non-linear. Furthermore, these dose-dependent differences in absorption indicate that the magnitude of risk overestimation by a linear low-dose extrapolation approach (e.g., SFo) increases and is likely to span one or perhaps more orders of magnitude as it is used to predict risk at progressively lower, more environmentally-relevant doses. An additional apparent implication is that no single SFo can reliably predict risk across potential environmental doses (e.g., doses corresponding to water concentrations⩽the federal MCL). A non-linear approach, consistent with available mode of action data, is most scientifically defensible for derivation of an oral toxicity factor for CrVI-induced carcinogenesis.

  2. Supercontinuum of a 3.9 -μ m filament in air: Formation of a two-octave plateau and nonlinearly enhanced linear absorption

    NASA Astrophysics Data System (ADS)

    Panov, Nikolay A.; Shipilo, Daniil E.; Andreeva, Vera A.; Kosareva, Olga G.; Saletsky, Alexander M.; Xu, Huailiang; Polynkin, Pavel

    2016-10-01

    Through numerical simulations we reveal the scenario of 3.9 -μ m filament spectrum enrichment in the atmosphere in the cases of linear and circular polarization of the incident pulse. The discrete spectrum of odd harmonics transforms into the two-octave plateau in the case of linear polarization. In contrast, in the case of circular polarization of the incident pulse, the harmonic-free flat supercontinuum appears with the plasma onset, reaching the tenth harmonic of the input radiation. We identify the energy balance specific to the filamentation near 4 μ m : the absorption on CO2 lines in the atmosphere is accelerated by the self-phase modulation in the Kerr nonlinearity early before the plasma channel is formed. This nonlinearly enhanced linear absorption overwhelms the plasma losses and conversion of the input pulse energy to the higher harmonics as well as the plateau.

  3. Circular dichroism and conformation of fish hemoglobins.

    PubMed

    Greenwood, C; Gibson, Q H

    1983-04-10

    The circular dichroism spectrum of fully liganded CO hemoglobin from the Atlantic bluefin tuna (Tunnus thynnus) shows a pH- and temperature-dependent feature at 416 nm. It is half-developed at pH 5.9 and 20 degrees C and its change with temperature corresponds to a heat of 34 kcal/mol (tetramer) for the transition. Correlation with studies on function (Morris, R. J., and Gibson, Q. H. (1982) J. Biol. Chem. 257, 4869-4874) shows that the dichroism feature changes at about 1 pH unit below the R-T transition. There is a close correlation between the 416 nm band and changes in circular dichroism at 287 nm. The new 416 nm band is seen in several fish hemoglobins, but not with human hemoglobin. With hemoglobin from Brevoortia tyrannus, which has been sufficiently studied to permit the comparison, there is a smaller gap between the change in dichroism spectrum and the functional R-T transition. So far, no change in function has been associated with the appearance of the 416 nm circular dichroism band. PMID:6833248

  4. Magnetic circular dichroism in the ion yield of polarized chromium atoms at the 2p edge

    SciTech Connect

    Pruemper, G.; Viefhaus, J.; Becker, U.; Kroeger, S.; Mueller, R.; Zimmermann, P.; Martins, M.

    2003-09-01

    The effect of magnetic dichroism in the partial and total ion yield of chromium, i.e., the absorption of polarized chromium vapor was observed in the gas phase. The measurements were performed at the 2p edge and at photon energies above the 2p edge. The structure of the dichroism at the 2p edge can be understood by including the coupling of the 2p hole with the 3d and 4s shells. Our experimental results for the dichroism at the 2p edge are similar to results of solid-state experiments. Implications for the sum rules used as a standard tool to calculate the spin and orbital momentum are discussed.

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

    ERIC Educational Resources Information Center

    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…

  6. Flow dichroism in critical colloidal fluids

    SciTech Connect

    Lenstra, T. A. J.; Dhont, J. K. G.

    2001-06-01

    Due to long-range correlations and slow dynamics of concentration fluctuations in the vicinity of the gas-liquid critical point, shear flow is very effective in distorting the microstructure of near-critical fluids. The anisotropic nature of the shear-field renders the microstructure highly anisotropic, leading to dichroism. Experiments on the dichroic behavior can thus be used to test theoretical predictions on microstructural order under shear flow conditions. We performed both static and dynamic dichroism and turbidity measurements on a colloid-polymer mixture, existing of silica spheres (radius 51 nm) and polydimethylsiloxane polymer (molar weight 204 kg/mol). Sufficiently far away from the critical point, in the mean-field region, the experimental data are in good agreement with theory. Very close to the critical point, beyond mean field, for which no theory exists yet, an unexpected decrease of dichroism on approach of the critical point is observed. Moreover, we do not observe critical slowing down of shear-induced dichroism, right up to the critical point, in contrast to the turbidity.

  7. Towards AB Initio Calculation of the Circular Dichroism of Peptides

    NASA Astrophysics Data System (ADS)

    Molteni, E.; Onida, G.; Tiana, G.

    2012-08-01

    In this work we plan to use ab initio spectroscopy calculations to compute circular dichroism (CD) spectra of peptides. CD provides information on protein secondary structure content; peptides, instead, remain difficult to address, due to their tendency to adopt multiple conformations in equilibrium. Therefore peptides are an interesting test-case for ab initio calculation of CD spectra. As a first application, we focus on the (83-92) fragment of HIV-1 protease, which is known to be involved in the folding and dimerization of this protein. As a preliminary step, we performed classical molecular dynamics (MD) simulations, in order to obtain a set of representative conformers of the peptide. Then, on some of the obtained conformations, we calculated absorption spectra at the independent particle, RPA and TDLDA levels, showing the presence of charge transfer excitations, and their influence on spectral features.

  8. Circular magnetic x-ray dichroism in rare earth compounds

    SciTech Connect

    Jonathan, L.

    1993-09-30

    This report discusses the following topics: Circular magnetic x-ray dichroism at the ER L{sub 3} Edge; angular dependence of circular magnetic x-ray dichroism in rare earth compounds: and circular magnetic x-ray dichroism in crystalline and amorphous GDFE{sub 2}.

  9. Dichroism of Photosensitive Pigment in Rhabdoms of the Crayfish Orconectes

    PubMed Central

    Waterman, Talbot H.; Fernández, Hector R.; Goldsmith, Timothy H.

    1969-01-01

    Microspectrophotometric measurements of isolated crayfish rhabdoms illuminated transversely show that their photosensitive absorption exhibits a dichroic ratio of 2 in situ. The major absorption axis matches the axial direction of the closely parallel microvilli comprising the receptor organelle. Since these microvilli are regularly oriented transversely in about 24 layers, with the axes of the microvilli at 90° in alternate layers, transverse illumination of a properly oriented rhabdom displays alternate dichroic and isotropic bands. Because all the microvilli from any one cell share the same orientation, the layers of microvilli constitute two sets of orthogonal polarization analyzers when illuminated along the normal visual axis. Furthermore, since the dichroic ratio is 2 and transverse absorption in isotropic bands is the same as that in the minor absorbing axis of dichroic bands, the simplest explanation of the analyzer action is that the absorbing dipoles of the chromophores, as in rod and cone outer segments, lie parallel to the membrane surface but are otherwise randomly oriented. The rhabdom's functional dichroism thus arises from its specific fine structural geometry. PMID:5806598

  10. Dichroism of photosensitive pigment in rhabdoms of the crayfish Orconectes.

    PubMed

    Waterman, T H; Fernández, H R; Goldsmith, T H

    1969-09-01

    Microspectrophotometric measurements of isolated crayfish rhabdoms illuminated transversely show that their photosensitive absorption exhibits a dichroic ratio of 2 in situ. The major absorption axis matches the axial direction of the closely parallel microvilli comprising the receptor organelle. Since these microvilli are regularly oriented transversely in about 24 layers, with the axes of the microvilli at 90 degrees in alternate layers, transverse illumination of a properly oriented rhabdom displays alternate dichroic and isotropic bands. Because all the microvilli from any one cell share the same orientation, the layers of microvilli constitute two sets of orthogonal polarization analyzers when illuminated along the normal visual axis. Furthermore, since the dichroic ratio is 2 and transverse absorption in isotropic bands is the same as that in the minor absorbing axis of dichroic bands, the simplest explanation of the analyzer action is that the absorbing dipoles of the chromophores, as in rod and cone outer segments, lie parallel to the membrane surface but are otherwise randomly oriented. The rhabdom's functional dichroism thus arises from its specific fine structural geometry.

  11. Absorption of a linear (L2) and a cyclic (D4) siloxane using different oils: application to biogas treatment.

    PubMed

    Rojas Devia, Carolina; Subrenat, Albert

    2013-01-01

    Hydrophobic volatile methyl siloxanes (VMS), such as hexamethyldisiloxane (L2) and octamethylcyclotetrasiloxane (D4), present a low solubility in water. An alternative treatment by absorption into hydrophobic absorbents was therefore studied. For this purpose, three different absorbents, motor oil, cutting oil and a water-cutting oil mixture, were selected with the aim of re-using a waste product. The set of experiments was carried out in a bubble column, where parameters such as inlet concentration, residence time and temperature were studied. The best performance for the removal of both siloxanes, in terms of absorption capacity, was observed for motor oil, particularly for D4. In fact, motor oil removal efficiency for D 4 was 80%, whereas for L2 it was 60%, indicating that D 4 is more easily absorbed than L2. In the case of water-cutting oil, this showed a mass transfer enhancement from the gas phase to the liquid phase compared with water alone. Furthermore, a removal efficiency of 70% was observed for D 4, showing that the addition of an oil fraction to a water system improves the absorption of VMS. These results show that VMS absorption into oils could be a promising way to achieve their abatement.

  12. Joint reconstruction of absorption and refractive properties in propagation-based x-ray phase-contrast tomography via a non-linear image reconstruction algorithm

    NASA Astrophysics Data System (ADS)

    Chen, Yujia; Wang, Kun; Gursoy, Doga; Soriano, Carmen; De Carlo, Francesco; Anastasio, Mark A.

    2016-03-01

    Propagation-based X-ray phase-contrast tomography (XPCT) provides the opportunity to image weakly absorbing objects and is being explored actively for a variety of important pre-clinical applications. Quantitative XPCT image reconstruction methods typically involve a phase retrieval step followed by application of an image reconstruction algorithm. Most approaches to phase retrieval require either acquiring multiple images at different object-to-detector distances or introducing simplifying assumptions, such as a single-material assumption, to linearize the imaging model. In order to overcome these limitations, a non-linear image reconstruction method has been proposed previously that jointly estimates the absorption and refractive properties of an object from XPCT projection data acquired at a single propagation distance, without the need to linearize the imaging model. However, the numerical properties of the associated non-convex optimization problem remain largely unexplored. In this study, computer simulations are conducted to investigate the feasibility of the joint reconstruction problem in practice. We demonstrate that the joint reconstruction problem is ill-posed and sensitive to system inconsistencies. Particularly, the method can generate accurate refractive index images only if the object is thin and has no phase-wrapping in the data. However, we also observed that, for weakly absorbing objects, the refractive index images reconstructed by the joint reconstruction method are, in general, more accurate than those reconstructed using methods that simply ignore the object's absorption.

  13. Generation of circularly polarized radiation from a compact plasma-based extreme ultraviolet light source for tabletop X-ray magnetic circular dichroism studies.

    PubMed

    Wilson, Daniel; Rudolf, Denis; Weier, Christian; Adam, Roman; Winkler, Gerrit; Frömter, Robert; Danylyuk, Serhiy; Bergmann, Klaus; Grützmacher, Detlev; Schneider, Claus M; Juschkin, Larissa

    2014-10-01

    Generation of circularly polarized light in the extreme ultraviolet (EUV) spectral region (about 25 eV-250 eV) is highly desirable for applications in spectroscopy and microscopy but very challenging to achieve in a small-scale laboratory. We present a compact apparatus for generation of linearly and circularly polarized EUV radiation from a gas-discharge plasma light source between 50 eV and 70 eV photon energy. In this spectral range, the 3p absorption edges of Fe (54 eV), Co (60 eV), and Ni (67 eV) offer a high magnetic contrast often employed for magneto-optical and electron spectroscopy as well as for magnetic imaging. We simulated and designed an instrument for generation of linearly and circularly polarized EUV radiation and performed polarimetric measurements of the degree of linear and circular polarization. Furthermore, we demonstrate first measurements of the X-ray magnetic circular dichroism at the Co 3p absorption edge with a plasma-based EUV light source. Our approach opens the door for laboratory-based, element-selective spectroscopy of magnetic materials and spectro-microscopy of ferromagnetic domains. PMID:25362374

  14. Generation of circularly polarized radiation from a compact plasma-based extreme ultraviolet light source for tabletop X-ray magnetic circular dichroism studies

    SciTech Connect

    Wilson, Daniel; Rudolf, Denis Juschkin, Larissa; Weier, Christian; Adam, Roman; Schneider, Claus M.; Winkler, Gerrit; Frömter, Robert; Danylyuk, Serhiy; Bergmann, Klaus; Grützmacher, Detlev

    2014-10-15

    Generation of circularly polarized light in the extreme ultraviolet (EUV) spectral region (about 25 eV–250 eV) is highly desirable for applications in spectroscopy and microscopy but very challenging to achieve in a small-scale laboratory. We present a compact apparatus for generation of linearly and circularly polarized EUV radiation from a gas-discharge plasma light source between 50 eV and 70 eV photon energy. In this spectral range, the 3p absorption edges of Fe (54 eV), Co (60 eV), and Ni (67 eV) offer a high magnetic contrast often employed for magneto-optical and electron spectroscopy as well as for magnetic imaging. We simulated and designed an instrument for generation of linearly and circularly polarized EUV radiation and performed polarimetric measurements of the degree of linear and circular polarization. Furthermore, we demonstrate first measurements of the X-ray magnetic circular dichroism at the Co 3p absorption edge with a plasma-based EUV light source. Our approach opens the door for laboratory-based, element-selective spectroscopy of magnetic materials and spectro-microscopy of ferromagnetic domains.

  15. New applications of x-ray magnetic circular dichroism

    NASA Astrophysics Data System (ADS)

    Schütz, G.; Fischer, P.; Attenkofer, K.; Ahlers, D.

    1997-01-01

    X-ray magnetic circular dichroism (X-MCD) in core-level absorption is intimately related to the local spin and orbital polarization distribution in the final states, as it is based on angular-momentum conservation and the interplay of exchange and spin-orbit interaction. It provides symmetry and element-selective information about magnetic aspects of electronic structure. In favourable cases spin and orbital contributions to the local magnetic moments can be deduced directly by applying the so-called "sum-rules". Recently studies of the dichroic contributions in the EXAFS energy range have attracted considerable attention. From systematic studies in various systems a direct proportionality between the strengths of the magnetic signal and the spin moment has been found. This can be easily explained by an exchange contribution to the Coulomb backscattering amplitude and gives important new insights into the exchange interactions of low-energy electrons in solids. With the advent of new intense x-ray sources a variety of other x-ray methods, which involve core-level absorption, can be used to study magnetism. Recent examples are magnetic anomalous small-angle x-ray scattering and imaging magnetic domains with a zone-plate x-ray microscope, which both provide a high-resolution quantitative details of the spatial magnetization contributions.

  16. Multicompartment kinetic models for lead. II. Linear kinetics and variable absorption in humans without excessive lead exposures

    SciTech Connect

    Marcus, A.H.

    1985-04-01

    Multicompartment models with constant fractional transfer rates have been fitted to experimental data on lead metabolism in four subjects studied by M.B. Rabinowitz, G.W. Wetherill, and J.D. Kopple. Long-term retention is estimated for blood, soft tissue, cortical and trabecular bone pools, and for facial hair. The absorption of lead from diet is shown to change with time, but no evidence was found for other variable or nonlinear kinetic mechanisms of lead metabolism in humans without excessive lead exposure.

  17. Exciton Theory for Supramolecular Chlorosomal Aggregates: 1. Aggregate Size Dependence of the Linear Spectra

    PubMed Central

    Prokhorenko, V. I.; Steensgaard, D. B.; Holzwarth, A. R.

    2003-01-01

    The interior of chlorosomes of green bacteria forms an unusual antenna system organized without proteins. The steady-spectra (absorption, circular dichroism, and linear dichroism) have been modeled using the Frenkel Hamiltonian for the large tubular aggregates of bacteriochlorophylls with geometries corresponding to those proposed for Chloroflexus aurantiacus and Chlorobium tepidum chlorosomes. For the Cf. aurantiacus aggregates we apply a structure used previously (V. I. Prokhorenko., D. B. Steensgaard, and A. R. Holzwarth, Biophys. J. 2000, 79:2105–2120), whereas for the Cb. tepidum aggregates a new extended model of double-tube aggregates, based on recently published solid-state nuclear magnetic resonance studies (B.-J. van Rossum, B. Y. van Duhl, D. B. Steensgaard, T. S. Balaban, A. R. Holzwarth, K. Schaffner, and H. J. M. de Groot, Biochemistry 2001, 40:1587–1595), is developed. We find that the circular dichroism spectra depend strongly on the aggregate length for both types of chlorosomes. Their shape changes from “type-II” (negative at short wavelengths to positive at long wavelengths) to the “mixed-type” (negative-positive-negative) in the nomenclature proposed in K. Griebenow, A. R. Holzwarth, F. van Mourik, and R. van Grondelle, Biochim. Biophys. Acta 1991, 1058:194–202, for an aggregate length of 30–40 bacteriochlorophyll molecules per stack. This “size effect” on the circular dichroism spectra is caused by appearance of macroscopic chirality due to circular distribution of the transition dipole moment of the monomers. We visualize these distributions, and also the corresponding Frenkel excitons, using a novel presentation technique. The observed size effects provide a key to explain many previously puzzling and seemingly contradictory experimental data in the literature on the circular and linear dichroism spectra of seemingly identical types of chlorosomes. PMID:14581217

  18. Donor impurity-related linear and nonlinear intraband optical absorption coefficients in quantum ring: effects of applied electric field and hydrostatic pressure.

    PubMed

    Barseghyan, Manuk G; Restrepo, Ricardo L; Mora-Ramos, Miguel E; Kirakosyan, Albert A; Duque, Carlos A

    2012-01-01

    : The linear and nonlinear intraband optical absorption coefficients in GaAs three-dimensional single quantum rings are investigated. Taking into account the combined effects of hydrostatic pressure and electric field, applied along the growth direction of the heterostructure, the energies of the ground and first excited states of a donor impurity have been found using the effective mass approximation and a variational method. The energies of these states are examined as functions of the dimensions of the structure, electric field, and hydrostatic pressure. We have also investigated the dependencies of the linear, nonlinear, and total optical absorption coefficients as a function of incident photon energy for several configurations of the system. It is found that the variation of distinct sizes of the structure leads to either a redshift and/or a blueshift of the resonant peaks of the intraband optical spectrum. In addition, we have found that the application of an electric field leads to a redshift, whereas the influence of hydrostatic pressure leads to a blueshift (in the case of on-ring-center donor impurity position) of the resonant peaks of the intraband optical spectrum. PMID:23021497

  19. Multicompartment kinetic models for lead. 2. Linear kinetics and variable absorption in humans without excessive lead exposures

    SciTech Connect

    Marcus, A.H.

    1985-01-01

    Multicompartment models with constant fractional transfer rates were fitted to experimental data on lead metabolism in four subjects studied by M. B. Rabinowitz, G. W. Wetherill, and J. D. Kopple (Science 182, 725-727, 1973; Environ. Health Perspect. 7, 145-153, 1974; Arch. Environ. Health 31, 220-223, 1976; J. Clin. Invest. 58, 260-270, 1976; J. Lab Clin. Med. 90, 238-248, 1977). Long-term retention is estimated for blood, soft tissue, cortical and trabecular bone pools, and for facial hair. The absorption of lead from diet is shown to change with time, but no evidence was found for other variable or nonlinear kinetic mechanisms of lead metabolism in humans without excessive lead exposure.

  20. Photophysics and non-linear absorption of Au(I) and Pt(II) acetylide complexes of a thienyl-carbazole chromophore.

    PubMed

    Goswami, Subhadip; Wicks, Geoffrey; Rebane, Aleksander; Schanze, Kirk S

    2014-12-21

    In order to understand the photophysics and non-linear optical properties of carbazole containing π-conjugated oligomers of the type ET-Cbz-TE (E = ethynylene, T = 2,5-thienylene, Cbz = 3,6-carbazole), a detailed investigation was carried out on a series of oligomers that feature Au(i) or Pt(ii) acetylide "end groups", as well as a Pt(ii)-acetylide linked polymer (CBZ-Au-1 and CBZ-Pt-1, CBZ-Poly-Pt). These organometallic chromophores were characterized by UV-visible absorption and variable temperature photoluminescence spectroscopy, nanosecond transient absorption spectroscopy, open aperture nanosecond z-scan and two photon absorption (2PA) spectroscopy. The Au(i) and Pt(ii) oligomers and polymer exhibit weak fluorescence in fluid solution at room temperature. Efficient phosphorescence is observed from the Pt(ii) systems below 150 K in a solvent glass; however, the Au(i) oligomer exhibits only weak phosphorescence at 77 K. Taken together, the emission results indicate that the intersystem crossing efficiency for the Pt(ii) chromophores is greater than for the Au(i) oligomer. Nonetheless, nanosecond transient absorption indicates that direct excitation affords moderately long-lived triplet states for all of the chromophores. Open aperture z-scan measurement shows effective optical attenuation can be achieved by using these materials. The 2PA cross section in the degenerate S0→S1 transition region was in the range 10-100 GM, and increased monotonically toward shorter wavelengths, reaching 800-1000 GM at 550 nm.

  1. Magnetic dichroism effect of binary alloys using circularly-polarized x-ray

    SciTech Connect

    Wu, S. Z.; Schumann, F.O.; Willis, R.F.; Goodman, K.W.; Tobin, J.G.; Carr, R.

    1997-05-01

    We have studies the magnetic propertied of CoNi binary alloy films with various atomic compositions using soft x-ray magnetic circular dichroism (XMCD) technique. The alloy films were deposited on single Cu(100) crystals in situ using our well-established epitaxial growth technique to achieve a layer-by-layer growth and a metastable fcc structure, with all films exhibiting an in-plane magnetic anistrophy. Utilizing the element-specific ability and nanostructure magnetization sensitivity of this technique, we have been able to perform the absorption measurements at L2 and L3 edge of Co and Ni atoms and observed large dichroism signals. The extraction of spin moment and orbital moment for varying elemental stoichiometry using magneto- optical sum rules is discussed.

  2. Dynamic linear response of atoms in plasmas and photo-absorption cross-section in the dipole approximation

    NASA Astrophysics Data System (ADS)

    Caizergues, C.; Blenski, T.; Piron, R.

    2016-03-01

    We report results on the self-consistent linear response theory of quantum average-atoms in plasmas. The approach is based on the two first orders of the cluster expansion of the plasma susceptibility. A change of variable is applied, which allows us to handle the diverging free-free transitions contribution in the self-consistent induced electron density and potential. The method is first tested on the case of rare gas isolated neutral atoms. A test of the Ehrenfest-type sum rule is then performed in a case of an actual average-atom in a plasma. At frequencies much higher than the plasma frequency, the sum rule seems to be fulfilled within the accuracy of the numerical methods. Close to the plasma frequency, the method seems not to account for the cold-plasma dielectric function renormalization in the sum rule, which was correctly reproduced in the case of the Thomas-Fermi-Bloch self-consistent linear response. This suggests the need for a better accounting for the outgoing waves in the asymptotic boundary conditions.

  3. Evolution of linear absorption and nonlinear optical properties in V-shaped ruthenium(II)-based chromophores.

    PubMed

    Coe, Benjamin J; Foxon, Simon P; Harper, Elizabeth C; Helliwell, Madeleine; Raftery, James; Swanson, Catherine A; Brunschwig, Bruce S; Clays, Koen; Franz, Edith; Garín, Javier; Orduna, Jesús; Horton, Peter N; Hursthouse, Michael B

    2010-02-10

    In this article, we describe a series of complexes with electron-rich cis-{Ru(II)(NH(3))(4)}(2+) centers coordinated to two pyridyl ligands bearing N-methyl/arylpyridinium electron-acceptor groups. These V-shaped dipolar species are new, extended members of a class of chromophores first reported by us (Coe, B. J. et al. J. Am. Chem. Soc. 2005, 127, 4845-4859). They have been isolated as their PF(6)(-) salts and characterized by using various techniques including (1)H NMR and electronic absorption spectroscopies and cyclic voltammetry. Reversible Ru(III/II) waves show that the new complexes are potentially redox-switchable chromophores. Single crystal X-ray structures have been obtained for four complex salts; three of these crystallize noncentrosymmetrically, but with the individual molecular dipoles aligned largely antiparallel. Very large molecular first hyperpolarizabilities beta have been determined by using hyper-Rayleigh scattering (HRS) with an 800 nm laser and also via Stark (electroabsorption) spectroscopic studies on the intense, visible d --> pi* metal-to-ligand charge-transfer (MLCT) and pi --> pi* intraligand charge-transfer (ILCT) bands. The latter measurements afford total nonresonant beta(0) responses as high as ca. 600 x 10(-30) esu. These pseudo-C(2v) chromophores show two substantial components of the beta tensor, beta(zzz) and beta(zyy), although the relative significance of these varies with the physical method applied. According to HRS, beta(zzz) dominates in all cases, whereas the Stark analyses indicate that beta(zyy) is dominant in the shorter chromophores, but beta(zzz) and beta(zyy) are similar for the extended species. In contrast, finite field calculations predict that beta(zyy) is always the major component. Time-dependent density functional theory calculations predict increasing ILCT character for the nominally MLCT transitions and accompanying blue-shifts of the visible absorptions, as the ligand pi-systems are extended. Such unusual

  4. Structural, thermal, linear and nonlinear optical studies of an organic optical limiter based on reverse saturable absorption

    NASA Astrophysics Data System (ADS)

    Menezes, Anthoni Praveen; Raghavendra, S.; Jayarama, A.; Sarveshwara, H. P.; Dharmaprakash, S. M.

    2016-09-01

    A new derivative of chalcone, 3-(4-bromophenyl)-1-(pyridin-4-yl) prop-2-en-1-one (4BP4AP), crystallizing in centrosymmetric structure has been synthesized using the Claisen-Schmidt condensation reaction method. The FTIR and FT-Raman spectral studies were carried out on 4BP4AP for structural conformation. The single crystals were grown using slow evaporation solution growth technique. The single crystal XRD of the crystal shows that the crystal system of 4BP4AP is triclinic with space group P-1. Scanning electron microscope images enunciate the surface smoothness and the two dimensional growth mechanisms in the crystal. The crystal is transparent in the entire visible region as indicated by the UV-VIS-NIR spectrum. The thermal stability and phase transition of the compound was studied by thermogravimetric and differential scanning calorimetric analysis and found to be stable up to 200 °C. By performing the open aperture z-scan experiment, nonlinear absorption and optical limiting behavior of the crystal were studied. The crystal can be used for optoelectronic application due to its excellent photo-physical properties.

  5. Circular dichroism spectroscopy of membrane proteins.

    PubMed

    Miles, A J; Wallace, B A

    2016-09-21

    Circular dichroism (CD) spectroscopy is a well-established technique for studying the secondary structures, dynamics, folding pathways, and interactions of soluble proteins, and is complementary to the high resolution but generally static structures produced by X-ray crystallography, NMR spectroscopy, and cryo electron microscopy. CD spectroscopy has special relevance for the study of membrane proteins, which are difficult to crystallise and largely ignored in structural genomics projects. However, the requirement for membrane proteins to be embedded in amphipathic environments such as membranes, lipid vesicles, detergent micelles, bicelles, oriented bilayers, or nanodiscs, in order for them to be soluble or dispersed in solution whilst maintaining their structure and function, necessitates the use of different experimental and analytical approaches than those employed for soluble proteins. This review discusses specialised methods for collecting and analysing membrane protein CD data, highlighting where protocols for soluble and membrane proteins diverge.

  6. Circular dichroism study of the hemocyanin thermostability

    NASA Astrophysics Data System (ADS)

    Nikolova Georgieva, Dessislava; Stoeva, Stanka; Abid Ali, Syed; Abbasi, Atiya; Genov, Nicolay; Voelter, Wolfgang

    1998-05-01

    Circular dichroism spectroscopy is used to investigate the thermostability of six arthropod hemocyanins (Hcs), representatives of the subphyla Crustacea (infraorder Brachyura) and Chelicerate (infraorders Xiphosura and Arachnida), and three molluscan Hcs from gastropod organisms. Melting points ( Tm) are determined from the temperature dependence of ellipticity of dioxygen-binding proteins from Maia squinado, Callinectes sapidus, Carcinus maenas, Limulus polyphemus, Buthus sindicus, Androctonus australis, Megathura crenulata, Haliotis tuberculata, and Rapana thomasiana. Both, arthropod and molluscan Hcs, are thermostable proteins with melting temperatures in the region 68-91°C. Binuclear dioxygen-binding sites contribute significantly to the thermostability and increase the Tm values of the apo-forms by 3-16°C. An elevated thermostability is observed in the case of the Limulus polyphemus Hc. One of the reasons is the high degree of hemocyanin oligomerization.

  7. Circular dichroism spectroscopy of membrane proteins.

    PubMed

    Miles, A J; Wallace, B A

    2016-09-21

    Circular dichroism (CD) spectroscopy is a well-established technique for studying the secondary structures, dynamics, folding pathways, and interactions of soluble proteins, and is complementary to the high resolution but generally static structures produced by X-ray crystallography, NMR spectroscopy, and cryo electron microscopy. CD spectroscopy has special relevance for the study of membrane proteins, which are difficult to crystallise and largely ignored in structural genomics projects. However, the requirement for membrane proteins to be embedded in amphipathic environments such as membranes, lipid vesicles, detergent micelles, bicelles, oriented bilayers, or nanodiscs, in order for them to be soluble or dispersed in solution whilst maintaining their structure and function, necessitates the use of different experimental and analytical approaches than those employed for soluble proteins. This review discusses specialised methods for collecting and analysing membrane protein CD data, highlighting where protocols for soluble and membrane proteins diverge. PMID:27347568

  8. Heparin-induced circular dichroism of an achiral, bicyclic species.

    PubMed

    Stanley, Floyd E; Warner, Andrew M; McWilliams, Kayla M; Stalcup, Apryll M

    2011-01-01

    Antimalarial drugs have shown potential in suppressing the role of glycosaminoglycans (GAGs) in the pathology of prion protein conformational disorders (e.g. "Mad Cow" disease) by competing for sites of electrostatic interaction. In this study, circular dichroism (CD) and UV/Visible (UV/Vis) absorption spectroscopy techniques were used to investigate the interactions between N-methyl-N'-(7-chloro-4-quinolyl)-1,3-diaminopropane (QD), an achiral, bicyclic compound similar to previously investigated antimalarial drugs, and heparin, a complex GAG that is frequently used as a clinical anticoagulant. Relatively intense heparin-induced CD features were observed for QD and were noted to be radically different from previous studies using related chiral drugs, underscoring the importance of the Pfieffer effect on this and similar heparin research. Additionally, the induced CD for QD was observed to be highly dependent upon drug concentration, heparin concentration, system pH, equilibration time, and ionic strength. These results, in connection with recent work, provide new insight into the nature of the association between GAGs and antimalarial species. PMID:21125690

  9. Optical properties and circular dichroism of chiral metal nanoparticles

    NASA Astrophysics Data System (ADS)

    Fan, Zhiyuan; Govorov, Alexander; OU Team

    2013-03-01

    In nature, biological systems are built up by homochiral building blocks, such as a sugar and protein. Circular dichroism (CD) is an effective tool of resolving molecular conformations. It utilizes circularly polarized light to detect differential absorption of chiral materials. In medicine, it will help us to develop new drugs and therapies, if we understand the connection between the physical or chemical properties of drug molecules and their conformations. With the rapid development of nanotechnologies, chiral nanomaterials attract lots of attention nowadays. CD signals of chiral molecules can be enhanced or shifted to the visible band in the presence of plasmonic nanocrystals. Here we present a plasmonic CD mechanism from a single chiral metal nanocrystal. The mechanism is essentially different from the dipolar plasmon-plasmon interaction in a chiral NP assembly, which mimics the CD mechanism of chiral molecules. Chiral metal nanocrystals are expected to have promising applications in biosensing. Recently a few experimental papers reported successful realizations of chiral nanocrystals in a macroscopic ensemble in solution. Particularly the paper described silver nanoparticles grown on chiral template molecules and demonstrating characteristic CD signals at a plasmonic wavelength. The plasmonic CD signals in Ref. can come from a dipolar plasmon-molecule interaction or from a chiral shape of nanocrystals. This work was supported by the NSF (project: CBET- 0933782) and by the Volkswagen Foundation.

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

    PubMed

    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.

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

    NASA Astrophysics Data System (ADS)

    Goings, Joshua J.; Li, Xiaosong

    2016-06-01

    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.

  12. Spin-Induced Polarizations and Nonreciprocal Directional Dichroism of the Room-Temperature Multiferroic BiFeO3

    DOE PAGES

    Fishman, Randy Scott; Lee, Jun Hee; Bordacs, Sandor; Kezsmarki, Istvan; Nagel, Urmas; Room, Toomas

    2015-09-14

    A microscopic model for the room-temperature multiferroic BiFeO3 that includes two Dzyaloshinskii-Moriya interactions and single-ion anisotropy along the ferroelectric polarization predicts both the zero-field spectroscopic modes as well as their splitting and evolution in a magnetic field. Due to simultaneously broken time-reversal and spatial-inversion symmetries, the absorption of light changes as the magnetic field or the direction of light propagation is reversed. We discuss three physical mechanisms that may contribute to this absorption asymmetry known as directional dichroism: the spin current, magnetostriction, and single-ion anisotropy. We conclude that the directional dichroism in BiFeO3 is dominated by the spin-current polarization andmore » is insensitive to the magnetostriction and easy-axis anisotropy. With three independent spin-current parameters, our model accurately describes the directional dichroism observed for magnetic field along [1, -1, 0]. Since some modes are almost transparent to light traveling in one direction but opaque for light traveling in the opposite direction, BiFeO3 can be used as a room-temperature optical diode at certain frequencies in the GHz to THz range. This work demonstrates that an analysis of the directional dichroism spectra based on an effective spin model supplemented by first-principles calculations can produce a quantitative microscopic theory of the magnetoelectric couplings in multiferroic materials.« less

  13. Photoemission and magnetic circular dichroism studies of magnetic semiconductors

    NASA Astrophysics Data System (ADS)

    Fujimori, Atsushi

    2005-03-01

    Recently, a series of novel ferromagnetic semiconductors have been synthesized using MBE and related techniques and have attracted much attention because of unknown mechanisms of carrier-induced ferromagnetism and potential applications as "spin electronics" devices. Some new materials show ferromagnetism even well above room temperature. Photoemission spectroscopy has been used to study the d orbitals of the dilute transition-metal atoms, mostly Mn, and their hybridization with the host band states [1]. Soft x-ray absorption spectroscopy (XAS) and magnetic circular dichroism (MCD) at the transition-metal 2p-3d absorption edges are useful techniques to study the valence and spin states of the transition-metal atoms. Furthermore, since MCD has different sensitivities to the ferromagnetic and paramagnetic components at different temperatures and magnetic fileds, if the sample is a mixture of ferromagnetic and non-ferromagnetic transition- metal atoms, it can be used to separate the two components and to study their electronic structures. In this talk, results are presented for the prototypical diluted ferromagnetic semiconductor Ga1-xMnxAs [2] and the room-temperature ferromagnets Zn1-xCoxO and Ti1-xCoxO2.I acknowledge collaboration with Y. Ishida, J.-I. Hwang, M. Kobayashi, Y. Takeda, Y. Saitoh, J. Okamoto, T. Okane, Y. Muramatsu, K. Mamiya, T. Koide, A. Tanaka, M. Tanaka, Hayashi, S. Ohya, T. Kondo, H. Munekata, H. Saeki, H. Tabata, T. Kawai, Y. Matsumoto, H. Koinuma, T. Fukumura and M. Kawasaki. This work was supported by a Grant-in-Aid for Scientific Research in Priority Area "Semiconductor nano-spintronics" (14076209) from MEXT, Japan.1. J. Okabayashi et al., Phys. Rev. B 64, 125304 (2001).2. A. Fujimori et al., J. Electron Spectrosc. Relat. Phenom., in press.

  14. Octupole Magnet For Soft X Ray Magnetic Dichroism Experiments: Design and Performance

    SciTech Connect

    Arenholz, Elke; Prestemon, Soren O.

    2004-05-12

    An octupole magnet endstation for soft x ray magnetic dichroism measurements has been developed at the Advanced Light Source. The system consists of an eight pole electromagnet that surrounds a small vacuum chamber. The magnet provides fields up to 0.9 T that can be applied in any direction relative to the incoming x ray beam. High precision magnetic circular and linear dichroism spectra can be obtained reversing the magnetic field for each photon energy in an energy scan. Moreover, the field dependence of all components of the magnetization vector can be studied in detail by choosing various angles of x ray incidence while keeping the relative orientation of magnetic field and sample fixed.

  15. Design and performance of an eight pole resistive magnet for softx-ray magnetic dichroism measurements

    SciTech Connect

    Arenholz, Elke; Prestemon, Soren O.

    2005-06-01

    To take full advantage of the strengths of soft x-ray magnetic dichroism (XMD) measurements for the detailed and quantitative characterization of multi-element magnetic materials, we developed an eight pole electromagnet that provides magnetic fields up to 0.9 T in any direction relative to the incoming x-ray beam. The setup allows us to measure magnetic circular and linear dichroism spectra as well as to thoroughly study magnetization reversal processes with very high precision. Design constraints and system optimization for maximum peak field are discussed. The predicted current-field relation is in excellent agreement with experimental findings. A brief discussion of the key technical difficulties in developing a similar superconducting device with peak fields of 5 T and ramping rates suitable for point-by-point full field reversal in an XMD experiment is presented.

  16. A magnetizing system for dichroism measurements in soft x-ray emission excited by synchrotron radiation

    SciTech Connect

    Dallera, C.; Ghiringhelli, G.; Braicovich, L.

    1996-02-01

    We present the design and performance of a magnetic circuit suitable for magnetizing solid samples in the measurements of soft x-ray emission dichroism excited by synchrotron radiation. The system allows a variety of samples to be magnetized and satisfies the rather stringent geometrical constraints due to the need for minimizing the effect of photon self-absorption by the sample. The magnetic circuit is ultrahigh vacuum compatible, can reach about 2800 G, and allows fine adjustment of sample position. {copyright} {ital 1996 American Institute of Physics.}

  17. Instrument for x-ray magnetic circular dichroism measurements at high pressures

    SciTech Connect

    Haskel, D.; Tseng, Y. C.; Lang, J. C.; Sinogeikin, S.

    2007-08-15

    An instrument has been developed for x-ray magnetic circular dichroism (XMCD) measurements at high pressures and low temperatures. This instrument couples a nonmagnetic copper-beryllium diamond anvil cell featuring perforated diamonds with a helium flow cryostat and an electromagnet. The applied pressure can be controlled in situ using a gas membrane and calibrated using Cu K-edge x-ray absorption fine structure measurements. The performance of this instrument was tested by measuring the XMCD spectra of the Gd{sub 5}Si{sub 2}Ge{sub 2} giant magnetocaloric material.

  18. Plasmonic Circular Dichroism of Chiral Nanoparticle Assemblies

    NASA Astrophysics Data System (ADS)

    Fan, Zhiyuan; Zhang, Hui; Govorov, Alexander; Ohio University Team

    2014-03-01

    Plasmonic circular dichroism(CD) of chiral metal nanoparticle(MNP) assemblies in the visible band results from dipolar and multipolar interaction between plasmons on MNPs. Both isotropic and anisotropic CD signals are extremely dimension-sensitive and strongly configuration-dependent. In this presentation, such geometry-dependence of plasmonic CD response will be analytically studied using an expansion of many-dipole interaction of the systems. In the multipole regime, numerical simulations show new features of multipole plasmon interactions. One interesting observation is that a chiral equilateral tetramer made of 4 different NPs shows nearly zero CD response in the point dipole interaction regime but moderately strong CD response from multipole interaction of closely packed NP assemblies. Generally, CD signals of closely packed MNP assemblies are significantly enhanced and more sensitive to the geometric parameters. They can be used in many novel sensing applications as either solid-state or colloidal systems. A.O.G. acknowledges the Science Foundation Ireland. This work was supported by the U.S. Army Research Laboratory and the U.S. Army Research Office under contract/grant number W911NF-12-1-0407 and by the Volkswagen Foundation (Germany).

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

    PubMed Central

    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

  20. On the existence of Jones birefringence and Jones dichroism.

    PubMed

    Arteaga, Oriol

    2010-05-01

    We claim that the so-called Jones birefringence and Jones dichroism effects, understood as new optical phenomena of difficult experimental observation, cannot be deduced from Jones publications and were proposed due to a misinterpretation of his original work.

  1. Relationship between the magnetic moment of Lu and the magnetic behavior of (Y{sub y}Lu{sub 1-y})(Co{sub 1-x}Al{sub x}){sub 2} from x-ray absorption spectroscopy and x-ray magnetic circular dichroism

    SciTech Connect

    Chaboy, J.; Piquer, C.; Laguna-Marco, M. A.; Kawamura, N.; Suzuki, M.; Takagaki, M.

    2007-02-01

    We present an x-ray magnetic circular dichroism (XMCD) study performed at both the Co K edge and the Lu L{sub 2,3} edges on (Y{sub y}Lu{sub 1-y})(Co{sub 1-x}Al{sub x}){sub 2} systems. The XMCD spectra reflect the different magnetic character of these systems, allowing us to monitor the transition from weak to strong ferromagnetism. The XMCD at the Lu L{sub 2,3} edges indicates the existence of an ordered 5d moment at the lutetium sites that is coupled antiparallel to the Co moment. Estimates of the magnetic moment of Lu have been obtained by applying the XMCD sum rules. Our results show that there is a correlation between the Lu 5d-induced magnetic moment and the magnetic character of the (Y{sub y}Lu{sub 1-y})(Co{sub 1-x}Al{sub x}){sub 2} compounds. These results suggest that the developing of the Lu moment plays an important role in reinforcing the magnetic interactions and favoring the ferromagnetic character of the Lu-rich compounds.

  2. Calculation of polarized IR absorption spectra for trans-1,4-polyisoprenes of various conformations

    NASA Astrophysics Data System (ADS)

    Abdulov, Kh. Sh.

    2008-07-01

    Polarized IR spectra for two conformations of trans-1,4-polyisoprene (α-and β-gutta-percha) were calculated. The IR dichroism of the absorption bands was calculated for both conformations. The computed results for polarized IR spectra and IR dichroism agree reasonably well with the respective experiment data.

  3. Circular dichroism of a finite number of identical chromophores in a helical arrangement.

    PubMed

    Dick, Bernhard

    2011-06-01

    Compact expressions to calculate the transition energies, absorption line strengths, and rotational line strengths of circular dichroism for the excitonic states in a helical arrangement of N identical chromophores are presented. The absorption spectrum A(ν) and the CD spectrum C(ν) are given in terms of the same function G(ν,α) as A(ν) = a(1)G(ν,0) + a(2)G(ν,α), C(ν) = (s(1) - s(2))G(ν,α) + s(3)(d/dα)G(ν,α). The function G(ν,α) depends only on the helical angle α and the number N of interacting chromophores. An analytical expression can be given when only next-neighbor interactions are considered. All other structural parameters of the system (e.g. orientation of transition dipoles and the translation vector of the helix) enter only into the prefactors a(j) and s(j).

  4. Strong coupling between adenine nucleobases in DNA single strands revealed by circular dichroism using synchrotron radiation

    NASA Astrophysics Data System (ADS)

    Kadhane, Umesh; Holm, Anne I. S.; Hoffmann, Søren Vrønning; Nielsen, Steen Brøndsted

    2008-02-01

    Circular dichroism (CD) experiments on DNA single strands (dAn) at the ASTRID synchrotron radiation facility reveal that eight adenine (A) bases electronically couple upon 190nm excitation. After n=8 , the CD signal increases linearly with n with a slope equal to the sum of the coupling terms. Nearest neighbor interactions account for only 24% of the CD signal whereas electronic communication is limited to nearest neighbors for two other exciton bands observed at 218 and 251nm (i.e., dimer excited states). Electronic coupling between bases in DNA is important for nonradiative deexcitation of electronically excited states since the hazardous energy is spread over a larger spatial region.

  5. Z-DNA: vacuum ultraviolet circular dichroism.

    PubMed

    Sutherland, J C; Griffin, K P; Keck, P C; Takacs, P Z

    1981-08-01

    In concentrated salt or ethanolic solutions, the self-complementary copolymer poly(dG-dC).poly(dG-dC) forms a left-handed double-helical structure that has been termed "Z-DNA." The first evidence for this structure came from changes observed in the circular dichroism (CD) spectrum between 230 and 300 nm for low- and high-salt solutions (Pohl, F. M. & Jovin, T. M. (1972) J. Mol. Biol. 67, 675-696). In 3 M NaCl, the CD spectrum is approximately inverted compared to the B-form spectrum observed in low-salt solution. We measured the vacuum ultraviolet CD spectrum of poly(dG-dC).poly(dG-dC) down to 180 nm under conditions in which the 230- to 300-nm spectrum is inverted. Below 200 nm, where the B form exhibits the large positive peak at 187 nm that is characteristic of right-handed double-helical DNAs, the Z form exhibits a large negative peak at 194 nm and a positive band below 186 nm. Therefore, the Z-form vacuum ultraviolet CD spectrum resembles an inverted and red-shifted B-form spectrum. The magnitudes of the differences observed between the B and Z forms in the CD spectrum below 200 nm are about 10 times greater than those observed between 230 and 300 nm. The vacuum ultraviolet CD spectrum of poly(dG-dC).poly(dG-dC) in 3 M Cs2SO4 also is inverted compared to the B-form spectrum; however, between 230 and 300 nm, it is nonconservative with a negative maximum at 290 nm and a weak positive CD signal above 300 nm, presumably reflecting differential light scattering and indicating the existence of molecular aggregates. Our results suggest that the vacuum ultraviolet CD spectrum is sensitive to the handedness of double-helical DNA structures. The CD spectrum in this region should complement other spectroscopic methods in relating the structures of poly(dG-dC).poly(dG-dC) existing in solution to those determined in the solid state by x-ray crystallography.

  6. X-ray absorption near edge structure/electron energy loss near edge structure calculation using the supercell orthogonalized linear combination of atomic orbitals method

    NASA Astrophysics Data System (ADS)

    Ching, Wai-Yim; Rulis, Paul

    2009-03-01

    Over the last eight years, a large number of x-ray absorption near edge structure (XANES) and/or electron energy loss near edge structure (ELNES) spectroscopic calculations for complex oxides and nitrides have been performed using the supercell-OLCAO (orthogonalized linear combination of atomic orbitals) method, obtaining results in very good agreement with experiments. The method takes into account the core-hole effect and includes the dipole matrix elements calculated from ab initio wavefunctions. In this paper, we describe the method in considerable detail, emphasizing the special advantages of this method for large complex systems. Selected results are reviewed and several hitherto unpublished results are also presented. These include the Y K edge of Y ions segregated to the core of a Σ31 grain boundary in alumina, O K edges of water molecules, C K edges in different types of single walled carbon nanotubes, and the Co K edge in the cyanocobalamin (vitamin B12) molecule. On the basis of these results, it is argued that the interpretation of specific features of the calculated XANES/ELNES edges is not simple for complex material systems because of the delocalized nature of the conduction band states. The long-standing notion of the 'fingerprinting' technique for spectral interpretation of experimental data is not tenable. A better approach is to fully characterize the structure under study, using either crystalline data or accurate ab initio modeling. Comparison between calculated XANES/ELNES spectra and available measurements enables us to ascertain the validity of the modeled structure. For complex crystals or structures, it is necessary to use the weighted sum of the spectra from structurally nonequivalent sites for comparison with the measured data. Future application of the supercell-OLCAO method to complex biomolecular systems is also discussed.

  7. Anisotropic Circular Dichroism Signatures of Oriented Thylakoid Membranes and Lamellar Aggregates of LHCII

    SciTech Connect

    Miloslavina Y.; Hind G.; Lambrev, P. H.; Javorfi, T.; Varkonyi, Z.; Karlicky, V.; Wall, J. S.; Garab, G.

    2012-03-01

    In photosynthesis research, circular dichroism (CD) spectroscopy is an indispensable tool to probe molecular architecture at virtually all levels of structural complexity. At the molecular level, the chirality of the molecule results in intrinsic CD; pigment-pigment interactions in protein complexes and small aggregates can give rise to excitonic CD bands, while 'psi-type' CD signals originate from large, densely packed chiral aggregates. It has been well established that anisotropic CD (ACD), measured on samples with defined non-random orientation relative to the propagation of the measuring beam, carries specific information on the architecture of molecules or molecular macroassemblies. However, ACD is usually combined with linear dichroism and can be distorted by instrumental imperfections, which given the strong anisotropic nature of photosynthetic membranes and complexes, might be the reason why ACD is rarely studied in photosynthesis research. In this study, we present ACD spectra, corrected for linear dichroism, of isolated intact thylakoid membranes of granal chloroplasts, washed unstacked thylakoid membranes, photosystem II (PSII) membranes (BBY particles), grana patches, and tightly stacked lamellar macroaggregates of the main light-harvesting complex of PSII (LHCII). We show that the ACD spectra of face- and edge-aligned stacked thylakoid membranes and LHCII lamellae exhibit profound differences in their psi-type CD bands. Marked differences are also seen in the excitonic CD of BBY and washed thylakoid membranes. Magnetic CD (MCD) spectra on random and aligned samples, and the largely invariable nature of the MCD spectra, despite dramatic variations in the measured isotropic and anisotropic CD, testify that ACD can be measured without substantial distortions and thus employed to extract detailed information on the (supra)molecular organization of photosynthetic complexes. An example is provided showing the ability of CD data to indicate such an

  8. Anisotropic Circular Dichroism Signatures of Oriented Thylakoid Membranes and Lamellar Aggregates of LHCII

    SciTech Connect

    Miloslavina, Y.; Hind, G.; Lambrev, P. H.; Javorfi, T.; Varkonyi, Z.; Karlicky, V.; Wall, J. S.; Garab, G.

    2011-06-12

    In photosynthesis research, circular dichroism (CD) spectroscopy is an indispensable tool to probe molecular architecture at virtually all levels of structural complexity. At the molecular level, the chirality of the molecule results in intrinsic CD; pigment-pigment interactions in protein complexes and small aggregates can give rise to excitonic CD bands, while 'psi-type' CD signals originate from large, densely packed chiral aggregates. It has been well established that anisotropic CD (ACD), measured on samples with defined non-random orientation relative to the propagation of the measuring beam, carries specific information on the architecture of molecules or molecular macroassemblies. However, ACD is usually combined with linear dichroism and can be distorted by instrumental imperfections, which given the strong anisotropic nature of photosynthetic membranes and complexes, might be the reason why ACD is rarely studied in photosynthesis research. In this study, we present ACD spectra, corrected for linear dichroism, of isolated intact thylakoid membranes of granal chloroplasts, washed unstacked thylakoid membranes, photosystem II (PSII) membranes (BBY particles), grana patches, and tightly stacked lamellar macroaggregates of the main light-harvesting complex of PSII (LHCII). We show that the ACD spectra of face- and edge-aligned stacked thylakoid membranes and LHCII lamellae exhibit profound differences in their psi-type CD bands. Marked differences are also seen in the excitonic CD of BBY and washed thylakoid membranes. Magnetic CD (MCD) spectra on random and aligned samples, and the largely invariable nature of the MCD spectra, despite dramatic variations in the measured isotropic and anisotropic CD, testify that ACD can be measured without substantial distortions and thus employed to extract detailed information on the (supra)molecular organization of photosynthetic complexes. An example is provided showing the ability of CD data to indicate such an

  9. Structural circular birefringence and dichroism quantified by differential decomposition of spectroscopic transmission Mueller matrices from Cetonia aurata.

    PubMed

    Arwin, H; Mendoza-Galván, A; Magnusson, R; Andersson, A; Landin, J; Järrendahl, K; Garcia-Caurel, E; Ossikovski, R

    2016-07-15

    Transmission Mueller-matrix spectroscopic ellipsometry is applied to the cuticle of the beetle Cetonia aurata in the spectral range 300-1000 nm. The cuticle is optically reciprocal and exhibits circular Bragg filter features for green light. By using differential decomposition of the Mueller matrix, the circular and linear birefringence as well as dichroism of the beetle cuticle are quantified. A maximum value of structural optical activity of 560°/mm is found.

  10. Structural circular birefringence and dichroism quantified by differential decomposition of spectroscopic transmission Mueller matrices from Cetonia aurata.

    PubMed

    Arwin, H; Mendoza-Galván, A; Magnusson, R; Andersson, A; Landin, J; Järrendahl, K; Garcia-Caurel, E; Ossikovski, R

    2016-07-15

    Transmission Mueller-matrix spectroscopic ellipsometry is applied to the cuticle of the beetle Cetonia aurata in the spectral range 300-1000 nm. The cuticle is optically reciprocal and exhibits circular Bragg filter features for green light. By using differential decomposition of the Mueller matrix, the circular and linear birefringence as well as dichroism of the beetle cuticle are quantified. A maximum value of structural optical activity of 560°/mm is found. PMID:27420518

  11. Chiral plasmonic DNA nanostructures with switchable circular dichroism

    NASA Astrophysics Data System (ADS)

    Schreiber, Robert; Luong, Ngoc; Fan, Zhiyuan; Kuzyk, Anton; Nickels, Philipp C.; Zhang, Tao; Smith, David M.; Yurke, Bernard; Kuang, Wan; Govorov, Alexander O.; Liedl, Tim

    2013-12-01

    Circular dichroism spectra of naturally occurring molecules and also of synthetic chiral arrangements of plasmonic particles often exhibit characteristic bisignate shapes. Such spectra consist of peaks next to dips (or vice versa) and result from the superposition of signals originating from many individual chiral objects oriented randomly in solution. Here we show that by first aligning and then toggling the orientation of DNA-origami-scaffolded nanoparticle helices attached to a substrate, we are able to reversibly switch the optical response between two distinct circular dichroism spectra corresponding to either perpendicular or parallel helix orientation with respect to the light beam. The observed directional circular dichroism of our switchable plasmonic material is in good agreement with predictions based on dipole approximation theory. Such dynamic metamaterials introduce functionality into soft matter-based optical devices and may enable novel data storage schemes or signal modulators.

  12. Giant local circular dichroism within an asymmetric plasmonic nanoparticle trimer

    NASA Astrophysics Data System (ADS)

    Wang, Hancong; Li, Zhipeng; Zhang, Han; Wang, Peijie; Wen, Shuangchun

    2015-02-01

    We investigated the near-field response in silver nanoparticle aggregates to the excitation of circular polarized light. In a right-angle trimer system, the local field intensity excited by right-hand circularly polarized light is almost one thousand times larger than the left-hand case. By analyzing the polarization and phase of the local field in plasmonic hotspots, we found this local circular dichroism is originated from the near-field interference excited by orthogonal polarized incident lights. The local circular dichroism can be tuned by the rotation of the third particle, the interparticle distance, and the dielectric environment. This phenomenon could also widely exist in more complicated nanoaggregates. These findings would benefit for resolving light handedness, and enhancing circular dichroism and optical activity.

  13. Dynamics of photoinduced dichroism and birefringence in optically thick azopolymers

    SciTech Connect

    Ponomarev, Yu V; Ivanov, Yu V; Rumyantsev, Yu A; Gromchenko, A A

    2009-01-31

    Dynamics of photoinduced dichroism and birefringence have been studied experimentally and theoretically (with the help of the Dumont model) by using some comb-shaped azopolymers. It is shown that the dynamics of trans-isomer concentration and their angular distribution anisotropy can be restored from the experimentally found dichroism dynamics, with the concentration and anisotropy being averaged over the thickness for optically thick samples. At the initial stage of photoinduced anisotropy when the active role of the polymer matrix can be neglected, the experimental time dependence of dichroism is shown to comply well with the Dumont model even if the orientation memory is neglected, provided that only a part of trans-isomers participates in trans-isomerisation. (nonlinear optical phenomena)

  14. Chiral plasmonic DNA nanostructures with switchable circular dichroism

    PubMed Central

    Schreiber, Robert; Luong, Ngoc; Fan, Zhiyuan; Kuzyk, Anton; Nickels, Philipp C.; Zhang, Tao; Smith, David M.; Yurke, Bernard; Kuang, Wan; Govorov, Alexander O.; Liedl, Tim

    2013-01-01

    Circular dichroism spectra of naturally occurring molecules and also of synthetic chiral arrangements of plasmonic particles often exhibit characteristic bisignate shapes. Such spectra consist of peaks next to dips (or vice versa) and result from the superposition of signals originating from many individual chiral objects oriented randomly in solution. Here we show that by first aligning and then toggling the orientation of DNA-origami-scaffolded nanoparticle helices attached to a substrate, we are able to reversibly switch the optical response between two distinct circular dichroism spectra corresponding to either perpendicular or parallel helix orientation with respect to the light beam. The observed directional circular dichroism of our switchable plasmonic material is in good agreement with predictions based on dipole approximation theory. Such dynamic metamaterials introduce functionality into soft matter-based optical devices and may enable novel data storage schemes or signal modulators. PMID:24336125

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

    PubMed

    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).

  16. Circular dichroism in the electron microscope: Progress and applications (invited)

    SciTech Connect

    Schattschneider, P.; Loeffler, S.; Ennen, I.; Stoeger-Pollach, M.; Verbeeck, J.

    2010-05-15

    According to theory, x-ray magnetic circular dichroism in a synchrotron is equivalent to energy loss magnetic chiral dichroism (EMCD) in a transmission electron microscope (TEM). After a synopsis of the development of EMCD, the theoretical background is reviewed and recent results are presented, focusing on the study of magnetic nanoparticles for ferrofluids and Heusler alloys for spintronic devices. Simulated maps of the dichroic strength as a function of atom position in the crystal allow evaluating the influence of specimen thickness and sample tilt on the experimental EMCD signal. Finally, the possibility of direct observation of chiral electronic transitions with atomic resolution in a TEM is discussed.

  17. Nanophotonic modal dichroism: mode-multiplexed modulators.

    PubMed

    Das, Susobhan; Fardad, Shima; Kim, Inki; Rho, Junsuk; Hui, Rongqing; Salandrino, Alessandro

    2016-09-15

    As the diffraction limit is approached, device miniaturization to integrate more functionality per area becomes more and more challenging. Here we propose a strategy to increase the functionality-per-area by exploiting the modal properties of a waveguide system. With such an approach the design of a mode-multiplexed nanophotonic modulator relying on the mode-selective absorption of a patterned indium-tin-oxide (ITO) is proposed. Full-wave simulations of a device operating at the telecom wavelength of 1550 nm show that two modes can be independently modulated, while maintaining performances in line with conventional single-mode ITO modulators reported in the recent literature. The proposed design principles can pave the way to a class of mode-multiplexed compact photonic devices able to effectively multiply the functionality-per-area in integrated photonic systems. PMID:27628406

  18. Bright circularly polarized soft X-ray high harmonics for X-ray magnetic circular dichroism

    PubMed Central

    Fan, Tingting; Grychtol, Patrik; Knut, Ronny; Hernández-García, Carlos; Hickstein, Daniel D.; Zusin, Dmitriy; Gentry, Christian; Dollar, Franklin J.; Mancuso, Christopher A.; Hogle, Craig W.; Kfir, Ofer; Legut, Dominik; Carva, Karel; Ellis, Jennifer L.; Dorney, Kevin M.; Chen, Cong; Shpyrko, Oleg G.; Fullerton, Eric E.; Cohen, Oren; Oppeneer, Peter M.; Milošević, Dejan B.; Becker, Andreas; Jaroń-Becker, Agnieszka A.; Popmintchev, Tenio; Murnane, Margaret M.; Kapteyn, Henry C.

    2015-01-01

    We demonstrate, to our knowledge, the first bright circularly polarized high-harmonic beams in the soft X-ray region of the electromagnetic spectrum, and use them to implement X-ray magnetic circular dichroism measurements in a tabletop-scale setup. Using counterrotating circularly polarized laser fields at 1.3 and 0.79 µm, we generate circularly polarized harmonics with photon energies exceeding 160 eV. The harmonic spectra emerge as a sequence of closely spaced pairs of left and right circularly polarized peaks, with energies determined by conservation of energy and spin angular momentum. We explain the single-atom and macroscopic physics by identifying the dominant electron quantum trajectories and optimal phase-matching conditions. The first advanced phase-matched propagation simulations for circularly polarized harmonics reveal the influence of the finite phase-matching temporal window on the spectrum, as well as the unique polarization-shaped attosecond pulse train. Finally, we use, to our knowledge, the first tabletop X-ray magnetic circular dichroism measurements at the N4,5 absorption edges of Gd to validate the high degree of circularity, brightness, and stability of this light source. These results demonstrate the feasibility of manipulating the polarization, spectrum, and temporal shape of high harmonics in the soft X-ray region by manipulating the driving laser waveform. PMID:26534992

  19. Bright circularly polarized soft X-ray high harmonics for X-ray magnetic circular dichroism.

    PubMed

    Fan, Tingting; Grychtol, Patrik; Knut, Ronny; Hernández-García, Carlos; Hickstein, Daniel D; Zusin, Dmitriy; Gentry, Christian; Dollar, Franklin J; Mancuso, Christopher A; Hogle, Craig W; Kfir, Ofer; Legut, Dominik; Carva, Karel; Ellis, Jennifer L; Dorney, Kevin M; Chen, Cong; Shpyrko, Oleg G; Fullerton, Eric E; Cohen, Oren; Oppeneer, Peter M; Milošević, Dejan B; Becker, Andreas; Jaroń-Becker, Agnieszka A; Popmintchev, Tenio; Murnane, Margaret M; Kapteyn, Henry C

    2015-11-17

    We demonstrate, to our knowledge, the first bright circularly polarized high-harmonic beams in the soft X-ray region of the electromagnetic spectrum, and use them to implement X-ray magnetic circular dichroism measurements in a tabletop-scale setup. Using counterrotating circularly polarized laser fields at 1.3 and 0.79 µm, we generate circularly polarized harmonics with photon energies exceeding 160 eV. The harmonic spectra emerge as a sequence of closely spaced pairs of left and right circularly polarized peaks, with energies determined by conservation of energy and spin angular momentum. We explain the single-atom and macroscopic physics by identifying the dominant electron quantum trajectories and optimal phase-matching conditions. The first advanced phase-matched propagation simulations for circularly polarized harmonics reveal the influence of the finite phase-matching temporal window on the spectrum, as well as the unique polarization-shaped attosecond pulse train. Finally, we use, to our knowledge, the first tabletop X-ray magnetic circular dichroism measurements at the N4,5 absorption edges of Gd to validate the high degree of circularity, brightness, and stability of this light source. These results demonstrate the feasibility of manipulating the polarization, spectrum, and temporal shape of high harmonics in the soft X-ray region by manipulating the driving laser waveform.

  20. Strong magneto-chiral dichroism in a paramagnetic molecular helix observed by hard X-ray

    PubMed Central

    Sessoli, Roberta; Boulon, Marie-Emmanuelle; Caneschi, Andrea; Mannini, Matteo; Poggini, Lorenzo; Wilhelm, Fabrice; Rogalev, Andrei

    2014-01-01

    Magneto-chiral dichroism (MχD) is a non-reciprocal, i. e. directional, effect observed in magnetised chiral systems featuring an unbalanced absorption of unpolarised light depending on the direction of the magnetisation. Despite the fundamental interest in a phenomenon breaking both parity and time reversal symmetries, MχD is one of the least investigated aspects of light-matter interaction because of the weakness of the effect in most reported experiments. Here we have exploited the element selectivity of hard X-ray radiation to investigate the magneto-chiral properties of enentiopure crsytals of two isostructural molecular helicoidal chains comprising Cobalt(II) and Manganese (II) ions, respectively. A strong magneto-chiral dichroism, with Kuhn asymmetry of the order of a few percent, has been observed in the Cobalt chain system, while it is practically absent for the Manganese derivative. The spectral features of the XMχD signal differ significantly from the natural and magnetic dichroic contributions and have been here rationalized using the simple multipolar expansion of matter-radiation interaction. PMID:25729401

  1. Analysis of conjugation of chloramphenicol and hemoglobin by fluorescence, circular dichroism and molecular modeling

    NASA Astrophysics Data System (ADS)

    Ding, Fei; Liu, Wei; Sun, Ye; Yang, Xin-Ling; Sun, Ying; Zhang, Li

    2012-01-01

    Chloramphenicol is a low cost, broad spectrum, highly active antibiotic, and widely used in the treatment of serious infections, including typhoid fever and other life-threatening infections of the central nervous system and respiratory tract. The purpose of the present study was to examine the conjugation of chloramphenicol with hemoglobin (Hb) and compared with albumin at molecular level, utilizing fluorescence, UV/vis absorption, circular dichroism (CD) as well as molecular modeling. Fluorescence data indicate that drug bind Hb generate quenching via static mechanism, this corroborates UV/vis absorption measurements that the ground state complex formation with an affinity of 10 4 M -1, and the driving forces in the Hb-drug complex are hydrophilic interactions and hydrogen bonds, as derived from computational model. The accurate binding site of drug has been identified from the analysis of fluorescence and molecular modeling, α1β2 interface of Hb was assigned to possess high-affinity for drug, which located at the β-37 Trp nearby. The structural investigation of the complexed Hb by synchronous fluorescence, UV/vis absorption, and CD observations revealed some degree of Hb structure unfolding upon complexation. Based on molecular modeling, we can draw the conclusion that the binding affinity of drug with albumin is superior, compared with Hb. These phenomena can provide salient information on the absorption, distribution, pharmacology, and toxicity of chloramphenicol and other drugs which have analogous configuration with chloramphenicol.

  2. Circular Dichroism Method for Heat Capacity Determination of Proteins

    ERIC Educational Resources Information Center

    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,…

  3. Cyanobacterial phycobilisomes: selective dissociation monitored by fluorescence and circular dichroism

    SciTech Connect

    Rigbi, M.; Rosinski, J.; Siegelman, H.W.; Sutherland, J.C.

    1980-04-01

    Phycobilisomes are supramolecular assemblies of phycobiliproteins responsible for photosynthetic light collection in red algae and cyanobacteria. They can be selectively dissociated by reduction of temperature and buffer concentration. Phycobilisomes isolated from Fremyella diplosiphon transfer energy collected by C-phycoerythrin and C-phycocyanin to allophycocyanin. The energy transfer to allophycocyanin is nearly abolished at 2/sup 0/C, as indicated by a blue shift in fluorescence emission, and is accompanied by a decrease in the circular dichroism in the region of allophycocyanin absorbance. Further dissociation of the phycobilisomes can be attained by reduction of buffer concentration and holding at 2/sup 0/C. Energy transfer to C-phycocyanin is nearly abolished, and decreases occur in the circular dichroism in the region of C-phycocyanin and C-phycoerythrin absorbance. Complete dissociation of the phycobilisomes at low buffer concentration and 2/sup 0/C requires extended time. Energy transfer to C-phycocyanin is further reduced and the circular dichroism maximum of C-phycoerythrin at 575 nm is lost. Circular dichroism provides information on the hexamer-monomer transitions of the phycobiliproteins, whereas fluorescence is indicative of hexamer-hexamer interactions. We consider that hydrophobic interactions are fundamental to the maintenance of the structure and function of phycobilisomes.

  4. Spin-Induced Polarizations and Nonreciprocal Directional Dichroism of the Room-Temperature Multiferroic BiFeO3

    SciTech Connect

    Fishman, Randy Scott; Lee, Jun Hee; Bordacs, Sandor; Kezsmarki, Istvan; Nagel, Urmas; Room, Toomas

    2015-09-14

    A microscopic model for the room-temperature multiferroic BiFeO3 that includes two Dzyaloshinskii-Moriya interactions and single-ion anisotropy along the ferroelectric polarization predicts both the zero-field spectroscopic modes as well as their splitting and evolution in a magnetic field. Due to simultaneously broken time-reversal and spatial-inversion symmetries, the absorption of light changes as the magnetic field or the direction of light propagation is reversed. We discuss three physical mechanisms that may contribute to this absorption asymmetry known as directional dichroism: the spin current, magnetostriction, and single-ion anisotropy. We conclude that the directional dichroism in BiFeO3 is dominated by the spin-current polarization and is insensitive to the magnetostriction and easy-axis anisotropy. With three independent spin-current parameters, our model accurately describes the directional dichroism observed for magnetic field along [1, -1, 0]. Since some modes are almost transparent to light traveling in one direction but opaque for light traveling in the opposite direction, BiFeO3 can be used as a room-temperature optical diode at certain frequencies in the GHz to THz range. This work demonstrates that an analysis of the directional dichroism spectra based on an effective spin model supplemented by first-principles calculations can produce a quantitative microscopic theory of the magnetoelectric couplings in multiferroic materials.

  5. Facility for combined in situ magnetron sputtering and soft x-ray magnetic circular dichroism

    SciTech Connect

    Telling, N. D.; Laan, G. van der; Georgieva, M. T.; Farley, N. R. S.

    2006-07-15

    An ultrahigh vacuum chamber that enables the in situ growth of thin films and multilayers by magnetron sputtering techniques is described. Following film preparation, x-ray absorption spectroscopy (XAS) and x-ray magnetic circular dichroism (XMCD) measurements are performed by utilizing an in vacuum electromagnet. XMCD measurements on sputtered thin films of Fe and Co yield spin and orbital moments that are consistent with those obtained previously on films measured in transmission geometry and grown in situ by evaporation methods. Thin films of FeN prepared by reactive sputtering are also examined and reveal an apparent enhancement in the orbital moment for low N content samples. The advantages of producing samples for in situ XAS and XMCD studies by magnetron sputtering are discussed.

  6. Electronic structure and x-ray magnetic circular dichroism in A2FeReO6 (A =Ca ,Sr ,andBa ) oxides

    NASA Astrophysics Data System (ADS)

    Antonov, V. N.; Bekenov, L. V.; Ernst, A.

    2016-07-01

    A systematic electronic structure study of A2FeReO6 (A =Ba ,Sr ,andCa ) has been performed by employing the local-spin-density approximation (LSDA) 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 between spin-orbit coupling, electron correlations, and lattice distortion on the electronic structure of double perovskites. Ca2FeReO6 has a large distortion in the Fe-O-Re bond, and the electronic structure is mainly determined by electron correlations and lattice distortion. In the Ba -Sr -Ca row, the correlation effects at the Fe site are increased. The correlations at the Re site are small in the Ba- and Sr-based compounds but significant in Ca2FeReO6 . Ca2FeReO6 behaves like an insulator only if considered with a relatively large value of Coulomb repulsion Ueff=2.3 eV at the Re site in addition to Ueff=3.1 eV at the Fe site. Ca2FeReO6 possesses a phase transition at 140 K where the metal-insulator transition (MIT) occurs between metallic high-temperature and insulating low-temperature phases. The spin and orbital magnetic moments are linear functions of temperature before and after the MIT but change abruptly at the point of the phase transition. From theoretically calculated magnetocrystalline anisotropy energy (MAE), we found that the easy axis of magnetization for the low-temperature phase is along the b direction, in agreement with experimental data. We found that the major contribution to the MAE is due to the orbital magnetic anisotropy at the Re site. X-ray-absorption spectra and x-ray magnetic circular dichroism at the Re, Fe, and Ba L2 ,3 and Fe, Ca, and O K edges were investigated theoretically in the frame of the LSDA +U method. A qualitative explanation of the x-ray magnetic circular dichroism spectra shape is provided by an analysis of the corresponding selection rules, orbital character, and occupation numbers of individual orbitals

  7. Remediation of Cr(VI) by biogenic magnetic nanoparticles: An x-ray magnetic circular dichroism study

    SciTech Connect

    Telling, N. D.; Coker, V. S.; Cutting, R. S.; van der Laan, G.; Pearce, C. I.; Pattrick, R. A. D.; Arenholz, E.; Lloyd, J. R.

    2009-09-04

    Biologically synthesized magnetite (Fe{sub 3}O{sub 4}) nanoparticles are studied using x-ray absorption and x-ray magnetic circular dichroism following exposure to hexavalent Cr solution. By examining their magnetic state, Cr cations are shown to exist in trivalent form on octahedral sites within the magnetite spinel surface. The possibility of reducing toxic Cr(VI) into a stable, non-toxic form, such as a Cr{sup 3+}-spinel layer, makes biogenic magnetite nanoparticles an attractive candidate for Cr remediation.

  8. Amide I vibrational circular dichroism of polypeptides: Generalized fragmentation approximation method

    NASA Astrophysics Data System (ADS)

    Choi, Jun-Ho; Kim, Joong-Soo; Cho, Minhaeng

    2005-05-01

    Fragment analyses of vibrational circular dichroic response of dipeptides were carried out recently [Choi and Cho, J. Chem. Phys. 120, 4383 (2004)]. In the present paper, by using a minimal size unit peptide containing two chiral carbons covalently bonded to the peptide group, a generalized fragmentation approximation method is discussed and applied to the calculations of infrared-absorption and vibrational circular dichroism (VCD) intensities of amide I vibrations in various secondary structure polypeptides. Unlike the dipole strength determining IR-absorption intensity, the rotational strength is largely determined by the cross terms that are given by the inner product between the transition electric dipole and the transition magnetic dipole of two different peptides. This explains why the signs and magnitudes of VCD peaks are far more sensitive to the relative orientation and distance between different peptide bonds in a given protein. In order to test the validity of fragmentation approximation, three different segments in a globular protein ubiquitin, i.e., right-handed α-helix, β-sheet, and β-turn regions, were chosen for density-functional theory (DFT) calculations of amide I vibrational properties and the numerically simulated IR-absorption and VCD spectra by using the fragmentation method are directly compared with DFT results. It is believed that the fragmentation approximation method will be of use in numerically simulating vibrational spectra of proteins in solutions.

  9. Tunable chirality and circular dichroism of a topological insulator with C2v symmetry as a function of Rashba and Dresselhaus parameters

    NASA Astrophysics Data System (ADS)

    Sengupta, Parijat; Bellotti, Enrico

    2016-01-01

    Polarization-sensitive devices rely on meta-materials to exhibit varying degrees of absorption of light of a given handedness. The chiral surface states of a topological insulator selectively absorb right- and left-circularly polarized light in the vicinity of the Dirac cone reaching its maximum of unity at the Γ point. In this letter, we show that a band gap open topological insulator with C2v symmetry, which is represented through a combination of Rashba and Dresselhaus Hamiltonians, alters the preferential absorption of left- and right-circularly polarized light allowing a smooth variation of the circular dichroism. This variation in circular dichroism, in a range of positive and negative values, is shown to be a function of the Rashba and Dresselhaus coupling parameters.

  10. Circular Dichroism Spectra of Granal and Agranal Chloroplasts of Maize

    PubMed Central

    Faludi-Dániel, Ágnes; Demeter, S.; Garay, A. S.

    1973-01-01

    Granum-containing chloroplasts from mesophyll cells of maize (Zea mays L. var. MV 861) leaves exhibited circular dichroism spectra with a large double signal; peaks at 696 nm (+) and 680 nm (−). In the circular dichroism spectra obtained with agranal chloroplasts of bundle sheath cells, this large double signal is absent. Separation of grana lamellae, in a medium of low salt concentration and in KSCN solution, resulted only in a slight decrease of the amplitude, while upon treatment with digitonin the large double signal disappeared. A negative signal of the chlorophyll b peak at 654 nm was observed in the case of both granal and agranal chloroplasts, and it was not affected either by low salt or by digitonin treatment. A positive peak at about 515 nm was higher in granal than in agranal chloroplasts. PMID:16658498

  11. Magnetically induced optical activity and dichroism of gadolinium oxide nanoparticle-based ferrofluids

    NASA Astrophysics Data System (ADS)

    Paul, Nibedita; Devi, Manasi; Mohanta, Dambarudhar; Saha, Abhijit

    2012-02-01

    The present work reports on magnetically induced optical activity (such as Faraday rotation and linear dichroism) of pristine and gamma-irradiated gadolinium oxide (Gd2O3) nanoparticle-based ferrofluids. The ferrofluids were produced by dispersing N-cetyl-N,N,N-trimethyl ammonium bromide (CTAB)-coated ˜9-nm-sized Gd2O3 particles in a carrier fluid of ethanol. The ferrofluids were then irradiated with 1.25 MeV energetic gamma rays (dose: 868 Gy and 2.635 kGy). Irradiation-led formation of a number of point defects was revealed through high resolution electron microscopy. The interaction of light with the ionized point defects is believed to have caused substantial improvement in the magneto-optic response of irradiated magnetic fluids.

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

    NASA Astrophysics Data System (ADS)

    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.

  13. Magnetically induced optical activity and dichroism of gadolinium oxide nanoparticle-based ferrofluids

    SciTech Connect

    Paul, Nibedita; Devi, Manasi; Mohanta, Dambarudhar; Saha, Abhijit

    2012-02-15

    The present work reports on magnetically induced optical activity (such as Faraday rotation and linear dichroism) of pristine and gamma-irradiated gadolinium oxide (Gd{sub 2}O{sub 3}) nanoparticle-based ferrofluids. The ferrofluids were produced by dispersing N-cetyl-N,N,N-trimethyl ammonium bromide (CTAB)-coated {approx}9-nm-sized Gd{sub 2}O{sub 3} particles in a carrier fluid of ethanol. The ferrofluids were then irradiated with 1.25 MeV energetic gamma rays (dose: 868 Gy and 2.635 kGy). Irradiation-led formation of a number of point defects was revealed through high resolution electron microscopy. The interaction of light with the ionized point defects is believed to have caused substantial improvement in the magneto-optic response of irradiated magnetic fluids.

  14. Magnetic order and interfacial coupling in oxide thin films and heterostructures probed with soft x-ray dichroism

    SciTech Connect

    Arenholz, Elke; van der Laan, G.

    2009-02-01

    The combination of novel magnetic properties induced by reduced dimensionality and strong magnetic interactions across interfaces leads to intriguing new properties in magnetic hetero- and nanostructures not observed in the constituent materials in bulk form. It is the careful optimization of the characteristics of the individual layers as well as the magnetic coupling across the interface that allows us to control the magnetic properties and tailor them for devices, e.g., in information storage and processing technology. Soft x-ray magnetic spectroscopies can make unique contributions to improving our understanding of complex magnetic nanostructures since these techniques provide elemental, valence- and site-symmetry specific information with high sensitivity and tunable probing depth. X-ray magnetic circular dichroism (XMCD) is sensitive to (unidirectional) ferromagnetic order, while x-ray magnetic linear dichroism (XMLD) can also detect (uniaxial) antiferromagnetic order. A crystalline electric field with cubic symmetry induces only a weak angular dependence in XMCD spectra [1] but can cause a very pronounced anisotropy in XMLD spectra [2]. Furthermore, non-magnetic sites with a distorted local cubic symmetry can give rise to an x-ray linear dichroism (XLD). In this presentation, we discuss how to distinguish between the individual contributions to soft x-ray dichroism spectra in order to extract the wealth of information about magnetic thin films, interfaces and hetero- and nanostructures contained in the data [3, 4, 5] We determined the magnetic structure of La{sub 0.7}Sr{sub 0.3}MnO{sub 3} (LSMO)/La{sub 0.7}Sr{sub 0.3}FeO{sub 3} (LSFO) superlattices with 6 unit cell thick sublayers using soft x-ray magnetic dichroism [5]. Circular dichroism was employed to study the characteristics of the ferromagnetic LSMO layer indicating a reduced magnetic ordering temperature of 200 K compared to the bulk value of 360 K. Linear dichroism is used to analyze the

  15. Recent Theoretical and Experimental Advances in the Electronic Circular Dichroisms of Planar Chiral Cyclophanes

    NASA Astrophysics Data System (ADS)

    Mori, Tadashi; Inoue, Yoshihisa

    The chiroptical properties, such as electronic and vibrational circular dichroism and optical rotation, of planar chiral cyclophanes have attracted much attention in recent years. Although the chemistry of cyclophanes has been extensively explored for more than 60 years, the studies on chiral cyclophanes are rather limited. Experimentally, the use of chiral stationary phases in HPLC becomes more popular and facilitates the enantiomer separation of chiral cyclophanes of interest. Almost all chiral cyclophanes can be readily separated, in analytical and preparative scales, most typically on a Daicel OD type column, which is based on cellulose tris(3,5-dimethylphenylcarbamate). The CD spectra of chiral cyclophanes are unique in their fairly large, significantly coupled Cotton effects observed in all the 1 B b, 1 L a, and 1 L b band regions. Theoretically, the time-dependent density functional theory, or TD-DFT, method becomes a cost-efficient, yet accurate, theoretical method to reproduce the electronic circular dichroisms and the absorption spectra of a variety of cyclophanes. The direct comparison of the experimental CD spectra with the theoretical ones readily leads to the unambiguous assignment of the absolute configuration of cyclophanes. In addition, the analysis of configuration interaction and molecular orbitals allows detailed interpretation of the electronic transitions and Cotton effects in the UV and CD spectra. Through the study of the CD spectra of chiral cyclophanes as model systems, the effects of intra- and intermolecular interactions on the chiroptical properties of molecules can be explored, and the results thus obtained are valuable in comprehensively elucidating the structure-chiroptical property relationship. In this review the recent progress in experimental and theoretical investigations of the electronic CD spectra of chiral cyclophanes is discussed.

  16. Time Resolved X-ray Magnetic Circular Dichroism at the Linac Coherent Light Source

    NASA Astrophysics Data System (ADS)

    Schlotter, W.; Higley, D.; Jal, E.; Dakovski, G.; Yuan, E.; MacArthur, J.; Lutman, A.; Hirsch, K.; Granitzka, P.; Chen, Z.; Coslovich, G.; Hoffman, M.; Mitra, A.; Reid, A.; Hart, P.; Nuhn, H.-D.; Duerr, H.; Arenholz, E.; Shafer, P.; Dennes, P.; Joseph, J.; Guyader, L.; Tsukamoto, A.

    We demonstrate ultrafast time resolved X-ray Magnetic Circular Dichroism on optically switchable GdFeCo thin film samples. This method extends the element specificity of time resolved x-ray absorption spectroscopy to characterize the evolution of electron spin and orbital angular momenta. These measurements were enabled by a recent upgrade at the Linac Coherent Light Source (LCLS) to generate circularly polarized x-rays. Additionally these measurements were enhanced by new detection systems that benefit all x-ray absorption spectroscopy experiments performed in transmission. Consequently static XMCD data are in excellent agreement with similar measurements at synchrotron light sources. The LCLS is an x-ray free electron laser user facility accessible via a peer-reviewed proposal process. Acknowledgement: The Linac Coherent Light Source (LCLS), SLAC National Accelerator Laboratory, is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract No. DE-AC02-76SF00515.

  17. Non-reciprocal directional dichroism in the AFM phase of BiFeO3 at THz frequencies

    NASA Astrophysics Data System (ADS)

    Nagel, Urmas; Rõõm, T.; Farkas, D.; Szaller, D.; Bordács, S.; Kézsmárki, I.; Engelkamp, H.; Ozaki, Y.; Tomiaki, Y.; Ito, T.; Fishman, Randy S.

    We did THz absorption spectroscopy of BiFeO3 single crystals in the AFM phase, where the spin cycloid is destroyed in magnetic fields between 18 T and 32 T in Voigt geometry at 1.6 K. If B0 ∥ [ 1 1 0 ] , we see strong directional dichroism (DD) of absorption of the magnon mode with light propagating along the direction of the ferroelectric polarization k ∥ P ∥ [ 111 ] and eω ∥ [ 1 1 0 ] , bω ∥ [ 1 1 2 ] . The sign of DD can be reversed (i) by reversing the direction of B0 or (ii) by flipping the sample, thus reversing the propagation direction of light. The observed effect is caused by the strong magneto-electric coupling in the collinear AFM phase. Research sponsored by the Estonian Ministry of Education and Research (IUT23-3).

  18. Irradiation induced ferromagnetism at room temperature in TiO{sub 2} thin films: X-ray magnetic circular dichroism characterizations

    SciTech Connect

    Thakur, Hardeep; Sharma, K. K.; Thakur, P.; Brookes, N. B.; Kumar, Ravi; Singh, A. P.; Kumar, Yogesh; Gautam, S.; Chae, K. H.

    2011-05-09

    We report on the room temperature ferromagnetism in the swift heavy ion (SHI) irradiated TiO{sub 2} thin films by x-ray absorption spectroscopy (XAS) and x-ray magnetic circular dichroism (XMCD) experiments at the O K and Ti L{sub 3,2} absorption edges. The XAS/XMCD measurements provide direct evidence of magnetic polarization of the O 2p and Ti 3d orbitals. The unquenched orbital magnetic moment within the O 2p shell is ferromagnetically coupled to the neighboring Ti moments, which illustrates the intense hybridization of the O 2p and Ti 3d orbitals induced by SHI irradiation.

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

    PubMed

    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).

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

    PubMed

    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). PMID:26780877

  1. Complementary Y-shaped chiral metamaterial with giant optical activity and circular dichroism simultaneously for terahertz waves

    NASA Astrophysics Data System (ADS)

    Zhi Cheng, Yong; Li Yang, Yong; Jie Zhou, Yu; Zhang, Zhe; Mao, Xue Song; Gong, Rong Zhou

    2016-09-01

    A complementary Y-shaped chiral metamaterial (CYCMM) is proposed for the realization of giant optical activity and circular polarization with strong circular dichroism (CD) simultaneously for terahertz (THz) waves. It is demonstrated that the proposed CYCMM can achieve 90° linear polarization rotation around 2.13 THz and a giant CD effect at 2.38 THz through full-wave simulations. The mechanism of the giant CD effect and optical activity is illustrated by simulated surface current distribution. Due to strong optical activity and the CD effect, the proposed CYCMM is useful for the development of integrated terahertz spectroscopic and imaging devices.

  2. A linear relationship between the Hall carrier concentration and the effective absorption coefficient measured by means of photothermal radiometry in IR semi-transparent n-type CdMgSe mixed crystals

    NASA Astrophysics Data System (ADS)

    Pawlak, M.; Maliński, M.; Firszt, F.; Pelzl, J.; Ludwig, A.; Marasek, A.

    2014-03-01

    In this work we demonstrate the ability to measure the effective infrared absorption coefficient in semiconductors by a photothermal infrared radiometry (PTR) experiment, and its correlation with the Hall carrier concentration. The amplitude and phase of the PTR signal were measured for Cd1-xMgxSe mixed crystals, with the magnesium content varying from x = 0 to x = 0.15. The PTR experiments were performed at room temperature in thermal reflection and transmission configurations using a mercury cadmium telluride infrared detector. The PTR data were analyzed in the frame of the one-dimensional heat transport model for infrared semi-transparent crystals. Based on the variation of the normalized PTR phase and amplitude on the modulation frequency, the thermal diffusivity and the effective infrared absorption coefficient were obtained by fitting the theoretical expression to experimental data and compared with the Hall carrier concentration determined by supplementary Hall experiments. A linear relationship between the effective infrared absorption coefficient and the Hall carrier concentration was found which is explained in the frame of the Drude theory. The uncertainty of the measured slope was 6%. The value of the slope depends on (1) the sample IR absorption spectrum and (2) the spectral range of the infrared detector. It has to be pointed out that this method is suitable for use in an industrial environment for a fast and contactless carrier concentration measurement. This method can be used for the characterization of other semiconductors after a calibration procedure is carried out. In addition, the PTR technique yields information on the thermal properties in the same experiment.

  3. Circular Dichroism in the Photoionization of Nanoparticles from Chiral Compounds

    SciTech Connect

    Paul, J.; Doerzbach, A.; Siegmann, K.

    1997-10-01

    The dichroism in photoemission from chiral molecules is observed for the first time. Particles consisting of chiral molecules are suspended in air and irradiated alternately with right and left circularly polarized uv light. We found a polarization dependence in the total photoelectric current. The asymmetries observed are of the order of 10{sup {minus}2} to 10{sup {minus}3} , as expected from perturbation theory, and reverse their sign when the handedness of the molecules is changed. {copyright} {ital 1997} {ital The American Physical Society}

  4. Light absorption dichroism and magnetic configuration of weakly ferromagnetic CoCO 3

    NASA Astrophysics Data System (ADS)

    Litvinenko, Yu. G.; Verdyan, A. I.; Shapiro, V. V.

    1980-01-01

    Investigation of light interaction with magnetically ordered crystals [1] revealed a correlation between certain spectral characteristics of a crystal on the one hand and its magnetic properties on the other.

  5. Magnetic circular dichroism in the hard X-ray range

    NASA Astrophysics Data System (ADS)

    Rogalev, A.; Wilhelm, F.

    2015-12-01

    An overview of X-ray magnetic circular dichroism (XMCD) spectroscopy in the hard X-ray range is presented. A short historical overview shows how this technique has evolved from the early days of X-ray physics to become a workhorse technique in the modern magnetism research As with all X-ray spectroscopies, XMCD has the advantage of being element specific. Interpretation of the spectra based on magneto-optical sum rules can provide unique information about spin and orbital moment carried by absorbing atom in both amplitude and direction, can infer magnetic interactions from element selective magnetization curves, can allow separation of magnetic and non-magnetic components in heterogeneous systems. The review details the technology currently available for XMCD measurements in the hard X-ray range referring to the ESRF beamline ID12 as an example. The strengths of hard X-ray magnetic circular dichroism technique are illustrated with a wide variety of representative examples, such as actinide based ferromagnets, paramagnetism in metals, pure metallic nanoparticles, exchange spring magnets, half metallic ferromagnets, magnetism at interfaces, and dilute magnetic semiconductors. In this way, we aim to encourage researchers from various scientific communities to consider XMCD as a tool to understanding the electronic and magnetic properties of their samples.

  6. Structural characterization of recombinant therapeutic proteins by circular dichroism.

    PubMed

    Bertucci, Carlo; Pistolozzi, Marco; De Simone, Angela

    2011-10-01

    Most of the protein therapeutics are now produced by recombinant DNA technology. The advantages of recombinant proteins are related to their higher specificity and to their safety as exposure to animal or human diseases. However, several problems are still present in development of recombinant proteins as therapeutics, such as low bioavailability, short serum half-life, and immune response. Their successful application hinges on the protein stereochemical stability, and on the folding and the tendency to aggregate induced by purification steps and storage. All these aspects determine the failure of many potential protein therapies, and limitations in the development of the formulation. The application of multiple analytical techniques is important in order to obtain a detailed product profile and to understand how manufacturing can influence product structure and activity. Surely the protein conformation is a key aspect to be assessed, because a specific conformation is often essential for the biological function of the protein. Thus, there is a growing need to perform structural studies under the conditions in which the proteins operate, and to monitor the structural changes of the protein. Circular dichroism has been increasingly recognised as a valuable and reliable technique to get this information. In particular, examples will be here reported on the use of circular dichroism spectroscopy in the structural characterization of free and formulated recombinant proteins, looking at the prediction of the secondary structure, propensity to conformational changes, stability, and tendency to aggregate.

  7. Spin polarization and magnetic dichroism in photoemission from core and valence states in localized magnetic systems. IV. Core-hole polarization in resonant photoemission

    NASA Astrophysics Data System (ADS)

    van der Laan, Gerrit; Thole, B. T.

    1995-12-01

    A simple theory is presented for core-hole polarization probed by resonant photoemission in a two-steps approximation. After excitation from a core level to the valence shell, the core hole decays into two shallower core holes under emission of an electron. The nonspherical core hole and the final state selected cause a specific angle and spin distribution of the emitted electron. The experiment is characterized by the ground-state moments, the polarization of the light, and the spin and angular distribution of the emitted electron. The intensity is a sum over ground-state expectation values of tensor operators times the probability to create a polarized core hole using polarized light, times the probability for decay of such a core hole into the final state. We give general expressions for the angle- and spin-dependent intensities in various regimes of Coulomb and spin-orbit interaction: LS, LSJ, and jjJ coupling. The core-polarization analysis, which generalizes the use of sum rules in x-ray absorption spectroscopy where the integrated peak intensities give ground-state expectation values of the spin and orbital moment operators, makes it possible to measure different linear combinations of these operators. As an application the 2p3/23p3p decay in ferromagnetic nickel is calculated using Hartree-Fock values for the radial matrix elements and phase factors, and compared with experiment, the dichroism is smaller in the 3P final state but stronger in the 1D, 1S peak.

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

    PubMed

    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.

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

    PubMed

    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. PMID:25813022

  10. Linear and nonlinear optical absorption coefficients and refractive index changes in GaN/Al{sub x}Ga{sub (1−x)}N double quantum wells operating at 1.55 μm

    SciTech Connect

    Dakhlaoui, Hassen

    2015-04-07

    In the present paper, the linear and nonlinear optical absorption coefficients and refractive index changes between the ground and the first excited states in double GaN/Al{sub x}Ga{sub (1−x)}N quantum wells are studied theoretically. The electronic energy levels and their corresponding wave functions are obtained by solving Schrödinger-Poisson equations self-consistently within the effective mass approximation. The obtained results show that the optical absorption coefficients and refractive index changes can be red- and blue-shifted through varying the left quantum well width and the aluminum concentration x{sub b2} of the central barrier, respectively. These structural parameters are found to present optimum values for carrying out the transition of 0.8 eV (1.55 μm). Furthermore, we show that the desired transition can also be achieved by replacing the GaN in the left quantum well with Al{sub y}Ga{sub (1−y)}N and by varying the aluminum concentration y{sub Al}. The obtained results give a new degree of freedom in optoelectronic device applications such as optical fiber telecommunications operating at (1.55 μm)

  11. Versatile transmission ellipsometry to study linear ferrofluid magneto-optics.

    PubMed

    Kooij, E S; Gâlcă, A C; Poelsema, B

    2006-12-01

    Linear birefringence and dichroism of magnetite ferrofluids are studied simultaneously using spectroscopic ellipsometry in transmission mode. It is shown that this versatile technique enables highly accurate characterisation of magneto-optical phenomena. Magnetic field-dependent linear birefringence and dichroism as well as the spectral dependence are shown to be in line with previous results. Despite the qualitative agreement with established models for magneto-optical phenomena, these fail to provide an accurate, quantitative description of our experimental results using the bulk dielectric function of magnetite. We discuss the results in relation to these models, and indicate how the modified dielectric function of the magnetite nanoparticles can be obtained. PMID:16997315

  12. A new soft X-ray magnetic circular dichroism facility at the BSRF beamline 4B7B

    NASA Astrophysics Data System (ADS)

    Guo, Zhi-Ying; Hong, Cai-Hao; Xing, Hai-Ying; Tang, Kun; Zheng, Lei; Xui, Wei; Chen, Dong-Liang; Cui, Ming-Qi; Zhao, Yi-Dong

    2015-04-01

    X-ray magnetic circular dichroism (XMCD) has become an important and powerful tool because it allows the study of material properties in combination with elemental specificity, chemical state specificity, and magnetic specificity. A new soft X-ray magnetic circular dichroism apparatus has been developed at the Beijing Synchrotron Radiation Facility (BSRF). The apparatus combines three experimental conditions: an ultra-high-vacuum environment, moderate magnetic fields and in-situ sample preparation to measure the absorption signal. We designed a C-type dipole electromagnet that provides magnetic fields up to 0.5 T in parallel (or anti-parallel) direction relative to the incoming X-ray beam. The performances of the electromagnet are measured and the results show good agreement with the simulation ones. Following film grown in situ by evaporation methods, XMCD measurements are performed. Combined polarization corrections, the magnetic moments of the Fe and Co films determined by sum rules are consistent with other theoretical predictions and experimental measurements. Supported by National Natural Science Foundation of China (61204008)

  13. Phosphorylation effect on the GSSS peptide conformation in water: Infrared, vibrational circular dichroism, and circular dichroism experiments and comparisons with molecular dynamics simulations

    NASA Astrophysics Data System (ADS)

    Lee, Kyung-Koo; Joo, Cheonik; Yang, Seongeun; Han, Hogyu; Cho, Minhaeng

    2007-06-01

    The phosphorylation effect on the small peptide conformation in water has not been clearly understood yet, despite the widely acknowledged notion that control of protein activity by phosphorylation works mainly by inducing conformational change. To elucidate the detailed mechanism, we performed infrared (IR) absorption and vibrational and electronic circular dichroism studies of both unphosphorylated and phosphorylated tetrapeptides, GSSS 1 and GSSpS 2. The solution structure of the tetrapeptide is found to be little dependent on the presence of the neutral or negatively charged phosphoryl group, and to be a mixture of extended structures including polyproline II (PII) and β-sheet conformations. The additional band at 1598cm-1 in the amide I IR spectrum of the phosphorylated peptide GSSpS at neutral pD appears to be clear spectroscopic evidence for direct intramolecular hydrogen-bonding interaction between the side chain dianionic phosphoryl group and the backbone amide proton. On the basis of amide I IR band analyses, the authors found that the probability of finding the phosphoryl group strongly H bonded to the backbone proton in GSSpS is about 43% at pD 7.0 and 37°C. Such a H-bonding interaction in GSSpS has the biological standard enthalpy and entropy of -15.1kJ /mol and -51.2J/Kmol, respectively. Comparisons between the experimentally measured IR and VCD spectra and the numerically simulated ones suggested that the currently available force field parameters need to be properly modified. The results in this paper may shed light on an unknown mechanism of controlling the peptide conformation by phosphorylation.

  14. Using Circular Dichroism Spectra to Estimate Protein Secondary Structure

    SciTech Connect

    Greenfield, N.

    2006-01-01

    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 {mu}g 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.

  15. A novel computational method for comparing vibrational circular dichroism spectra.

    PubMed

    Shen, Jian; Zhu, Chengyue; Reiling, Stephan; Vaz, Roy

    2010-08-01

    A novel method, SimIR/VCD, for comparing experimental and calculated VCD (vibrational circular dichroism) spectra is developed, based on newly defined spectra similarities. With computationally optimized frequency scaling and shifting, a calculated spectrum can be easily identified to match an observed spectrum, which leads to an unbiased molecular chirality assignment. The time-consuming manual band-fitting work is greatly reduced. With (1S)-(-)-alpha-pinene as an example, it demonstrates that the calculated VCD similarity is correlated with VCD spectra matching quality and has enough sensitivity to identify variations in the spectra. The study also compares spectra calculated using different DFT methods and basis sets. Using this method should facilitate the spectra matching, reduce human error and provide a confidence measure in the chiral assignment using VCD spectroscopy.

  16. Determination of drug levels in human serum by circular dichroism.

    PubMed

    Gortázar, P; Roën, A; Vázquez, J T

    1998-01-01

    A study of the applicability of circular dichroism (CD) for the determination of drug levels in human serum is described and a new method for the quantitative determination of optically active absorbing drugs having Cotton effects at wavelengths about 250 nm in human serum and/or plasma is proposed. The principal advantages of this method are speed, economy, and simplicity, no derivatization or chromatographic separation steps being needed. The validity of the CD determination was confirmed by analysis of variance, beta-lactam antibiotics being chosen as model drugs. In addition, the validation studies performed confirm the accuracy and precision of the proposed method. For beta-lactam antibiotics lacking Cotton effects above 250 nm, an alternative method based on the extraction of the drug from serum is considered.

  17. Using circular dichroism spectra to estimate protein secondary structure

    PubMed Central

    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

  18. Tailorable Plasmonic Circular Dichroism Properties of Helical Nanoparticle Superstructures

    PubMed Central

    Song, Chengyi; Blaber, Martin G.; Zhao, Gongpu; Zhang, Peijun; Fry, H. Christopher; Schatz, George C.

    2015-01-01

    We utilize a peptide-based methodology to prepare a diverse collection of double-helical gold nanoparticle superstructures having controllable handedness and structural metrics. These materials exhibit well-defined circular dichroism signatures at visible wavelengths owing to the collective dipole–dipole interactions between the nanoparticles. We couple theory and experiment to show how tuning the metrics and structure of the helices results in predictable and tailorable chirooptical properties. Finally, we experimentally and theoretically demonstrate that the intensity, position, and nature of the chirooptical activity can be carefully adjusted via silver overgrowth. These studies illustrate the utility of peptide-based nanoparticle assembly platforms for designing and preparing complex plasmonic materials with tailorable optical properties. PMID:23777529

  19. The sequence dependence of circular dichroism spectra of DNA duplexes.

    PubMed

    Arnott, S; Arnott, S

    1975-09-01

    The three satellite DNAs of Drosophila virilis, that approximate to poly d(CAAACTA)-poly d(TAGTTTG), poly d(TAAACTA)-poly d(TAGTTTA), poly d(CAAATTA)-poly d(TAATTTG), the satellite DNA of Drosophila melanogaster that approximates to poly d(AATAT)-poly d(ATATT), the synthetic DNA duplexes, poly dG-poly dC, poly d(AT)-poly d(AT), poly d(AAT)-poly d(ATT), poly d(AAC)-poly d(GTT), poly d(TAC)-poly d(GTA) and the block copolymer d(C15A15)-d(T15G15) all have circular dichroism spectra consistent with the propositions that they have the same molecular geometry in solution and that it is the kind and frequency of nucleotide triplet sequences that determines their spectral characteristics. Poly dA-poly dT is apparently an exception.

  20. Uncertainty in measurement of protein circular dichroism spectra

    NASA Astrophysics Data System (ADS)

    Cox, Maurice G.; Ravi, Jascindra; Rakowska, Paulina D.; Knight, Alex E.

    2014-02-01

    Circular dichroism (CD) spectroscopy of proteins is widely used to measure protein secondary structure, and to detect changes in secondary and higher orders of structure, for applications in research and in the quality control of protein products such as biopharmaceuticals. However, objective comparison of spectra is challenging because of a limited quantitative understanding of the sources of error in the measurement. Statistical methods can be used for comparisons, but do not provide a mechanism for dealing with systematic, as well as random, errors. Here we present a measurement model for CD spectroscopy of proteins, incorporating the principal sources of uncertainty, and use the model in conjunction with experimental data to derive an uncertainty budget. We show how this approach could be used in practice for the objective comparison of spectra, and discuss the benefits and limitations of this strategy.

  1. Molecular magnetic dichroism in spectra of white dwarfs.

    PubMed

    Berdyugina, S V; Berdyugin, A V; Piirola, V

    2007-08-31

    We present novel calculations of the magnetic dichroism appearing in molecular bands in the presence of a strong magnetic field, which perturbs the internal structure of the molecule and results in net polarization due to the Paschen-Back effect. Based on that, we analyze new spectropolarimetric observations of the cool magnetic helium-rich white dwarf G99-37, which shows strongly polarized molecular bands in its spectrum. In addition to previously known molecular bands of the C2 Swan and CH A-X systems, we find a firm evidence for the violet CH B-X bands at 390 nm and C2 Deslandres-d'Azambuja bands at 360 nm. Combining the polarimetric observations with our model calculations, we deduce a dipole magnetic field of 7.5+/-0.5 MG with the positive pole pointing towards the Earth. We conclude that the developed technique is an excellent tool for studying magnetic fields on cool magnetic stars.

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

    ERIC Educational Resources Information Center

    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…

  3. Binding of dihydromyricetin to human hemoglobin: Fluorescence and circular dichroism studies

    NASA Astrophysics Data System (ADS)

    Chen, Tingting; Zhu, Shajun; Shang, Yanfang; Ge, Cunwang; Jiang, Guoqing

    The binding reaction between dihydromyricetin (DMY) and human hemoglobin (HHb) was investigated systematically with various spectroscopic methods including fluorescence quenching technique, ultraviolet (UV)-vis absorption, synchronous fluorescence, circular dichroism (CD) spectroscopy. The experimental results showed that DMY effectively quenched the intrinsic fluorescence of HHb via static quenching. DMY binds to HHb with a stoichiometry that varies from 0.972:1 to 0.906:1 as the temperature increases from 296 to 304 K. The DMY-HHb binding constants were determined to be K296 = 2.79 × 104 and K304 = 1.18 × 104 L mol-1. The reaction is characterized by negative enthalpy (ΔH = -80.46 kJ mol-1) and negative entropy (ΔS = -186.72 kJ mol-1), indicating that the predominant forces in the DMY-HHb complex are van der Waals and hydrogen bonding forces. Based on the Förster's theory of non-radiative energy transfer, the binding distance between DMY and the inner tryptophan residues of HHb was determined to be 3.15 nm. Furthermore, the CD spectroscopy indicated the secondary structure of HHb is not changed in the presence of DMY.

  4. Giant circular dichroism of a molecule in a plasmonic nanoparticle dimer

    NASA Astrophysics Data System (ADS)

    Zhang, Hui; Govorov, A. O.

    2013-03-01

    We report on giant circular dichroism (CD) of a molecule inserted into a plasmonic hot spot. Naturally occurring molecules and biomolecules have typically CD signals in the UV range, whereas plasmonic nanocrystals exhibit strong plasmon resonances in the visible spectral interval. Therefore, excitations of chiral molecules and plasmon resonances are typically off-resonant. Nevertheless, we demonstrate theoretically that it is possible to create strongly-enhanced molecular CD utilizing the plasmons. Specifically, by employing a nanoparticle dimer, we gain simultaneously a strong plasmonic enhancement and a shift of optical CD from the UV range to the visible. The associated mechanism of giant CD comes from the Coulomb interaction which is greatly amplified in a plasmonic hot spot. Two key factors play a role in the described effect: One is the Coulomb interaction within the molecule-dimer complex giving rise to the plasmon peak in the CD spectrum, whereas the other one is the plasmonic enhancement of the absorption process in a chiral molecule. We propose that, by using the hot spot effect and plasmon-induced CD signals, one can design optical sensors to study chirality of biomolecules. This work was supported by Volkswagen Foundation and NSF (project number CBET-0933415).

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

    NASA Astrophysics Data System (ADS)

    Ikeno, Hidekazu

    2016-10-01

    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 L2,3 XMCD from 3d transition metal complex oxides, such as NiFe2O4 and FeTiO3. 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 NiFe2O4 can be unambiguously determined. A first-principles analysis of XMCD in FeTiO3 revealed the presence of Fe3+ and Ti3+ ions, which indicates that the charge transfer from Fe to Ti ions occurs. The origin of magnetic polarization of Ti ions in FeTiO3 was also discussed.

  6. Polarization dependent two-photon absorption spectroscopy on a naturally occurring biomarker (curcumin) in solution: A theoretical-experimental study

    NASA Astrophysics Data System (ADS)

    Tiburcio-Moreno, Jose A.; Alvarado-Gil, J. J.; Diaz, Carlos; Echevarria, Lorenzo; Hernández, Florencio E.

    2013-09-01

    We report on the theoretical-experimental analysis of the two-photon absorption (TPA) and two-photon circular-linear dichroism (TPCLD) spectra of (1E,6E)-1,7-bis(4-hydroxy-3-methoxyphenyl)-1,6-heptadiene-3,5-dione (curcumin) in Tetrahydrofuran (THF) solution. The measurement of the full TPA spectrum of this molecule reveals a maximum TPA cross-section at 740 nm, i.e. more than 10 times larger than the maximum reported in the literature at 800 nm for the application of curcumin in bioimaging. The TPCLD spectrum exposes the symmetry of the main excited-states involved in the two-photon excitation process. TD-DFT calculations support the experimental results. These outcomes are expected to expand the application of natural-occurring dyes in bioimaging.

  7. Measurement of c-axis angular orientation in calcite (CaCO3) nanocrystals using X-ray absorption spectroscopy

    PubMed Central

    Gilbert, P. U. P. A.; Young, Anthony; Coppersmith, Susan N.

    2011-01-01

    We demonstrate that the ability to manipulate the polarization of synchrotron radiation can be exploited to enhance the capabilities of X-ray absorption near-edge structure (XANES) spectroscopy, to include linear dichroism effects. By acquiring spectra at the same photon energies but different polarizations, and using a photoelectron emission spectromicroscope (PEEM), one can quantitatively determine the angular orientation of micro- and nanocrystals with a spatial resolution down to 10 nm. XANES-PEEM instruments are already present at most synchrotrons, hence these methods are readily available. The methods are demonstrated here on geologic calcite (CaCO3) and used to investigate the prismatic layer of a mollusk shell, Pinctada fucata. These XANES-PEEM data reveal multiply oriented nanocrystals within calcite prisms, previously thought to be monocrystalline. The subdivision into multiply oriented nanocrystals, spread by more than 50°, may explain the excellent mechanical properties of the prismatic layer, known for decades but never explained. PMID:21693647

  8. Structure vs. excitonic transitions in self-assembled porphyrin nanotubes and their effect on light absorption and scattering.

    PubMed

    Arteaga, Oriol; Canillas, Adolf; El-Hachemi, Zoubir; Crusats, Joaquim; Ribó, Josep M

    2015-12-28

    The optical properties of diprotonated meso-tetrakis(4-sulphonatophenyl)porphyrin (TPPS(4)) J-aggregates of elongated thin particles (nanotubes in solution and ribbons when deposited on solid interfaces) are studied by different polarimetric techniques. The selective light extinction in these structures, which depends on the alignment of the nanoparticle with respect to the polarization of light, is contributed by excitonic absorption bands and by resonance light scattering. The optical response as a function of the polarization of light is complex because, although the quasi-one-dimensional structure confines the local fields along the nanotube axis, there are two orthogonal excitonic bands, of H- and J-character, that can work in favor of or against the field confinement. Results suggest that resonance light scattering is the dominant effect in solid state preparations, i.e. in collective groups (bundles) of ribbons but in diluted solutions, i.e. with isolated nanotubes, the absorption at the excitonic transitions remains dominant and linear dichroism spectra can be a direct probe of the exciton orientations. Therefore, by analyzing scattering and absorption data we can determine the alignment of the excitonic bands within the nanoparticle, i.e. of the orientation of the basic 2D porphyrin architecture in the nanoparticle. This is a necessary first step for understanding the directions of energy transport, charge polarization and non-linear optical properties in these materials.

  9. The high-field magnet endstation for X-ray magnetic dichroism experiments at ESRF soft X-ray beamline ID32.

    PubMed

    Kummer, K; Fondacaro, A; Jimenez, E; Velez-Fort, E; Amorese, A; Aspbury, M; Yakhou-Harris, F; van der Linden, P; Brookes, N B

    2016-03-01

    A new high-field magnet endstation for X-ray magnetic dichroism experiments has been installed and commissioned at the ESRF soft X-ray beamline ID32. The magnet consists of two split-pairs of superconducting coils which can generate up to 9 T along the beam and up to 4 T orthogonal to the beam. It is connected to a cluster of ultra-high-vacuum chambers that offer a comprehensive set of surface preparation and characterization techniques. The endstation and the beam properties have been designed to provide optimum experimental conditions for X-ray magnetic linear and circular dichroism experiments in the soft X-ray range between 400 and 1600 eV photon energy. User operation started in November 2014. PMID:26917134

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

    PubMed Central

    DiLullo, Andrew; Shirato, Nozomi; Cummings, Marvin; Kersell, Heath; Chang, Hao; Rosenmann, Daniel; Miller, Dean; Freeland, John W.; Hla, Saw-Wai; Rose, Volker

    2016-01-01

    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 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. PMID:26917146

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

    DOE PAGES

    DiLullo, Andrew; Shirato, Nozomi; Cummings, Marvin; Kersell, Heath; Chang, Hao; Rosenmann, Daniel; Miller, Dean; Freeland, John W.; Hla, Saw -Wai; Rose, Volker

    2016-01-28

    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 FeL2,3-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.

  12. Searching for minicharged particles via birefringence, dichroism and Raman spectroscopy of the vacuum polarized by a high-intensity laser wave

    SciTech Connect

    Villalba-Chávez, S. Müller, C.

    2013-12-15

    Absorption and dispersion of probe photons in the field of a high-intensity circularly polarized laser wave are investigated. The optical theorem is applied for determining the absorption coefficients in terms of the imaginary part of the vacuum polarization tensor. Compact expressions for the vacuum refraction indices and the photon absorption coefficients are obtained in various asymptotic regimes of interest. The outcomes of this analysis reveal that, far from the region relatively close to the threshold of the two-photon reaction, the birefringence and dichroism of the vacuum are small and, in some cases, strongly suppressed. On the contrary, in a vicinity of the region in which the photo-production of a pair occurs, these optical properties are manifest with lasers of moderate intensities. We take advantage of such a property in the search of minicharged particles by considering high-precision polarimetric experiments. In addition, Raman-like electromagnetic waves resulting from the inelastic part of the vacuum polarization tensor are suggested as an alternative form for finding exclusion limits on these hypothetical charge carriers. The envisaged parameters of upcoming high-intensity laser facilities are used for establishing upper bounds on the minicharged particles. -- Highlights: •Via dichroism and birefringence of the vacuum by a strong laser wave, minicharged particles can be probed. •The discovery potential is the highest in a vicinity of the first pair production threshold. •As alternative observable, Raman scattered waves are put forward.

  13. Well Plate Circular Dichroism Reader for the Rapid Determination of Enantiomeric Excess

    PubMed Central

    Metola, P.; Nichols, S.M.; Kahr, B.; Anslyn, E.V.

    2014-01-01

    Circular dichroism (CD) spectropolarimeters typically employ one photoelastic modulator. However, spectropolarimeters employing two or even four modulators are more versatile and can be used to subvert common measurement errors arising from imperfectly isotropic samples or sample holders. Small linear anisotropies that can cause large errors in CD measurement can be associated with multi-well sample holders. Thus, high-throughput CD analyses in multi-well plates have not yet been demonstrated. One such application is the determination of enantiomeric excess of a library of reaction products. Herein, a spectropolarimeter employing four photoelastic modulators and a translation stage was used to determine the enantiomeric excess of a family of chiral amine complexes much more rapidly than could be achieved with a robotic fluid injection system. These experiments are proof of concept for high-throughput CD analysis. In practice, commercially available glass bottomed well plates are sufficiently strain free such that a simple instrument with just one photoelastic modulator and a vertical optical train should be able to deliver the CD without special considerations given herein. On the other hand, polystyrene well plates cannot be used in this way. PMID:25386332

  14. Dichroism and order parameter coupling in BiFeO3 Films

    NASA Astrophysics Data System (ADS)

    Barry, Mikel; Zhao, T.; Zavaliche, F.; Cruz, M. P.; Chu, Y. H.; Ramesh, R.; Scholl, A.; Doran, A.

    2006-03-01

    BiFeO3 is an attractive material because it is a possible multiferroic and lead-free replacement for ferroelectric memory cells and piezoelectric sensors and actuators. We are probing the possibility of coupling between ferroelectricity and antiferromagnetism in epitaxial thin films of this system. X-ray linear dichroism based PEEM images were obtained using a high spatial resolution photoelectron emission microscope (PEEM). This combination of XLD and PEEM provides high spatial resolution along with elemental and chemical specificity and surface sensitivity. A Piezoforce microscope (PFM) was used to switch the ferroelectric state in micron-sized regions of the film, which were subsequently probed using temperature dependent PEEM measurements. Temperature dependent structural measurements were carried out to probe the changes in the ferroelectric order parameter with temperature. We observe a strong change in XLD as the temperature is raised to and beyond the Neel temperature. We will present the results of our approaches to decouple the XLD responses that arise from purely the structural distortion (i.e., due to ferroelectricity) and that arising from the antiferromagnetic state, as well as the results of the coupling experiments. This work is supported by an LBL-LDRD program and by the ONR under a MURI program.

  15. Sequence effects of aminofluorene-modified DNA duplexes: thermodynamic and circular dichroism properties

    PubMed Central

    Meneni, Srinivasa Rao; D'Mello, Rhijuta; Norigian, Gregory; Baker, Gregory; Gao, Lan; Chiarelli, M. Paul; Cho, Bongsup P.

    2006-01-01

    Circular dichroism (CD) and UV-melting experiments were conducted with 16 oligodeoxynucleotides modified by the carcinogen 2-aminofluorene, whose sequence around the lesion was varied systematically [d(CTTCTNG[AF]NCCTC), N = G, A, C, T], to gain insight into the factors that determine the equilibrium between base-displaced stacked (S) and external B-type (B) duplex conformers. Differing stabilities among the duplexes can be attributed to different populations of S and B conformers. The AF modification always resulted in sequence-dependent thermal (Tm) and thermodynamic (−ΔG°) destabilization. The population of B-type conformers derived from eight selected duplexes (i.e. -AG*N- and -CG*N-) was inversely proportional to the −ΔG° and Tm values, which highlights the importance of carcinogen/base stacking in duplex stabilization even in the face of disrupted Watson–Crick base pairing in S-conformation. CD studies showed that the extent of the adduct-induced negative ellipticities in the 290–350 nm range is correlated linearly with −ΔG° and Tm, but inversely with the population of B-type conformations. Taken together, these results revealed a unique interplay between the extent of carcinogenic interaction with neighboring base pairs and the thermodynamic properties of the AF-modified duplexes. The sequence-dependent S/B heterogeneities have important implications in understanding how arylamine–DNA adducts are recognized in nucleotide excision repair. PMID:16449208

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

    SciTech Connect

    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 {phi} 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 {phi} and the helicity of the circularly polarized laser light. For intensities above 5x10{sup 12} W/cm{sup 2} our model predicts a noticeable circular dichroism in the capture probability for slow proton-hydrogen collisions, which persists after averaging over {phi}. 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 {phi}.

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

    NASA Astrophysics Data System (ADS)

    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 .

  18. Circular dichroism and its application to the study of biomolecules.

    PubMed

    Martin, Stephen R; Schilstra, Maria J

    2008-01-01

    Circular dichroism (CD) is an excellent method for the study of the conformations adopted by proteins and nucleic acids in solution. Although not able to provide the beautifully detailed residue-specific information available from nuclearmagnetic resonance (NMR) and X-ray crystallography, CD measurements have two major advantages: they can be made on small amounts of material in physiological buffers and they provide one of the best methods for monitoring any structural alterations that might result from changes in environmental conditions, such as pH, temperature, and ionic strength. This chapter describes the important basic steps involved in obtaining reliable CD spectra: careful instrument and sample preparation, the selection of appropriate parameters for data collection, and methods for subsequent data processing. The principal features of protein and nucleic acid CD spectra are then described, and the main applications of CD are discussed. These include: methods for analyzing CD data to estimate the secondary structure composition of proteins, methods for following the unfolding of proteins as a function of temperature or added chemical denaturants, the study of the effects of mutations on protein structure and stability, and methods for studying macromolecule-ligand and macromolecule-macromolecule interactions. PMID:17964935

  19. Molecular magnetic dichroism in spectra of white dwarfs.

    PubMed

    Berdyugina, S V; Berdyugin, A V; Piirola, V

    2007-08-31

    We present novel calculations of the magnetic dichroism appearing in molecular bands in the presence of a strong magnetic field, which perturbs the internal structure of the molecule and results in net polarization due to the Paschen-Back effect. Based on that, we analyze new spectropolarimetric observations of the cool magnetic helium-rich white dwarf G99-37, which shows strongly polarized molecular bands in its spectrum. In addition to previously known molecular bands of the C2 Swan and CH A-X systems, we find a firm evidence for the violet CH B-X bands at 390 nm and C2 Deslandres-d'Azambuja bands at 360 nm. Combining the polarimetric observations with our model calculations, we deduce a dipole magnetic field of 7.5+/-0.5 MG with the positive pole pointing towards the Earth. We conclude that the developed technique is an excellent tool for studying magnetic fields on cool magnetic stars. PMID:17930997

  20. Optical activity and circular dichroism of plasmonic nanorod assemblies

    NASA Astrophysics Data System (ADS)

    Khosravi Khorashad, Larousse; Liu, Na; Govorov, Alexander O.

    Plasmonic circular dichroism (CD) has offered an efficient spectroscopy method for the electronic, chemical, and structural properties of different types of light active molecules in the subwavelength regime. Among the different chiral geometries of metal nanoparticles utilized by the plasmonic CD spectroscopy, gold nanorods (AuNRs) have shown strong CD signals in the visible frequency range. In this work, we theoretically study the CD signals of AuNR arrangements in order to mimic structures and chemical bonds of chiral biomolecules. In particular, our twisted three-AuNR geometries resemble a molecular structure of tartaric acid. This molecule played an important role in the discovery of chemical chirality. In our study, we show that the strength of CD signals changes dramatically by tuning the interparticle distances and angles. Since the CD signals are typically weak, we develop reliable computational approaches to calculate the plasmonic CD. Manipulating interparticle distances, size, and molecular bond angles result in full control over peak positions, handedness, and positive and negative bands which are observed in the CD spectra. This work has been supported under the grant from Volkswagen Foundation. We also acknowledge the financial support of Condensed Matter and Surface Science program of Ohio University.

  1. Magnetic circular dichroism spectroscopy on the Cr₈ antiferromagnetic ring.

    PubMed

    van Slageren, Joris; Piligkos, Stergios; Neese, Frank

    2010-05-28

    A Magnetic Circular Dichroism (MCD) spectroscopic study of the antiferromagnetic ring [Cr₈F₈Piv₁₆] (Piv = pivalate) is reported. From the splitting of the MCD bands, the single ion anisotropy parameters in the cluster spin ground state at different fields were determined to be d(Cr) = -0.33 ± 0.02 cm⁻¹, e(Cr) = 0.11 ± 0.01 cm⁻¹. Analysis of the MCD intensity as a function of field and temperature revealed the influence of spin mixing effects and yielded independent estimates of the single ion anisotropies (d(Cr) = -0.19 cm⁻¹, e(Cr) = 4.3 × 10-4 cm⁻¹), as well as yielding the isotropic exchange interaction strength (J = -6.00 cm⁻¹). Thus it is shown that MCD is a powerful method to unravel the relation between single-ion and cluster anisotropy, furthering the design of molecular magnets with desired properties.

  2. Circular dichroism study of the carbohydrate-modified opioid peptides

    NASA Astrophysics Data System (ADS)

    Horvat, Štefica; Otvos, Laszlo; Urge, Laszlo; Horvat, Jaroslav; Čudić, Mare; Varga-Defterdarović, Lidija

    1999-09-01

    The conformational preferences of enkephalins and the related glycoconjugates in which free or protected carbohydrate moieties were linked to the opioid peptides through an ether, ester or amide bond were investigated by circular dichroism spectroscopy in water, trifluoroethanol and water-trifluoroethanol mixtures. The analysis of the spectra revealed that the conformation of the enkephalin molecule is very sensitive to slight changes in the peptide structure around the C-terminal region. It was found that the type II β-turn structures are populated in N-terminal tetrapeptide enkephalin fragment, while leucine-enkephalin amide feature a type I (III) β-turn structure in solution. Incorporation of the sugar moiety into opioid peptide compound did not significantly influence the overall conformation of the peptide backbone, although minor intensity changes may reflect shifts in the population of the different turn systems. These small structural alterations can be responsible for the receptor-subtype selectivity of the various carbohydrate-modified enkephalin analogs.

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

    PubMed

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

    2016-01-01

    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. PMID:27329108

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

    PubMed Central

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

    2016-01-01

    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. PMID:27329108

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

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

    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.

  6. Theoretical modeling of peptide α-helical circular dichroism in aqueous solution.

    PubMed

    Kaminský, Jakub; Kubelka, Jan; Bour, Petr

    2011-03-10

    Reliable modeling of protein and peptide circular dichroism (CD) spectra in the far UV presents a challenge for current theoretical approaches. In this study, the time-dependent density functional theory (TDDFT), configuration interaction with single excitation (CIS), and transition dipole coupling (TDC) were used to assess the most important factors contributing to the CD spectra of the α-helical secondary structure. The dependence on the peptide chain length and also the role of the flexibility and solvent environment were investigated with a model oligopeptide Ac-(Ala)(N)-NH-Me, (N = 1, ..., 18). Both the TDDFT and TDC-like methods suggest that the CD curve typical for the α-helix arises gradually, but its basic characteristic is discernible already for peptides with 4-5 amino acid residues. The calculated dependence was in a qualitative agreement with experimental spectra of short α-helices stabilized by the histidine-metal binding. The TDDFT computations of the CD were found to be unusually sensitive to the basis set and solvent model. Explicit hydration and temperature fluctuations of the peptide geometry, simulated with the aid of molecular dynamics (MD), significantly influenced the CD and absorption spectral shapes. An extensive averaging over MD configurations is thus required to obtain a converged spectral profile in cluster simulations. On the other hand, both the TDDFT and TDC models indicate only a minor influence of the alanine side chains. The CIS and TDC calculations also point toward a relatively small effect of the helix-helix interaction on the CD spectral profiles. For a model system of two helices, the CIS method predicted larger changes in the spectra than TDC. This suggests other than interactions between peptide chains, such as mutual polarization, can have a minor, but measurable, effect on the CD spectrum.

  7. Tryptophan contributions to the unusual circular dichroism of fd bacteriophage.

    PubMed

    Arnold, G E; Day, L A; Dunker, A K

    1992-09-01

    The circular dichroism (CD) spectrum of fd bacteriophage has a deep minimum at 222 nm characteristic of highly alpha-helical protein, but there is a shoulder at 208 nm rather than a minimum, with a 222/208-nm amplitude ratio near 1.5 rather than near 1. Oxidation of fd phage with the tryptophan reagent N-bromosuccinimide (NBS) changes the ratio. In this report, the NBS titration of fd is followed by CD and three other spectroscopies, the results of which yield an explanation of the unusual CD spectrum. Absorbance, fluorescence, and Raman data show the oxidation to have two phases, the first of which involves the destruction of tryptophan and the second, tryptophan and tyrosine. Raman spectra reveal the invariance of an environmentally-sensitive tyrosine Fermi resonance doublet during the first oxidative phase. Raman spectra also show that little or no change of alpha-helicity occurs in the first or second oxidation phase, although very slight changes in the helix parameters might be occurring. Concurrent with the destruction of tryptophan during the first phase is the appearance in CD difference spectra ([theta]NBS-treated fd - [theta]native fd) of positive maxima at 208-210 nm and negative maxima at 224 nm, with crossovers at 217 nm. Enormous difference ellipticities, per oxidized subunit of 50 amino acids, of +490,000 +/- 80,000 deg cm2 dmol-1 at 208 nm and -520,000 +/- 110,000 deg cm2 dmol-1 at 224 nm have been derived from the data.(ABSTRACT TRUNCATED AT 250 WORDS)

  8. Transient absorption spectroscopy of laser shocked explosives

    SciTech Connect

    Mcgrane, Shawn D; Dang, Nhan C; Whitley, Von H; Bolome, Cindy A; Moore, D S

    2010-01-01

    Transient absorption spectra from 390-890 nm of laser shocked RDX, PETN, sapphire, and polyvinylnitrate (PVN) at sub-nanosecond time scales are reported. RDX shows a nearly linear increase in absorption with time after shock at {approx}23 GPa. PETN is similar, but with smaller total absorption. A broad visible absorption in sapphire begins nearly immediately upon shock loading but does not build over time. PVN exhibits thin film interference in the absorption spectra along with increased absorption with time. The absorptions in RDX and PETN are suggested to originate in chemical reactions happening on picosecond time scales at these shock stresses, although further diagnostics are required to prove this interpretation.

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

    PubMed

    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.

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

    PubMed

    Friese, Daniel H

    2015-09-01

    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.

  11. Time-Resolved X-Ray Magnetic Circular Dichroism - A Selective Probe of Magnetization Dynamics on Nanosecond Timescales

    NASA Astrophysics Data System (ADS)

    Pizzini, Stefania; Vogel, Jan; Bonfim, Marlio; Fontaine, Alain

    Many synchrotron radiation techniques have been developed in the last 15 years for studying the magnetic properties of thin-film materials. The most attractive properties of synchrotron radiation are its energy tunability and its time structure. The first property allows measurements in resonant conditions at an absorption edge of each of the magnetic elements constituting the probed sample, and the latter allows time-resolved measurements on subnanosecond timescales. In this review, we introduce some of the synchrotron-based techniques used for magnetic investigations. We then describe in detail X-ray magnetic circular dichroism (XMCD) and how time-resolved XMCD studies can be carried out in the pump-probe mode. Finally, we illustrate some applications to magnetization reversal dynamics in spin valves and tunnel junctions, using fast magnetic field pulses applied along the easy magnetization axis of the samples. Thanks to the element-selectivity of X-ray absorption spectroscopy, the magnetization dynamics of the soft (Permalloy) and the hard (cobalt) layers can be studied independently. In the case of spin valves, this allowed us to show that two magnetic layers that are strongly coupled in a static regime can become uncoupled on nanosecond timescales.Present address: Universidade Federal do Paraná, Centro Politécnico CP 19011, Curitiba - PR CEP 81531-990, Brazil

  12. Cadmium binding studies to the earthworm Lumbricus rubellus metallothionein by electrospray mass spectrometry and circular dichroism spectroscopy

    SciTech Connect

    Ngu, Thanh T.; Sturzenbaum, Stephen R.; Stillman, Martin J. . E-mail: Martin.Stillman@uwo.ca

    2006-12-08

    The earthworm Lumbricus rubellus has been found to inhabit cadmium-rich soils and accumulate cadmium within its tissues. Two metallothionein (MT) isoforms (1 and 2) have been identified and cloned from L. rubellus. In this study, we address the metalation status, metal coordination, and structure of recombinant MT-2 from L. rubellus using electrospray ionization mass spectrometry (ESI-MS), UV absorption, and circular dichroism (CD) spectroscopy. This is the first study to show the detailed mass and CD spectral properties for the important cadmium-containing earthworm MT. We report that the 20-cysteine L. rubellus MT-2 binds seven Cd{sup 2+} ions. UV absorption and CD spectroscopy and ESI-MS pH titrations show a distinct biphasic demetalation reaction, which we propose results from the presence of two metal-thiolate binding domains. We propose stoichiometries of Cd{sub 3}Cys{sub 9} and Cd{sub 4}Cys{sub 11} based on the presence of 20 cysteines split into two isolated regions of the sequence with 11 cysteines in the N-terminal and 9 cysteines in the C-terminal. The CD spectrum reported is distinctly different from any other metallothionein known suggesting quite different binding site structure for the peptide.

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

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

    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.

  14. Acid-Base Titration of (S)-Aspartic Acid: A Circular Dichroism Spectrophotometry Experiment

    NASA Astrophysics Data System (ADS)

    Cavaleiro, Ana M. V.; Pedrosa de Jesus, Júlio D.

    2000-09-01

    The magnitude of the circular dichroism of (S)-aspartic acid in aqueous solutions at a fixed wavelength varies with the addition of strong base. This laboratory experiment consists of the circular dichroism spectrophotometric acid-base titration of (S)-aspartic acid in dilute aqueous solutions, and the use of the resulting data to determine the ionization constant of the protonated amino group. The work familiarizes students with circular dichroism and illustrates the possibility of performing titrations using a less usual instrumental method of following the course of a reaction. It shows the use of a chiroptical property in the determination of the concentration in solution of an optically active molecule, and exemplifies the use of a spectrophotometric titration in the determination of an ionization constant.

  15. Four-wave mixing using polarization grating induced thermal grating in liquids exhibiting circular dichroism

    SciTech Connect

    Nunes, J.A.; Tong, W.G.; Chandler, D.W.; Rahn, L.A.

    1995-04-01

    A novel four-wave mixing technique for the detection of circular dichroism in optically active liquid samples is demonstrated. When two cross-polarized laser beams are crossed at a small angle in a circular dichroic liquid a weak thermal grating is produced with a phase depending on the sign of the circular dichroism. The authors show that the polarization of one of the beams can be modified to allow coherent interference with an intensity-grating induced thermal grating. A probe beam scattering from the composite grating results in a signal that reveals the sign and magnitude of the circular dichroism. The use of this technique to optimize the signal-to-noise ratio in the presence of scattered light and laser intensity noise is discussed.

  16. Scanning differential polarization microscope: Its use to image linear and circular differential scattering

    SciTech Connect

    Mickols, W.; Maestre, M.F.

    1988-06-01

    A differential polarization microscope that couples the sensitivity of single-beam measurement of circular dichroism and circular differential scattering with the simultaneous measurement of linear dichroism and linear differential scattering has been developed. The microscope uses a scanning microscope stage and single-point illumination to give the very shallow depth of field found in confocal microscopy. This microscope can operate in the confocal mode as well as in the near confocal condition that can allow one to program the coherence and spatial resolution of the microscope. This microscope has been used to study the change in the structure of chromatin during the development of sperm in Drosophila.

  17. Isotope effect on the circular dichroism spectrum of methyl α-D-glucopyranoside in aqueous solution

    PubMed Central

    Kanematsu, Yusuke; Kamiya, Yukiko; Matsuo, Koichi; Gekko, Kunihiko; Kato, Koichi; Tachikawa, Masanori

    2015-01-01

    H/D isotope effect on the circular dichroism spectrum of methyl α-D-glucopyranoside in aqueous solution has been analyzed by multicomponent density functional theory calculations using the polarizable continuum model. By comparing the computational spectra with the corresponding experimental spectrum obtained with a vacuum-ultraviolet circular dichroism spectrophotometer, it was demonstrated that the isotope effect provides insights not only into the isotopic difference of the intramolecular interactions of the solutes, but also into that of the solute–solvent intermolecular interaction. PMID:26658851

  18. Spectropolarimetric investigation of the photoinduced dichroism and birefringence in malachite green/dichromated gelatin films

    NASA Astrophysics Data System (ADS)

    Markova, Bistra; Hristov, Boyan; Todorov, Todor; Nikolova, Ludmila; Stoilov, Georgi

    2009-06-01

    We report a spectropolarimetric investigation of the photoinduced anisotropy in dichromated gelatin films containing the dye malachite green. The investigation is done with a novel Spectral Stokesmeter which measures simultaneously and in real time (20 ms) the spectra of all the Stokes parameters of light in the spectral range 500-750 nm. This made it possible to measure not only the spectrum of the dichroism but also, for the first time to our knowledge, the spectrum of the photoinduced birefringence in these films. The results show that we can measure trustworthy dichroism larger than 0.02 and birefringence larger than 2 × 10-4.

  19. Ab initio calculations of X-ray magnetic circular dichroism spectra within the projector augmented wave method: An implementation into the VASP code

    NASA Astrophysics Data System (ADS)

    Dixit, Anant; Alouani, M.

    2016-10-01

    X-ray absorption and X-ray magnetic circular dichroism (XMCD) are very powerful tools for probing the orbital and spin moments of each atomic species orbital of magnetic materials. In this work, we present the implementation of a module for computing the X-ray absorption and XMCD spectra into the VASP code. We provide a derivation of the absorption cross-section in the electric dipole approximation. The matrix elements, which make up the X-ray absorption cross-section for a given polarization of light, are then computed using either the momentum operator p or the position operator r, within the projector augmented wave method. The core electrons are described using the relativistic basis-set whereas for the valence electrons, the spin-orbit coupling is added perturbatively to the semi-relativistic Hamiltonian. We show that both the p and the r implementations lead to the same results. The results for the K-edge and L23-edges of bcc-iron are then computed and compared to experiment.

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

    ERIC Educational Resources Information Center

    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…

  1. Linear Accelerators

    SciTech Connect

    Sidorin, Anatoly

    2010-01-05

    In linear accelerators the particles are accelerated by either electrostatic fields or oscillating Radio Frequency (RF) fields. Accordingly the linear accelerators are divided in three large groups: electrostatic, induction and RF accelerators. Overview of the different types of accelerators is given. Stability of longitudinal and transverse motion in the RF linear accelerators is briefly discussed. The methods of beam focusing in linacs are described.

  2. The effects of self-aggregation on the vibrational circular dichroism and optical rotation measurements of glycidol.

    PubMed

    Yang, Guochun; Xu, Yunjie

    2008-12-01

    The noncovalent interactions between glycidol molecules in the CDCl3 solvent have been studied by means of vibrational absorption (VA), vibrational circular dichroism (VCD), optical rotation (OR) spectroscopy and density functional theory (DFT) calculations. The concentration dependence of the VA and VCD spectra and OR measurements at five excitation wavelengths, i.e. 589, 578, 546, 436 and 365 nm, has been reported. To model the effects of self-aggregation of glycidol on the measurements, the energetic and conformational properties of the glycidol monomer, dimer and trimer were evaluated and the corresponding VA, VCD and OR spectra were simulated. The results show that at 0.2 M or lower concentrations the self-aggregation of glycidol is negligible since the simulated VA and VCD spectra, with the contribution from only the monomeric glycidol conformers, reproduce well the features in the experimental spectra. At 3.5 M, the binary conformers dominate, while at the intermediate concentration of 1.1 M, both the monomeric and binary conformers are important. The comparison of the experimental and theoretical OR values supports the above conclusions. This work shows the potential of using multiple chiroptical spectroscopic methods in combination with theoretical calculations to probe the self-aggregation process of chiral molecules in solution. Such studies can in turn help to achieve reliably absolute configuration determinations in the cases when chiral molecules self-aggregate profusely.

  3. Vibronic Coupling Explains the Different Shape of Electronic Circular Dichroism and of Circularly Polarized Luminescence Spectra of Hexahelicenes.

    PubMed

    Liu, Yanli; Cerezo, Javier; Mazzeo, Giuseppe; Lin, Na; Zhao, Xian; Longhi, Giovanna; Abbate, Sergio; Santoro, Fabrizio

    2016-06-14

    We present the simulation of the absorption (ABS), electronic circular dichroism (ECD), emission (EMI), and circularly polarized luminescence (CPL) spectra for the weak electronic transition between the ground (S0) and the lowest excited state (S1) of hexahelicene, 2-methylhexahelicene, 2-bromohexahelicene, and 5-azahexahelicene. Vibronic contributions have been computed at zero Kelvin and at room temperature in harmonic approximation including Duschinsky effects and accounting for both Franck-Condon and Herzberg-Teller contributions. Our results nicely capture the effects of the different substituents on the experimental spectra. They also show that HT effects dominate the shape of ECD and CPL spectra where they even induce changes of signs; HT effects are also relevant in ABS and EMI, tuning the relative intensities of the different vibronic bands. HT effects are the main reason for the differences in the line shapes of ABS and ECD and of EMI and CPL spectra and for the mirror-symmetry breaking between ABS and EMI and between ECD and CPL spectra. In order to check the robustness of our results, given also that few examples of calculations of vibronic CPL spectra exist, we adopted both adiabatic and vertical approaches to define the model potential energy surfaces of the (S0) and the (S1) states; moreover we expanded the electric and magnetic dipole transition moments around both the S0 and S1 equilibrium geometries. PMID:27120334

  4. Comparative Analysis of IR and Vibrational Circular Dichroism Spectra for a Series of Camphor-Related Molecules

    NASA Astrophysics Data System (ADS)

    Abbate, Sergio; Burgi, Luigi Filippo; Gangemi, Fabrizio; Gangemi, Roberto; Lebon, France; Longhi, Giovanna; Pultz, Vaughan M.; Lightner, David A.

    2009-09-01

    The absorption spectra and vibrational circular dichroism (VCD) spectra in the mid-IR range 1600-950 cm-1 of 10 camphor-related compounds have been recorded and compared to DFT calculated spectra at the B3PW91/TZ2P level and have been examined together with the corresponding data of the parent molecules. The rigidity of the bridged structure common to all compounds investigated permits (a) identification of three spectroscopic regions in the mid-IR range that can be "used" separately by the interested stereochemist for structural diagnosis and assignment of some major characteristics of the VCD spectra in these regions to what we call "skeletal chiral sense" and (b) recognition of possible conformers for flexible substituent groups, when present. VCD spectra of the 10 molecules have been recorded and analyzed also in the CH-stretching region, 3100-2800 cm-1. Here, we have been able to identify and characterize features of vibrational excitons by comparison of data within the 10-molecule class. To find a theoretical justification of result (a), we have examined the potential energy distribution of the normal modes in the mid-IR range, the partitioning of the calculated rotational strengths in terms of contributions from all couples of internal coordinates, the angle formed by the two vectors, the electric dipole transition moment and the magnetic dipole transition moment, and finally the overlap of normal modes of different molecules. A discussion is provided as to the usability of the introduced algorithms.

  5. Magnetic field induced directional dichroism of spin waves in multiferroic BiFeO3 at THz frequencies

    NASA Astrophysics Data System (ADS)

    Nagel, Urmas; Rõõm, T.; Bordács, S.; Kézsmárki, I.; Yi, H. T.; Cheong, S.-W.; Lee, Jun Hee; Fishman, Randy S.

    2015-03-01

    Using far infrared spectroscopy in high magnetic fields we show that spin excitations in BiFeO3 simultaneously interact with the electric and magnetic field components of light resulting in directional dichroism (DD) of absorption. DD in BiFeO3 arises because an applied static magnetic field induces a toroidal moment in the cycloidal spin structure. Strong DD is observed even in the room-temperature state of the material. The results are explained on the microscopic level as an interplay of five different interactions: isotropic exchange couplings between nearest and next nearest neighbors, an easy-axis anisotropy along the ferroelectric polarization, Dzyaloshinskii-Moriya (DM) interaction that creates the cycloid and DM interaction that causes spin canting. Research sponsored by the Estonian Ministry of Education and Research (IUT23-3), Estonian Science Foundation (ETF8703), and U.S. Department of Energy (JL), Office of Science, Materials Sciences and Engineering Division (RF and JL) and Office of Basis En.

  6. Ground-state wave function of plutonium in PuSb as determined via x-ray magnetic circular dichroism

    SciTech Connect

    Janoschek, M.; Haskel, D.; Fernandez-Rodriguez, J.; van Veenendaal, M.; Rebizant, J.; Lander, G. H.; Zhu, J. -X.; Thompson, J. D.; Bauer, E. D.

    2015-01-14

    Measurements of x-ray magnetic circular dichroism (XMCD) and x-ray absorption near-edge structure (XANES) spectroscopy at the Pu M₄,₅ edges of the ferromagnet PuSb are reported. Using bulk magnetization measurements and a sum rule analysis of the XMCD spectra, we determine the individual orbital [μL = 2.8(1)μB/Pu] and spin moments [μS = –2.0(1)μB/Pu] of the Pu 5f electrons for the first time. Atomic multiplet calculations of the XMCD and XANES spectra reproduce well the experimental data and are consistent with the experimental value of the spin moment. These measurements of Lz and Sz are in excellent agreement with the values that have been extracted from neutron magnetic form factor measurements, and confirm the local character of the 5f electrons in PuSb. We demonstrate that a split M₅ as well as a narrow M₄ XMCD signal may serve as a signature of 5f electron localization in actinide compounds.

  7. Ground-state wave function of plutonium in PuSb as determined via x-ray magnetic circular dichroism

    DOE PAGES

    Janoschek, M.; Haskel, D.; Fernandez-Rodriguez, J.; van Veenendaal, M.; Rebizant, J.; Lander, G. H.; Zhu, J. -X.; Thompson, J. D.; Bauer, E. D.

    2015-01-14

    Measurements of x-ray magnetic circular dichroism (XMCD) and x-ray absorption near-edge structure (XANES) spectroscopy at the Pu M₄,₅ edges of the ferromagnet PuSb are reported. Using bulk magnetization measurements and a sum rule analysis of the XMCD spectra, we determine the individual orbital [μL = 2.8(1)μB/Pu] and spin moments [μS = –2.0(1)μB/Pu] of the Pu 5f electrons for the first time. Atomic multiplet calculations of the XMCD and XANES spectra reproduce well the experimental data and are consistent with the experimental value of the spin moment. These measurements of Lz and Sz are in excellent agreement with the values thatmore » have been extracted from neutron magnetic form factor measurements, and confirm the local character of the 5f electrons in PuSb. We demonstrate that a split M₅ as well as a narrow M₄ XMCD signal may serve as a signature of 5f electron localization in actinide compounds.« less

  8. Polarized x-ray-absorption spectroscopy of the uranyl ion: Comparison of experiment and theory

    SciTech Connect

    Hudson, E.A.; Allen, P.G.; Terminello, L.J.; Denecke, M.A.; Reich, T.

    1996-07-01

    The x-ray linear dichroism of the uranyl ion (UO{sub 2}{sup 2+}) in uranium {ital L}{sub 3}-edge extended x-ray-absorption fine structure (EXAFS), and {ital L}{sub 1}- and {ital L}{sub 3}-edge x-ray-absorption near-edge structure (XANES), has been investigated both by experiment and theory. A striking polarization dependence is observed in the experimental XANES and EXAFS for an oriented single crystal of uranyl acetate dihydrate [UO{sub 2}(CH{sub 3}CO{sub 2}){sub 2}{center_dot}2H{sub 2}O], with the x-ray polarization vector aligned either parallel or perpendicular to the bond axis of the linear uranyl cation (O-U-O). Single-crystal results are compared to experimental spectra for a polycrystalline uranyl acetate sample and to calculations using the {ital ab} {ital initio} multiple-scattering (MS) code FEFF 6. Theoretical XANES spectra for uranyl fluoride (UO{sub 2}F{sub 2}) reproduce all the features of the measured uranyl acetate spectra. By identifying scattering paths which contribute to individual features in the calculated spectrum, a detailed understanding of the {ital L}{sub 1}-edge XANES is obtained. MS paths within the uranyl cation have a notable influence upon the XANES. The measured {ital L}{sub 3}-edge EXAFS is also influenced by MS, especially when the x-ray polarization is parallel to the uranyl species. These MS contributions are extracted from the total EXAFS and compared to calculations. The best agreement with the isolated MS signal is obtained by using nonoverlapped muffin-tin spheres in the FEFF 6 calculation. This contrasts the {ital L}{sub 1}-edge XANES calculations, in which overlapping was required for the best agreement with experiment. {copyright} {ital 1996 The American Physical Society.}

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

    ERIC Educational Resources Information Center

    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…

  10. Magnetic Circular Dichroism Studies XXV. A Preliminary Investigation of Microsomal Cytochromes*

    PubMed Central

    Dolinger, Peter M.; Kielczewski, Michael; Trudell, James R.; Barth, Günter; Linder, Robert E.; Bunnenberg, Edward; Djerassi, Carl

    1974-01-01

    The application of magnetic circular dichroism as an optical probe for simultaneous identification and determination of at least two microsomal cytochromes is demonstrated. The assignments of the bands in the spectra of microsomal suspensions are made from the spectra of soluble preparations of cytochrome P-450 obtained from Pseudomonas putida and of cytochrome b5 obtained from rat livers. PMID:4521811

  11. Room-temperature ferromagnetism of Cu-doped ZnO films probed by soft X-ray magnetic circular dichroism.

    PubMed

    Herng, T S; Qi, D-C; Berlijn, T; Yi, J B; Yang, K S; Dai, Y; Feng, Y P; Santoso, I; Sánchez-Hanke, C; Gao, X Y; Wee, Andrew T S; Ku, W; Ding, J; Rusydi, A

    2010-11-12

    We report direct evidence of room-temperature ferromagnetic ordering in O-deficient ZnO:Cu films by using soft x-ray magnetic circular dichroism and x-ray absorption. Our measurements have revealed unambiguously two distinct features of Cu atoms associated with (i) magnetically ordered Cu ions present only in the oxygen-deficient samples and (ii) magnetically disordered regular Cu2+ ions present in all the samples. We find that a sufficient amount of both oxygen vacancies (V(O)) and Cu impurities is essential to the observed ferromagnetism, and a non-negligible portion of Cu impurities is uninvolved in the magnetic order. Based on first-principles calculations, we propose a microscopic "indirect double-exchange" model, in which alignments of localized large moments of Cu in the vicinity of the V(O) are mediated by the large-sized vacancy orbitals.

  12. Room-Temperature Ferromagnetism of Cu-Doped ZnO Films Probed by Soft X-Ray Magnetic Circular Dichroism

    SciTech Connect

    Herng, T.S.; Ku, W.; Qi, D.-C.; Berlijn, T.; Yi, J.B.; Yang, K.S.; Dai, Y.; Feng, Y.P.; Santoso, I.; Sanchez-Hanke, C.; Gao, X.Y.; Wee, A.T.S.; Ding, J.; Rusydi, A.

    2010-11-08

    We report direct evidence of room-temperature ferromagnetic ordering in O-deficient ZnO:Cu films by using soft x-ray magnetic circular dichroism and x-ray absorption. Our measurements have revealed unambiguously two distinct features of Cu atoms associated with (i) magnetically ordered Cu ions present only in the oxygen-deficient samples and (ii) magnetically disordered regular Cu{sup 2+} ions present in all the samples. We find that a sufficient amount of both oxygen vacancies (V{sub O}) and Cu impurities is essential to the observed ferromagnetism, and a non-negligible portion of Cu impurities is uninvolved in the magnetic order. Based on first-principles calculations, we propose a microscopic 'indirect double-exchange' model, in which alignments of localized large moments of Cu in the vicinity of the V{sub O} are mediated by the large-sized vacancy orbitals.

  13. Direct observation of high-spin states in manganese dimer and trimer cations by x-ray magnetic circular dichroism spectroscopy in an ion trap

    SciTech Connect

    Zamudio-Bayer, V.; Hirsch, K.; Langenberg, A.; Kossick, M.; Ławicki, A.; Lau, J. T.; Terasaki, A.; Issendorff, B. von

    2015-06-21

    The electronic structure and magnetic moments of free Mn{sub 2}{sup +} and Mn{sub 3}{sup +} 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 directly show that localized magnetic moments of 5 μ{sub B} are created by 3d{sup 5}({sup 6}S) states at each ionic core, which are coupled ferromagnetically 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 antibonding molecular orbital with an unpaired spin. This leads to total magnetic moments of 11 μ{sub B} for Mn{sub 2}{sup +} and 16 μ{sub B} for Mn{sub 3}{sup +}, with no contribution of orbital angular momentum.

  14. Indication of intrinsic room-temperature ferromagnetism in Ti1-xCoxO2-δ thin film: An x-ray magnetic circular dichroism study

    NASA Astrophysics Data System (ADS)

    Mamiya, K.; Koide, T.; Fujimori, A.; Tokano, H.; Manaka, H.; Tanaka, A.; Toyosaki, H.; Fukumura, T.; Kawasaki, M.

    2006-08-01

    Soft x-ray magnetic circular dichroism (XMCD) measurements at the Co L2,3 edges of Co-doped rutile TiO2 at room temperature revealed clear multiplet features characteristic of ferromagnetic Co2+ ions coordinated by O2- ions, being in sharp contrast to the featureless XMCD spectrum of Co metal or metallic clusters. The absorption and XMCD spectra agree well with a full atomic-multiplet calculation for the Co2+ high-spin state in the D2h-symmetry crystal field at the Ti site in rutile TiO2. The results indicate that the ferromagnetism arises from the Co2+ ions substituting the Ti4+ ions.

  15. Linear Colliders

    NASA Astrophysics Data System (ADS)

    Yamamoto, Akira; Yokoya, Kaoru

    2015-02-01

    An overview of linear collider programs is given. The history and technical challenges are described and the pioneering electron-positron linear collider, the SLC, is first introduced. For future energy frontier linear collider projects, the International Linear Collider (ILC) and the Compact Linear Collider (CLIC) are introduced and their technical features are discussed. The ILC is based on superconducting RF technology and the CLIC is based on two-beam acceleration technology. The ILC collaboration completed the Technical Design Report in 2013, and has come to the stage of "Design to Reality." The CLIC collaboration published the Conceptual Design Report in 2012, and the key technology demonstration is in progress. The prospects for further advanced acceleration technology are briefly discussed for possible long-term future linear colliders.

  16. Linear Colliders

    NASA Astrophysics Data System (ADS)

    Yamamoto, Akira; Yokoya, Kaoru

    An overview of linear collider programs is given. The history and technical challenges are described and the pioneering electron-positron linear collider, the SLC, is first introduced. For future energy frontier linear collider projects, the International Linear Collider (ILC) and the Compact Linear Collider (CLIC) are introduced and their technical features are discussed. The ILC is based on superconducting RF technology and the CLIC is based on two-beam acceleration technology. The ILC collaboration completed the Technical Design Report in 2013, and has come to the stage of "Design to Reality." The CLIC collaboration published the Conceptual Design Report in 2012, and the key technology demonstration is in progress. The prospects for further advanced acceleration technology are briefly discussed for possible long-term future linear colliders.

  17. Electronic circular dichroism of highly conjugated π-systems: breakdown of the Tamm-Dancoff/configuration interaction singles approximation.

    PubMed

    Bannwarth, Christoph; Grimme, Stefan

    2015-04-16

    We show that the electronic circular dichroism (ECD) of delocalized π-systems represents a worst-case scenario for Tamm-Dancoff approximated (TDA) linear response methods. We mainly consider density functional theory (TDA-DFT) variants together with range-separated hybrids, but the conclusions also apply for other functionals as well as the configuration interaction singles (CIS) approaches. We study the effect of the TDA for the computation of ECD spectra in some prototypical extended π-systems. The C76 fullerene, a chiral carbon nanotube fragment, and [11]helicene serve as model systems for inherently chiral, π-chromophores. Solving the full linear response problem is inevitable in order to obtain accurate ECD spectra for these systems. For the C76 fullerene and the nanotube fragment, TDA and CIS approximated methods yield spectra in the origin-independent velocity gauge formalism of incorrect sign which would lead to the assignment of the opposite (wrong) absolute configuration. As a counterexample, we study the ECD of an α-helix polypeptide chain. Here, the lowest-energy transitions are dominated by localized excitations within the individual peptide units, and TDA methods perform satisfactorily. The results may have far-reaching implications for simple semiempirical methods which often employ TDA and CIS for huge molecules. Our recently presented simplified time-dependent DFT approach proves to be an excellent low-cost linear response method which together with range-separated density functionals like ωB97X-D3 produces ECD spectra in very good agreement with experiment. PMID:25798823

  18. X-ray magnetic dichroism studies of magnetic multilayer systems

    NASA Astrophysics Data System (ADS)

    Antel, William Joseph, Jr.

    X-ray magnetic circular/linear dichoism (XMCD/XMLD) are powerful techniques used for element specific determination of magnetic moments. They are used with magneto-optic Kerr magnetometry (MOKE) and x-ray diffraction in the study of three different systems. The magnetic moments of Fe and Pt are determined as a function of Pt thickness in an Fe/Pt (001) multilayer. Additionally, MOKE is used to study the in plane anisotropy of the system. The ≈0.5 mB Pt induced moment is found to strongly effect the anisotropy of the system. A ferromagnetic rare-earth monopnictide, GdN, is studied as part of a Fe/GdN multilayer. XMCD is used to determine the moments of Gd and Fe in the system. It is demonstrated that it is possible to significantly enhance the Curie temperature of the GdN. Finally, the spin structure of antiferromagnetic FeMn is determined in an exchange biased FeMn/Co bilayer. It is found that four FeMn monolayers at the interface are aligned parallel to the Co in an alternating collinear spin arrangement. Beyond this the FeMn reverts to its bulk tetrahedral spin structure. Uncompensated Fe spins at the interface are the probable source of the exchange bias in this system. Lastly, a surface analysis chamber is built for the collection of angle-resolved Auger electron diffraction data.

  19. Linear Collisions

    ERIC Educational Resources Information Center

    Walkiewicz, T. A.; Newby, N. D., Jr.

    1972-01-01

    A discussion of linear collisions between two or three objects is related to a junior-level course in analytical mechanics. The theoretical discussion uses a geometrical approach that treats elastic and inelastic collisions from a unified point of view. Experiments with a linear air track are described. (Author/TS)

  20. Validation of a method using an achiral liquid chromatography sorbent and a circular dichroism detector. Analysis of the efaroxan enantiomers.

    PubMed

    Lorin, Marie; Delépée, Raphaël; Ribet, Jean-Paul; Morin, Philippe

    2007-02-01

    The known HPLC method using an achiral C8 silica sorbent and a circular dichroism (CD) detector for the determination of efaroxan enantiomeric excess has been validated. After optimization of the mobile phase, the enantiomers were detected at 278 nm offering maximum ellipticity between two optically active forms. The calibration curve of the anisotropy factor (g) versus the enantiomeric excess was linear with a correlation coefficient (r2) of 0.9985. The accuracy of the method was assessed by comparing the enantiomeric excess obtained by measuring the g factor (C8 column, CD and UV detections) with those determined by enantioselective HPLC (Chiralpak AD-H column, UV detection). Statistical tests (level of confidence of 95%) were assessed to compare the two orthogonal methods. The straight line gave a correlation coefficient of 0.9995, an intercept not significantly different from zero (0.0549) and a slope of 1.026. The precision evaluated on retention time (RSD<0.6%), g factor (RSD<8.3%) and CD peak area (RSD<7.5%) was suitable both in term of intra- and inter-day precisions. The proposed method has the advantages of being fast and precise without using expensive chiral column. Non-enantioselective HPLC-CD was suitable for the simultaneous determination of the optical and chemical purity of efaroxan.

  1. ABSORPTION ANALYZER

    DOEpatents

    Brooksbank, W.A. Jr.; Leddicotte, G.W.; Strain, J.E.; Hendon, H.H. Jr.

    1961-11-14

    A means was developed for continuously computing and indicating the isotopic assay of a process solution and for automatically controlling the process output of isotope separation equipment to provide a continuous output of the desired isotopic ratio. A counter tube is surrounded with a sample to be analyzed so that the tube is exactly in the center of the sample. A source of fast neutrons is provided and is spaced from the sample. The neutrons from the source are thermalized by causing them to pass through a neutron moderator, and the neutrons are allowed to diffuse radially through the sample to actuate the counter. A reference counter in a known sample of pure solvent is also actuated by the thermal neutrons from the neutron source. The number of neutrons which actuate the detectors is a function of a concentration of the elements in solution and their neutron absorption cross sections. The pulses produced by the detectors responsive to each neu tron passing therethrough are amplified and counted. The respective times required to accumulate a selected number of counts are measured by associated timing devices. The concentration of a particular element in solution may be determined by utilizing the following relation: T2/Ti = BCR, where B is a constant proportional to the absorption cross sections, T2 is the time of count collection for the unknown solution, Ti is the time of count collection for the pure solvent, R is the isotopic ratlo, and C is the molar concentration of the element to be determined. Knowing the slope constant B for any element and when the chemical concentration is known, the isotopic concentration may be readily determined, and conversely when the isotopic ratio is known, the chemical concentrations may be determined. (AEC)

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

    SciTech Connect

    Takahashi, S.; Ota, Y.; Tatebayashi, J.; Tajiri, T.; Iwamoto, S.; Arakawa, Y.

    2014-08-04

    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° 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 1.3 μm. The obtained results show good agreement with numerical simulations.

  3. First enantioseparation and circular dichroism spectra of Au38 clusters protected by achiral ligands

    PubMed Central

    Dolamic, Igor; Knoppe, Stefan; Dass, Amala; Bürgi, Thomas

    2012-01-01

    Bestowing chirality to metals is central in fields such as heterogeneous catalysis and modern optics. Although the bulk phase of metals is symmetric, their surfaces can become chiral through adsorption of molecules. Interestingly, even achiral molecules can lead to locally chiral, though globally racemic, surfaces. A similar situation can be obtained for metal particles or clusters. Here we report the first separation of the enantiomers of a gold cluster protected by achiral thiolates, Au38(SCH2CH2Ph)24, achieved by chiral high-performance liquid chromatography. The chirality of the nanocluster arises from the chiral arrangement of the thiolates on its surface, forming 'staple motifs'. The enantiomers show mirror-image circular dichroism responses and large anisotropy factors of up to 4×10−3. Comparison with reported circular dichroism spectra of other Au38 clusters reveals that the influence of the ligand on the chiroptical properties is minor. PMID:22531183

  4. Birefringence and anisotropic optical absorption in porous silicon

    SciTech Connect

    Efimova, A. I. Krutkova, E. Yu.; Golovan', L. A.; Fomenko, M. A.; Kashkarov, P. K.; Timoshenko, V. Yu.

    2007-10-15

    The refractive indices and the coefficients of optical absorption by free charge carriers and local vibrations in porous silicon (por-Si) films, comprising nanometer-sized silicon residues (nanocrystals) separated by nanometer-sized pores (nanopores) formed in the course of electrochemical etching of the initial single crystal silicon, have been studied by polarization-resolved IR absorption spectroscopy techniques. It is shown that the birefringence observed in por-Si is related to the anisotropic shapes of nanocrystals and nanopores, while the anisotropy (dichroism) of absorption by the local vibrational modes is determined predominantly by the microrelief of the surface of nanocrystals. It is demonstrated that silicon-hydrogen surface bonds in nanocrystals can be restored by means of selective hydrogen thermodesorption with the formation of a considerable number of H-terminated surface Si-Si dimers.

  5. Polarizable continuum model study of solvent effects on electronic circular dichroism parameters

    NASA Astrophysics Data System (ADS)

    Pecul, Magdalena; Marchesan, Domenico; Ruud, Kenneth; Coriani, Sonia

    2005-01-01

    We present an implementation of the polarizable continuum model for the calculation of solvent effects on electronic circular dichroism spectra. The computational model used is density functional theory in the length-gauge formulation, and gauge-origin independence is ensured through the use of London atomic orbitals. Results of calculations carried out for methyloxirane and bicyclic ketones, camphor, norcamphor, norbornenone, and fenchone are presented, and the theoretically obtained solvent effects are compared with experimental observations.

  6. MICROFLUIDIC MIXERS FOR THE INVESTIGATION OF PROTEIN FOLDING USING SYNCHROTRON RADIATION CIRCULAR DICHROISM SPECTROSCOPY

    SciTech Connect

    Kane, A; Hertzog, D; Baumgartel, P; Lengefeld, J; Horsley, D; Schuler, B; Bakajin, O

    2006-03-20

    The purpose of this study is to design, fabricate and optimize microfluidic mixers to investigate the kinetics of protein secondary structure formation with Synchrotron Radiation Circular Dichroism (SRCD) spectroscopy. The mixers are designed to rapidly initiate protein folding reaction through the dilution of denaturant. The devices are fabricated out of fused silica, so that they are transparent in the UV. We present characterization of mixing in the fabricated devices, as well as the initial SRCD data on proteins inside the mixers.

  7. Synchrotron Radiation Circular Dichroism (SRCD) Spectroscopy - An Enhanced Method for Examining Protein Conformations and Protein Interactions

    SciTech Connect

    B Wallace; R Janes

    2011-12-31

    CD (circular dichroism) spectroscopy is a well-established technique in structural biology. SRCD (synchrotron radiation circular dichroism) spectroscopy extends the utility and applications of conventional CD spectroscopy (using laboratory-based instruments) because the high flux of a synchrotron enables collection of data at lower wavelengths (resulting in higher information content), detection of spectra with higher signal-to-noise levels and measurements in the presence of absorbing components (buffers, salts, lipids and detergents). SRCD spectroscopy can provide important static and dynamic structural information on proteins in solution, including secondary structures of intact proteins and their domains, protein stability, the differences between wild-type and mutant proteins, the identification of natively disordered regions in proteins, and the dynamic processes of protein folding and membrane insertion and the kinetics of enzyme reactions. It has also been used to effectively study protein interactions, including protein-protein complex formation involving either induced-fit or rigid-body mechanisms, and protein-lipid complexes. A new web-based bioinformatics resource, the Protein Circular Dichroism Data Bank (PCDDB), has been created which enables archiving, access and analyses of CD and SRCD spectra and supporting metadata, now making this information publicly available. To summarize, the developing method of SRCD spectroscopy has the potential for playing an important role in new types of studies of protein conformations and their complexes.

  8. Q & a Experiment to Search for Vacuum Dichroism, Pseudoscalar-Photon Interaction and Millicharged Fermions

    NASA Astrophysics Data System (ADS)

    Chen, Sheng-Jui; Mei, Hsien-Hao; Ni, Wei-Tou

    A number of experiments are underway to detect vacuum birefringence and dichroism — PVLAS, Q & A, and BMV. Recently, PVLAS experiment has observed optical rotation in vacuum by a magnetic field (vacuum dichroism). Theoretical interpretations of this result include a possible pseudoscalar-photon interaction and the existence of millicharged fermions. Here, we report the progress and first results of Q & A (QED [quantum electrodynamics] and Axion) experiment proposed and started in 1994. We use a 3.5-m high-finesse (around 30,000) Fabry-Perot prototype detector extendable to 7-m with the cavity mirrors suspended using X-pendulum-double pendulums. To polarize the vacuum, we use a 2.3-T dipole permanent magnet rotated at 5-10 rev/s, with 27-mm-diameter clear borehole and 0.6-m field length. Our ellipsometer/polarization-rotation-detection-system is formed by a pair of Glan-Taylor type polarizing prisms with extinction ratio lower than 10-8 together with a polarization modulating Faraday Cell with/without a quarter wave plate. Our first results give (-0.2 ± 2.8) × 10-13 rad/pass with 18,700 passes through a 2.3 T 0.6 m long magnet for vacuum dichroism measurement. We present our experimental limit on pseudo-scalar-photon interaction and millicharged fermions.

  9. Magnetic dichroism in angle-resolved hard x-ray photoemission from buried layers

    NASA Astrophysics Data System (ADS)

    Kozina, Xeniya; Fecher, Gerhard H.; Stryganyuk, Gregory; Ouardi, Siham; Balke, Benjamin; Felser, Claudia; Schönhense, Gerd; Ikenaga, Eiji; Sugiyama, Takeharu; Kawamura, Naomi; Suzuki, Motohiro; Taira, Tomoyuki; Uemura, Tetsuya; Yamamoto, Masafumi; Sukegawa, Hiroaki; Wang, Wenhong; Inomata, Koichiro; Kobayashi, Keisuke

    2011-08-01

    This work reports the measurement of magnetic dichroism in angular-resolved photoemission from in-plane magnetized buried thin films. The high bulk sensitivity of hard x-ray photoelectron spectroscopy (HAXPES) in combination with circularly polarized radiation enables the investigation of the magnetic properties of buried layers. HAXPES experiments with an excitation energy of 8 keV were performed on exchange-biased magnetic layers covered by thin oxide films. Two types of structures were investigated with the IrMn exchange-biasing layer either above or below the ferromagnetic layer: one with a CoFe layer on top and another with a Co2FeAl layer buried beneath the IrMn layer. A pronounced magnetic dichroism is found in the Co and Fe 2p states of both materials. The localization of the magnetic moments at the Fe site conditioning the peculiar characteristics of the Co2FeAl Heusler compound, predicted to be a half-metallic ferromagnet, is revealed from the magnetic dichroism detected in the Fe 2p states.

  10. LINEAR ACCELERATOR

    DOEpatents

    Christofilos, N.C.; Polk, I.J.

    1959-02-17

    Improvements in linear particle accelerators are described. A drift tube system for a linear ion accelerator reduces gap capacity between adjacent drift tube ends. This is accomplished by reducing the ratio of the diameter of the drift tube to the diameter of the resonant cavity. Concentration of magnetic field intensity at the longitudinal midpoint of the external sunface of each drift tube is reduced by increasing the external drift tube diameter at the longitudinal center region.

  11. Novel approach for non-invasive glucose sensing using vibrational contrast CD absorption measurements (Conference Presentation)

    NASA Astrophysics Data System (ADS)

    Yakovlev, Vladislav V.; Tovar, Carlos; Hokr, Brett; Petrov, Georgi I.

    2016-03-01

    Noninvasive glucose sensing is a Holy Grail of diabetes mellitus management. Unfortunately, despite a number of innovative concepts and a long history of continuous instrumental improvements, the problem remains largely unsolved. Here we propose and experimentally demonstrate the first successful implementation of a novel strategy based on vibrational overtone circular dichroism absorption measurements. Such an approach uses a short-wavelength infrared excitation (1000-2000 nm), which takes the advantage of lower light scattering and intrinsic chemical contrast provided by the chemical structure of D-glucose molecule. We model the propagation of circular polarized light in scattering medium using Monte Carlo simulations to show the feasibility of such approach in turbid medium and demonstrate the proof of principle using optical detection. We also investigate the possibility of using ultrasound detection through circular dichroism absorption measurements to achieve simple and sensitive glucose monitoring.

  12. Magnetic circular dichroism spectroscopic characterization of the NOS-like protein from Geobacillus stearothermophilus (gsNOS).

    PubMed

    Kinloch, Ryan D; Sono, Masanori; Sudhamsu, Jawahar; Crane, Brian R; Dawson, John H

    2010-03-01

    Nitric oxide synthase (NOS) catalyzes the NADPH- and O(2)-dependent oxidation of l-arginine (l-Arg) to nitric oxide (NO) and citrulline via an N(G)-hydroxy-l-arginine (NHA) intermediate. Mammalian NOSs have been studied quite extensively; other eukaryotes and some prokaryotes appear to express NOS-like proteins comparable to the oxygenase domain of mammalian NOSs. In this study, a recombinant NOS-like protein from the thermostable bacterium Geobacillus stearothermophilus (gsNOS) has been characterized using magnetic circular dichroism (MCD) and UV-Vis absorption spectroscopic techniques. Spectral comparisons of ligand complexes (with O(2), NO and CO) of substrate-bound (l-Arg or NHA) gsNOS, including the key oxyferrous complex studied at -50 degrees C in cryogenic mixed solvents, with analogous mammalian NOS complexes indicate overall spectroscopic similarities between gsNOS and mammalian NOSs. However, more detailed spectral comparisons reflect subtle structural differences between gsNOS and mammalian NOSs. This may be due to an incomplete tetrahydrobiopterin (BH(4))-binding site and low BH(4)-binding affinity, which may become even lower in the presence of cryosolvent in gsNOS. Although BH(4)-binding may be altered, gsNOS appears to require the pterin for NO production since formation of the stable ferric-NO product complex was only observed when excess BH(4) (>150muM) over gsNOS was present upon single turnover reaction in which O(2) was bubbled into dithionite-reduced NHA-bound protein solution at -35 degrees C or -50 degrees C. PMID:20110129

  13. Naturally crystalline hemoglobin of the nematode Mermis nigrescens. An in situ microspectrophotometric study of chemical properties and dichroism.

    PubMed Central

    Burr, A H; Harosi, F I

    1985-01-01

    A dichroic microspectrophotometer was used to measure isotropic and dichroic absorbance spectra of this unique cytoplasmic hemoglobin and its derivatives. A perfusion slide enabled changing the media bathing the Mermis head. The native spectrum, which has an exceptionally low alpha-band extinction, was shown to be entirely due to oxyhemoglobin. The CO-hemoglobin spectrum is more typical, however, the alpha- and beta-bands are unusually closely spaced. A ferric hemochrome was formed on oxidation with ferricyanide or hydroxylamine and was readily converted to ferric hemoglobin cyanide on adding cyanide. Aquoferric hemoglobin and ferric hemoglobin fluoride were not easily formed. Deoxyhemoglobin, identified by its typical absorption spectrum, was formed only under the extremely low O2 pressures attainable in the presence of dithionite. A glucose oxidase, catalase solution deoxygenated hemoglobin in human erythrocytes but not in adjacent Mermis preparations. The affinity for O2 is much greater than for CO. Also, spectral evidence points to an oxyheme environment that is different than in vertebrate hemoglobin and myoglobin. The polarization ratio (PR) magnitude and the PR spectrum were unaffected by perfusion with high refractive index solvents; therefore, form dichroism due to the rodlike crystals is negligible. Maximum extinction is approximately perpendicular to the long axis of the microscopic crystals, which are oriented parallel to the body axis within the hypodermal cells. The PR spectra of the hemoglobin derivatives strongly resemble the corresponding spectra previously reported of single crystals made of horse hemoglobin, whale myoglobin, or Aplysia myoglobin and change appropriately when the ligand is changed. This confirms that the intracellular crystals of Mermis are of oxyhemoglobin. PMID:3986282

  14. Zeeman Splitting of Ferromagnetic GaMnAs on InP Observed by Magnetic Circular Dichroism in Reflection Mode

    NASA Astrophysics Data System (ADS)

    Tanaka, H.; Bsatee, M.; Jadwisienczak, W. M.

    2016-08-01

    Systematic investigations of Ga1- x Mn x As grown on InP with different Mn concentrations have been conducted using magnetic circular dichroism (MCD) in reflection mode. The MCD spectrum of Ga0.97Mn0.03As/InP was decomposed into two dispersion curves originating from E 1 and E 1 + Δ1 optical transitions using the energy derivative of a Gaussian function. The Zeeman splitting energy E 1 at the L critical point (0.6 meV) of ferromagnetic Ga0.97Mn0.03As/InP was estimated using a rigid band shift model. Based on the relationship between E 1 and E 0 (Γ critical point) observed in Cd1- x Mn x Te dilute magnetic semiconductor (DMS), the Zeeman splitting energy E 1 (9.6 meV) of ferromagnetic Ga1- x Mn x As/InP was calculated. In addition, it was established that the peaks in the MCD spectra at L critical points shift toward the lower energy side as the Mn concentration is increased, and the observed shift saturates for Mn content of x = 0.001. Furthermore, the measured absorption spectra for Ga1- x Mn x As/InP did not show noticeable peak shifts with increasing Mn content. This suggests that the s, p- d exchange interaction induced in Ga1- x Mn x As/InP has localized nature due to the presence of a Mn rigid sphere of influence.

  15. Molecular organization of the antifungal and anticancer drug 2-(2,4-dihydroxyphenylo)-5,6-dichlorobenzothiazole (dHBBT) in solution and in lipid membranes studied by means of electronic absorption spectroscopy.

    PubMed

    Gagoś, Mariusz; Niewiadomy, Andrzej; Gruszecki, Wiesław I

    2004-10-25

    2-(2,4-Dihydroxyphenylo)-5,6-dichlorobenzthiazole (dHBBT) is a new drug from the group of chemical compounds characterized by documented antifungal, antibacterial, cytostatic as well as antitumour activity. Despite general knowledge regarding pharmacological importance of dHBBT its interaction to biomembranes has not been investigated. In this work, we present the electronic absorption spectroscopic study on molecular organization of dHBBT in organic solvents and on its localization and molecular organization within model lipid membranes formed with dipalmitoylphosphatidylcholine (DPPC). The spectroscopic measurements are interpreted within the framework of the exciton splitting theory. It is concluded that complex absorption spectrum of dHBBT both in the organic solvents and incorporated to DPPC represents superposition of two spectral forms: representing monomers and hypsochromically shifted spectrum representing molecular dimers. Analysis of the temperature dependencies of the absorption spectra of dHBBT incorporated to DPPC liposomes suggests localization of the drug in the polar head-group region of the membrane or in the region of the polar-nonpolar interface. Linear dichroism measurements of dHBBT incorporated to DPPC multibilayers reveal roughly vertical orientation of the drug molecules with respect to the plane of the membrane. A model is presented of molecular organization of dHBBT in lipid membranes. Potential effects of dHBBT on membrane physical properties is briefly discussed. PMID:15488713

  16. Characterization of intermolecular structure of β(2)-microglobulin core fragments in amyloid fibrils by vacuum-ultraviolet circular dichroism spectroscopy and circular dichroism theory.

    PubMed

    Matsuo, Koichi; Hiramatsu, Hirotsugu; Gekko, Kunihiko; Namatame, Hirofumi; Taniguchi, Masaki; Woody, Robert W

    2014-03-20

    Intermolecular structures are important factors for understanding the conformational properties of amyloid fibrils. In this study, vacuum-ultraviolet circular dichroism (VUVCD) spectroscopy and circular dichroism (CD) theory were used for characterizing the intermolecular structures of β2-microglobulin (β2m) core fragments in the amyloid fibrils. The VUVCD spectra of β2m20-41, β2m21-31, and β2m21-29 fragments in the amyloid fibrils exhibited characteristic features, but they were affected not only by the backbone conformations but also by the aromatic side-chain conformations. To estimate the contributions of aromatic side-chains to the spectra, the theoretical spectra were calculated from the simulated structures of β2m21-29 amyloid fibrils with various types of β-sheet stacking (parallel or antiparallel) using CD theory. We found that the experimental spectrum of β2m21-29 fibrils is largely affected by aromatic-backbone couplings, which are induced by the interaction between transitions within the aromatic and backbone chromophores, and these couplings are sensitive to the type of stacking among the β-sheets of the fibrils. Further theoretical analyses of simulated structures incorporating mutated aromatic residues suggested that the β2m21-29 fibrils are composed of amyloid accumulations in which the parallel β-sheets stack in an antiparallel manner and that the characteristic Phe-Tyr interactions among the β-sheet stacks affect the aromatic-backbone coupling. These findings indicate that the coupling components, which depend on the characteristic intermolecular structures, induce the spectral differences among three fragments in the amyloid fibrils. These advanced spectral analyses using CD theory provide a useful method for characterizing the intermolecular structures of protein and peptide fragment complexes.

  17. Determination of bromhexine in cough-cold syrups by absorption spectrophotometry and multivariate calibration using partial least-squares and hybrid linear analyses. Application of a novel method of wavelength selection.

    PubMed

    Goicoechea, H C; Olivieri, A C

    1999-07-12

    The mucolitic bromhexine [N-(2-amino-3,5-dibromobenzyl)-N-methylcyclohexylamine] has been determined in cough suppressant syrups by multivariate spectrophotometric calibration, together with partial least-squares (PLS-1) and hybrid linear analysis (HLA). Notwithstanding the spectral overlapping between bromhexine and syrup excipients, as well as the intrinsic variability of the latter in unknown samples, the recoveries are excellent. A novel method of wavelength selection was also applied, based on the concept of net analyte signal regression, as adapted to the HLA methodology. This method allows one to improve the performance of both PLS-1 and HLA in samples containing nonmodeled interferences. PMID:18967655

  18. Magnetic properties of neodynium atoms in Nd-Fe multilayers studied by magnetic x-ray dichroism on Nd LII and Fe K edges

    NASA Astrophysics Data System (ADS)

    Baudelet, F.; Dartyge, E.; Fontaine, A.; Brouder, C.; Krill, G.; Kappler, J. P.; Piecuch, M.

    1991-03-01

    In this paper we present an experimental investigation of the magnetic properties of metallic multilayers (here Nd-Fe) by magnetic x-ray dichroism (MXD). The magnetic absorption cross sections have been measured, using a dispersive optics, on both the LII edge of Nd and the K edge of Fe in several Nd-Fe multilayers (Λ~=40-100 Å), for temperatures ranging from 77 to 300 K. We will show that the intensity of the magnetic absorption can be roughly correlated to the ordered magnetic moments present either on Nd or Fe, and thus the MXD allows direct information to be obtained on the local magnetic properties on a given atom. Moreover, by performing systematic studies as a function of the modulation length Λ, we discuss the efficiency of such experiments to yield direct information about the magnetic properties of the interfaces themselves. MXD experiments also give the sense of the coupling (ferromagnetic in the present case) between the magnetic moments of Nd and Fe in those systems. MXD results are compared to those given by bulk magnetization measurements and Mössbauer experiments on 57Fe.

  19. Infrared and circular dichroism spectroscopic characterisation of secondary structure components of a water treatment coagulant protein extracted from Moringa oleifera seeds.

    PubMed

    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. PMID:18296034

  20. X-ray magnetic circular dichroism on La2/3Ca1/3Mn0.97Fe0.03O3 thin films

    NASA Astrophysics Data System (ADS)

    Figueroa, Adriana I.; Campillo, Gloria E.; Baker, Alexander A.; Osorio, Jaime A.; Arnache, Oscar L.; van der Laan, Gerrit

    2015-11-01

    The element-selective technique of X-ray magnetic circular dichroism (XMCD) has been used to study the magnetic properties of La2/3Ca1/3Mn0.97Fe0.03O3 (LCMFO) thin films. XMCD measurements below the ferromagnetic ordering temperature at the Mn and Fe L2,3 absorption edges allow the determination of the contributions and relative orientations of the Mn and Fe magnetic moments. A reduction in the Mn L2,3 XMCD signal of the LCMFO sample compared to that for the parent La2/3Ca1/3MnO3 (LCMO) system reveals important modifications in the electronic and magnetic properties with the presence of Fe. The Fe L2,3 X-ray absorption (XAS) for the LCMFO film is characteristic of Fe3+, and the comparison with multiplet calculations shows that the Fe dopants occupy octahedral sites in the crystal, which is consistent with Fe3+ substituting Mn3+ in LCMO. The magnetic moments of Mn and Fe are found to align antiparallel, which suggests the presence of Mn-O-Fe superexchange coupling. This result is consistent with macroscopic magnetometry measurements on the LCMFO system, which show a decrease in saturation magnetization of LCMO with Fe doping.

  1. The tunable chirality and circular dichroism of topological Kondo insulator SmB6 with C2v symmetry as a function of Rashba and Dresselhaus parameters

    NASA Astrophysics Data System (ADS)

    Sengupta, Parijat; Bellotti, Enrico

    A manifestation of optical chirality is circular dichroism (CD) due to a differential absorption of left- and right-circularly polarized light. This effect is an enabler for the design of meta-materials used in polarization sensitive imaging devices and display technologies. Concurrently, topological insulators with helical surface states offer an active control over chiral handedness that can be observed through a varying degree of polarization-dependent absorption. We show that in a band gap open topological Kondo insulator SmB6 with C2v symmetry at the X point of the surface Brillouin zone, CD can be smoothly varied without any microscopic reconfiguration of the surface. We also show that CD, measured by the degree of circular polarization, can assume both positive and negative values. These findings suggest that left- and right- circularly polarized light can be selectively absorbed in the vicinity of the Dirac point by an adjustment of the Rashba- and Dresselhaus-like parameters that describe the Hamiltonian at the X point. The CD is an experimentally measurable quantity and related to Berry curvature which is an outcome of the parameter-dependent Hamiltonian. We calculate the Berry curvature and establish a pathway to alter CD through the Hamiltonian parameters.

  2. Differentiation between transmembrane helices and peripheral helices by the deconvolution of circular dichroism spectra of membrane proteins.

    PubMed Central

    Park, K.; Perczel, A.; Fasman, G. D.

    1992-01-01

    The interpretation of the circular dichroism (CD) spectra of proteins to date requires additional secondary structural information of the proteins to be analyzed, such as X-ray or NMR data. Therefore, these methods are inappropriate for a CD database whose secondary structures are unknown, as in the case of the membrane proteins. The convex constraint analysis algorithm (Perczel, A., Hollósi, M., Tusnády, G., & Fasman, G. D., 1991, Protein Eng. 4, 669-679), on the other hand, operates only on a collection of spectral data to extract the common spectral components with their spectral weights. The linear combinations of these derived "pure" CD curves can reconstruct the original data set with great accuracy. For a membrane protein data set, the five-component spectra so obtained from the deconvolution consisted of two different types of alpha helices (the alpha helix in the soluble domain and the alpha T helix, for the transmembrane alpha helix), a beta-pleated sheet, a class C-like spectrum related to beta turns, and a spectrum correlated with the unordered conformation. The deconvoluted CD spectrum for the alpha T helix was characterized by a positive red-shifted band in the range 195-200 nm (+95,000 deg cm2 dmol-1), with the intensity of the negative band at 208 nm being slightly less negative than that of the 222-nm band (-50,000 and -60,000 deg cm2 dmol-1, respectively) in comparison with the regular alpha helix, with a positive band at 190 nm and two negative bands at 208 and 222 nm with magnitudes of +70,000, -30,000, and -30,000 deg cm2 dmol-1, respectively. PMID:1338977

  3. Identification of beta,beta-turns and unordered conformations in polypeptide chains by vacuum ultraviolet circular dichroism.

    PubMed

    Brahms, S; Brahms, J; Spach, G; Brack, A

    1977-08-01

    Different conformations of polypeptides were characterized by measurements of the circular dichroism (CD) extended into the vacuum ultraviolet region. (i) The linear beta-pleated sheet structure was characterized in a broad ultraviolet region down to 165 nm by examination of copolypeptides composed of alternating hydrophobic and hydrophilic amino-acid residues, e.g., poly(Lys-Leu-Lys-Leu). A short-wavelength intense band was found at about 169 nm, which is characteristic of beta-pleated sheet conformation. (ii) The beta-turns were experimentally measured using poly(Ala(2)-Gly(2)) in a broad spectral region down to 165 nm with accuracy. The observed CD spectrum is in excellent qualitative agreement with the theoretical curve calculated by Woody for the beta-turns of type II and/or I of Venkatachalam. The similarity in shape between the theoretical curve and the observed CD spectra suggests a dominance of beta-turn segments in the poly(Ala(2)-Gly(2)) structure. The presence of beta-turns in poly(Ala(2)-Gly(2)) is also in agreement with the characterization of this polypeptide by solid state methods (electron microscopy and x-ray diffraction). The CD spectrum of beta-turns is characterized by a very intense band at 207.5 nm and strong negative bands at 191 and 169 nm. Copolypeptides such as poly(Ala(2)-Gly(3)) and poly(Ala(3)-Gly(3)) yielded a similar type of CD spectrum, analysis of which indicates that a large fraction of their residues is contained in beta-turn regions. (iii) The CD spectrum of the unordered chain of these alternating copolypeptides in salt-free solution is observed in the vacuum ultraviolet region.

  4. Structure of epitaxial (Fe,N) codoped rutile TiO2 thin films by x-ray absorption

    NASA Astrophysics Data System (ADS)

    Kaspar, T. C.; Ney, A.; Mangham, A. N.; Heald, S. M.; Joly, Y.; Ney, V.; Wilhelm, F.; Rogalev, A.; Yakou, F.; Chambers, S. A.

    2012-07-01

    Homoepitaxial thin films of Fe:TiO2 and (Fe,N):TiO2 were deposited on rutile(110) by molecular beam epitaxy. X-ray absorption near edge spectroscopy (XANES) spectra were collected at the Ti L-edge, Fe L-edge, Ti K-edge, O K-edge, and N K-edge. No evidence of structural disorder associated with a high concentration of oxygen vacancies is observed. Substitution of Fe for Ti could be inferred, and secondary phases such as Fe2O3, Fe3O4, and FeTiO3 can be ruled out. The similarity of the N K-edge spectra to O, and the presence of a strong x-ray linear dichroism signal for the N K-edge, indicates that N is substitutional for O in the rutile lattice and is not present as a secondary phase such as TiN. Simulations of the XANES spectra confirm substitution, although N appears to be present in more than one local environment. Neither Fe:TiO2 nor (Fe,N):TiO2 exhibit intrinsic room temperature ferromagnetism, despite the presence of mixed valent Fe(II)/Fe(III) in the reduced (Fe,N):TiO2 film.

  5. Circular Dichroism studies on the interactions of antimicrobial peptides with bacterial cells

    NASA Astrophysics Data System (ADS)

    Avitabile, Concetta; D'Andrea, Luca Domenico; Romanelli, Alessandra

    2014-03-01

    Studying how antimicrobial peptides interact with bacterial cells is pivotal to understand their mechanism of action. In this paper we explored the use of Circular Dichroism to detect the secondary structure of two antimicrobial peptides, magainin 2 and cecropin A, with E. coli bacterial cells. The results of our studies allow us to gain two important information in the context of antimicrobial peptides- bacterial cells interactions: peptides fold mainly due to interaction with LPS, which is the main component of the Gram negative bacteria outer membrane and the time required for the folding on the bacterial cells depends on the peptide analyzed.

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

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

    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

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

    SciTech Connect

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

    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

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

    PubMed

    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.

  9. Magnetic circular x-ray dichroisms of Fe-Ni alloys at K edge.

    SciTech Connect

    Freeman, A. J.; Gofron, K. J.; Kimball, C. W.; Lee, P. L.; Montano, P. A.; Rao, F.; Wang, X.

    1997-04-03

    Magnetic Circular X-ray Dichroism (MCXD) studies at K edges of Fe-Ni alloys reveal changes of the MCXD signal with composition and crystal structure. We observe that the signal at the invar composition is of comparable strength as other compositions. Moreover, the edge position is strongly dependent on lattice constant. First principles calculations demonstrate that the shape and strength of the signal strongly depends on the crystal orientation, composition, and lattice constant. We find direct relation between the MCXD signal and the p DOS. We find that the MCXD at K edge probes the magnetism due to itinerant electrons.

  10. Chiral imaging of collagen by second-harmonic generation circular dichroism

    PubMed Central

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

    2013-01-01

    We provide evidence that the chirality of collagen can give rise to strong second-harmonic generation circular dichroism (SHG-CD) responses in nonlinear microscopy. Although chirality is an intrinsic structural property of collagen, most of the previous studies ignore that property. We demonstrate chiral imaging of individual collagen fibers by using a laser scanning microscope and type-I collagen from pig ligaments. 100% contrast level of SHG-CD is achieved with sub-micrometer spatial resolution. As a new contrast mechanism for imaging chiral structures in bio-tissues, this technique provides information about collagen morphology and three-dimensional orientation of collagen molecules. PMID:23761852

  11. LINEAR ACCELERATOR

    DOEpatents

    Colgate, S.A.

    1958-05-27

    An improvement is presented in linear accelerators for charged particles with respect to the stable focusing of the particle beam. The improvement consists of providing a radial electric field transverse to the accelerating electric fields and angularly introducing the beam of particles in the field. The results of the foregoing is to achieve a beam which spirals about the axis of the acceleration path. The combination of the electric fields and angular motion of the particles cooperate to provide a stable and focused particle beam.

  12. Giant circular dichroism in extrinsic chiral metamaterials excited by off-normal incident laser beams

    NASA Astrophysics Data System (ADS)

    Feng, C.; Wang, Z. B.; Lee, S.; Jiao, J.; Li, L.

    2012-05-01

    Recently it was shown by experiments that circular dichroism (CD) can be observed in the metamaterials of non-chiral structures when they were subjected to obliquely incident light (E. Plum, et al., Physical Review Letters 102, 113902, 2009). By far, external chirality simulation was only done for a particle array embedded in a homogenous medium (V. Yannopapas, Optics Letters 34, 5, 2009); no attempt has been made on simulating and modelling of circular dichroism in layered metamaterials (e.g., thin film on substrate structure). In this paper, we present the simulation of CD effect in layered external chiral metamaterials using CST software, theoretically investigate this intriguing phenomenon through a frequency domain finite integration technique, and optimize the metamaterial unit cell configurations (size, periodicity and film thickness) to maximize the CD phenomenon in near-infrared spectrum range. We show that the CD effect can be enhanced by five times using an optimized unit cell configuration, which is more than three times higher than the existing maximum theoretical results. The CD generation mechanism was elaborated with the help of induced surface current distributions.

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

    NASA Astrophysics Data System (ADS)

    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.

  14. Vibrational Circular Dichroism Spectra for Large Molecules through Molecules-in-Molecules Fragment-Based Approach.

    PubMed

    Jose, K V Jovan; Beckett, Daniel; Raghavachari, Krishnan

    2015-09-01

    We present the first implementation of the vibrational circular dichroism (VCD) spectrum of large molecules through the Molecules-in-Molecules (MIM) fragment-based method. An efficient projection of the relevant higher energy derivatives from smaller fragments to the parent molecule enables the extension of the MIM method for the evaluation of VCD spectra (MIM-VCD). The overlapping primary subsystems in this work are constructed from interacting fragments using a number-based scheme and the dangling bonds are saturated with link hydrogen atoms. Independent fragment calculations are performed to evaluate the energies, Hessian matrix, atomic polar tensor (APT), and the atomic axial tensor (AAT). Subsequently, the link atom tensor components are projected back onto the corresponding host and supporting atoms through the Jacobian projection method, as in the ONIOM approach. In the two-layer model, the long-range interactions between fragments are accounted for using a less computationally intensive lower level of theory. The performance of the MIM model is calibrated on the d- and l-enantiomers of 10 carbohydrate benchmark molecules, with strong intramolecular interactions. The vibrational frequencies and VCD intensities are accurately reproduced relative to the full, unfragmented, results for these systems. In addition, the MIM-VCD method is employed to predict the VCD spectra of perhydrotriphenylene and cryptophane-A, yielding spectra in agreement with experiment. The accuracy and performance of the benchmark systems validate the MIM-VCD model for exploring vibrational circular dichroism spectra of large molecules.

  15. Angle and temperature dependence of magnetic circular dichroism in core-level photoemission from Gd(0001)

    SciTech Connect

    Denecke, R.; Morais, J.; Ynzunza, R. X.; Menchero, J. G.; Liesegang, J.; Rice, M.; Kortright, J.; Hussain, Z.; Fadley, C. S.

    1997-04-01

    Magnetic dichroism in core-level photoelectron emission from solids represents a promising new element-specific probe of surface and interface atomic structure and magnetic order. One way of measuring such effects is by using photoelectrons excited by circular polarized radiation, thus leading to magnetic circular dichroism (MCD) if the intensity with right-circular polarized (RCP) light is not equal to that with left-circular polarized (LCP) light. The spin-integrated photoelectron intensity in a certain emission direction also in general depends on the direction of the magnetization in a magnetic material. In fact, if the magnetization lies in a surface mirror plane, then inverting its direction can provide a second way of measuring MCD. Purely atomic theoretical models have been successful in explaining many aspects of such data. By varying the emission direction one also probes the geometric structure of the sample. But such MCD in photoelectron angular distributions (MCDAD) then has to be interpreted also in terms of photoelectron diffraction. Measuring the temperature dependence of such MCD effects also provides a useful tool for studying magnetic transition temperatures. The authors have here studied such effects in core-level emission from Gd(0001).

  16. Linear Clouds

    NASA Technical Reports Server (NTRS)

    2006-01-01

    [figure removed for brevity, see original site] Context image for PIA03667 Linear Clouds

    These clouds are located near the edge of the south polar region. The cloud tops are the puffy white features in the bottom half of the image.

    Image information: VIS instrument. Latitude -80.1N, Longitude 52.1E. 17 meter/pixel resolution.

    Note: this THEMIS visual image has not been radiometrically nor geometrically calibrated for this preliminary release. An empirical correction has been performed to remove instrumental effects. A linear shift has been applied in the cross-track and down-track direction to approximate spacecraft and planetary motion. Fully calibrated and geometrically projected images will be released through the Planetary Data System in accordance with Project policies at a later time.

    NASA's Jet Propulsion Laboratory manages the 2001 Mars Odyssey mission for NASA's Office of Space Science, Washington, D.C. The Thermal Emission Imaging System (THEMIS) was developed by Arizona State University, Tempe, in collaboration with Raytheon Santa Barbara Remote Sensing. The THEMIS investigation is led by Dr. Philip Christensen at Arizona State University. Lockheed Martin Astronautics, Denver, is the prime contractor for the Odyssey project, and developed and built the orbiter. Mission operations are conducted jointly from Lockheed Martin and from JPL, a division of the California Institute of Technology in Pasadena.

  17. The structure of tri-proline in water probed by polarized Raman, Fourier transform infrared, vibrational circular dichroism, and electric ultraviolet circular dichroism spectroscopy.

    PubMed

    Schweitzer-Stenner, Reinhard; Eker, Fatma; Perez, Alejandro; Griebenow, Kai; Cao, Xiaolin; Nafie, Laurence A

    2003-01-01

    Tripeptidesserve as model systems for understanding the so-called random-coil state of peptides and proteins. While it is well known that polyproline or proline-rich polypeptides adopt the very regular polyproline-II (PPII) or left-handed 3(1)-helix conformation, it was thus far not clear whether this is also the predominant structure adopted by proline-containing tripeptides. To clarify this issue, we have investigated the amide I' band profile in the ir, isotropic, and anisotropic Raman, and vibrational circular dichroism (VCD) spectrum of cationic and zwitterionic tri-proline in D(2)O. The data were analyzed by modifying a recently developed algorithm, which allows one to obtain the central dihedral angles of tripeptides from the amide I' band intensities (R. Schweitzer-Stenner, Biophysical Journal, 2002, Vol. 83, pp. 523-532). Our analysis revealed that the peptide adopts a nearly canonical PPII structure in water with psi and phi values in the range of 175 degrees -165 degrees and -70 degrees -(-80 degrees ), respectively. This is fully confirmed by the respective electronic ultraviolet-CD spectra. Our result indicates that the strong PPII propensity of trans proline results from local interactions between the pyrrolidine ring and the backbone and is not due to any long-range interactions.

  18. Slow light and saturable absorption

    NASA Astrophysics Data System (ADS)

    Selden, A. C.

    2009-06-01

    Quantitative analysis of slow light experiments utilising coherent population oscillation (CPO) in a range of saturably absorbing media, including ruby and alexandrite, Er3+:Y2SiO5, bacteriorhodopsin, semiconductor quantum devices and erbium-doped optical fibres, shows that the observations may be more simply interpreted as saturable absorption phenomena. A basic two-level model of a saturable absorber displays all the effects normally associated with slow light, namely phase shift and modulation gain of the transmitted signal, hole burning in the modulation frequency spectrum and power broadening of the spectral hole, each arising from the finite response time of the non-linear absorption. Only where hole-burning in the optical spectrum is observed (using independent pump and probe beams), or pulse delays exceeding the limits set by saturable absorption are obtained, can reasonable confidence be placed in the observation of slow light in such experiments. Superluminal (“fast light”) phenomena in media with reverse saturable absorption (RSA) may be similarly explained.

  19. Achieving atomic resolution magnetic dichroism by controlling the phase symmetry of an electron probe

    SciTech Connect

    Rusz, Jan; Idrobo, Juan -Carlos; Bhowmick, Somnath

    2014-09-30

    The calculations presented here reveal that an electron probe carrying orbital angular momentum is just a particular case of a wider class of electron beams that can be used to measure electron magnetic circular dichroism (EMCD) with atomic resolution. It is possible to obtain an EMCD signal with atomic resolution by simply breaking the symmetry of the electron probe phase front using the aberration-corrected optics of a scanning transmission electron microscope. The probe’s required phase distribution depends on the sample’s magnetic symmetry and crystal structure. The calculations indicate that EMCD signals that use the electron probe’s phase are as strong as those obtained by nanodiffraction methods.

  20. Fano resonance assisting plasmonic circular dichroism from nanorice heterodimers for extrinsic chirality

    PubMed Central

    Hu, Li; Huang, Yingzhou; Fang, Liang; Chen, Guo; Wei, Hua; Fang, Yurui

    2015-01-01

    In this work, the circular dichroisms (CD) of nanorice heterodimers consisting of two parallel arranged nanorices with the same size but different materials are investigated theoretically. Symmetry-breaking is introduced by using different materials and oblique incidence to achieve strong CD at the vicinity of Fano resonance peaks. We demonstrate that all Au-Ag heterodimers exhibit multipolar Fano resonances and strong CD effect. A simple quantitative analysis shows that the structure with larger Fano asymmetry factor has stronger CD. The intensity and peak positions of the CD effect can be flexibly tuned in a large range by changing particle size, shape, the inter-particle distance and surroundings. Furthermore, CD spectra exhibit high sensitivity to ambient medium in visible and near infrared regions. Our results here are beneficial for the design and application of high sensitive CD sensors and other related fields. PMID:26538460

  1. Optically detected electron paramagnetic resonance by microwave modulated magnetic circular dichroism

    NASA Astrophysics Data System (ADS)

    Börger, Birgit; Bingham, Stephen J.; Gutschank, Jörg; Schweika, Marc Oliver; Suter, Dieter; Thomson, Andrew J.

    1999-11-01

    Electron paramagnetic resonance (EPR) can be detected optically, with a laser beam propagating perpendicular to the static magnetic field. As in conventional EPR, excitation uses a resonant microwave field. The detection process can be interpreted as coherent Raman scattering or as a modulation of the laser beam by the circular dichroism of the sample oscillating at the microwave frequency. The latter model suggests that the signal should show the same dependence on the optical wavelength as the MCD signal. We check this for two different samples [cytochrome c-551, a metalloprotein, and ruby (Cr3+:Al2O3)]. In both cases, the observed wavelength dependence is almost identical to that of the MCD signal. A quantitative estimate of the amplitude of the optically detected EPR signal from the MCD also shows good agreement with the experimental results.

  2. Strong intermolecular exciton couplings in solid-state circular dichroism of aryl benzyl sulfoxides.

    PubMed

    Padula, Daniele; Di Pietro, Sebastiano; Capozzi, Maria Annunziata M; Cardellicchio, Cosimo; Pescitelli, Gennaro

    2014-09-01

    A series of 13 enantiopure aryl benzyl sulfoxides () with different substituents on the two aromatic rings has been previously analyzed by means of electronic circular dichroism (CD) spectroscopy. Most of these compounds are crystalline and their X-ray structure is established. For almost one-half of the series, CD spectra measured in the solid state were quite different from those in acetonitrile solution. We demonstrate that the difference is due to strong exciton couplings between molecules packed closely together in the crystal. The computational approach consists of time-dependent density functional theory (TDDFT) calculations run on "dimers" composed of nearest neighbors found in the lattice. Solid-state CD spectra are well reproduced by the average of all possible pairwise terms. The relation between the crystal space group and conformation, and the appearance of solid-state CD spectra, is also discussed.

  3. Vacuum-ultraviolet circular dichroism reveals DNA duplex formation between short strands of adenine and thymine.

    PubMed

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

    2012-11-21

    Absorbance spectroscopy is used extensively to tell when two DNA single strands come together and form a double strand. Here we show that circular dichroism in the vacuum ultraviolet region provides an even stronger indication for duplex formation in the case of short strands of adenine and thymine (4 to 16 bases in each strand). Indeed, our results show that a strong positive CD band appears at 179 nm when double strands are formed. Melting experiments were done in aqueous solution with and without added Na(+) counter ions. With additional salt present a huge increase in the 179 nm CD band was observed when lowering the temperature. A 179 nm CD marker band for duplex formation can be used to measure the kinetics for the association of two single strands. Such experiments rely on large changes at one particular wavelength since it is too time-consuming to record a full-wavelength spectrum.

  4. Circular dichroism and Raman spectroscopic study of the spider venom toxin V50F17

    NASA Astrophysics Data System (ADS)

    Alix, A. J. P.; Berjot, M.; Dauchez, M. A. M.; Dhalluin, C.; Lippens, G.

    1999-05-01

    V50F17 is a small 45 amino acid neurotoxin fractionated (F17) from the venom V50 of the spider Segestria florentina, which has eight cysteine residues constituting four disulfide bridges. Using circular dichroism data and vibrational Raman data at both pH 2.9 and 7.0 and preliminary NMR results obtained at pH 2.9, we derived structural information for this small protein. From these data, it is seen that it is possible to characterise well the local conformation of the disulfide bridges and the overall shape of the globular protein. Moreover, using optical spectroscopic data, it is shown that consequent local and/or global modifications are obtained on changing the pH. Results of the secondary structure states, the local conformations of the disulfide bridges, the exposure of side chains of residues and particularly of Tyr41 are discussed.

  5. Chirality transfer from gold nanocluster to adsorbate evidenced by vibrational circular dichroism

    PubMed Central

    Dolamic, Igor; Varnholt, Birte; Bürgi, Thomas

    2015-01-01

    The transfer of chirality from one set of molecules to another is fundamental for applications in chiral technology and has likely played a crucial role for establishing homochirality on earth. Here we show that an intrinsically chiral gold cluster can transfer its handedness to an achiral molecule adsorbed on its surface. Solutions of chiral Au38(2-PET)24 (2-PET=2-phenylethylthiolate) cluster enantiomers show strong vibrational circular dichroism (VCD) signals in vibrations of the achiral adsorbate. Density functional theory (DFT) calculations reveal that 2-PET molecules adopt a chiral conformation. Chirality transfer from the cluster to the achiral adsorbate is responsible for the preference of one of the two mirror images. Intermolecular interactions between the adsorbed molecules on the crowded cluster surface seem to play a dominant role for the phenomena. Such chirality transfer from metals to adsorbates likely plays an important role in heterogeneous enantioselective catalysis. PMID:25960309

  6. Structural characterization of hydroperoxide lyase in dodecyl maltoside by using circular dichroism.

    PubMed

    Panagakou, I; Touloupakis, E; Ghanotakis, D F

    2013-01-01

    Fatty acid hydroperoxide lyase (HPL) is a membrane protein, member of the lipoxygenase pathway, which holds a central role in plant defense. Green bell pepper fatty acid hydroperoxide lyase, overexpressed in Escherichia coli, was purified and solubilized in two different non ionic detergents, Triton X-100 and dodecyl maltoside (DM). DM is considered to be more useful compared to Triton X-100, as it allows characterization of the protein with spectroscopic techniques, for which Triton X-100 was inapplicable. Circular dichroism demonstrated that HPL's secondary structure in DM consists of 13.53 % α-helix, 32.73 % β-sheet, 21.76 % turn and 31.13 % unordered. PMID:23076732

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

    NASA Astrophysics Data System (ADS)

    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. Rashba splitting in an image potential state investigated by circular dichroism two-photon photoemission spectroscopy

    NASA Astrophysics Data System (ADS)

    Nakazawa, T.; Takagi, N.; Kawai, Maki; Ishida, H.; Arafune, R.

    2016-09-01

    We have explored the band splitting and spin texture of the image potential state (IPS) on Au(001) derived from the Rashba-type spin-orbit interaction (SOI) by using angle-resolved bichromatic two-photon photoemission (2PPE) spectroscopy in combination with circular dichroism (CD). The Rashba parameter for the first (n =1 ) IPS is determined to be 48-20+8meV Å , which is consistent with the spin-polarized band structure calculated from the embedded Green's function technique for semi-infinite crystals. The present results demonstrate that bichromatic CD-2PPE spectroscopy is powerful for mapping the spin-polarized unoccupied band structures originating from SOIs in various classes of condensed matter.

  9. Infrared, Raman and ultraviolet with circular dichroism analysis and theoretical calculations of tedizolid

    NASA Astrophysics Data System (ADS)

    Michalska, Katarzyna; Mizera, Mikołaj; Lewandowska, Kornelia; Cielecka-Piontek, Judyta

    2016-07-01

    Tedizolid is the newest antibacterial agent from the oxazolidinone class. For its identification, FT-IR (2000-400 cm-1) and Raman (2000-400 cm-1) analyses were proposed. Studies of the enantiomeric purity of tedizolid were conducted based on ultraviolet-circular dichroism (UV-CD) analysis. Density functional theory (DFT) with the B3LYP hybrid functional and 6-311G(2df,2pd) basis set was used for support of the analysis of the FT-IR and Raman spectra. Theoretical methods made it possible to conduct HOMO and LUMO analysis, which was used to determine the charge transfer for two tedizolid enantiomers. Molecular electrostatic potential maps were calculated with the DFT method for both tedizolid enantiomers. The relationship between the results of ab initio calculations and knowledge about the chemical-biological properties of R- and S-tedizolid enantiomers is also discussed.

  10. Induced circular dichroism of thioflavin T interacting with acetylcholinesterase: A computational study

    NASA Astrophysics Data System (ADS)

    Rybicka, Anna; Pecul, Magdalena

    2015-12-01

    Induced circular dichroism of thioflavin T (ThT) intercalated in acetylcholinesterase has been modeled by means of density functional theory. ThT in acetylcholinesterase is reported to be flat and thus cannot exhibit induced CD associated with a 'chiral twist' mechanism, i.e. stabilization of one of the enantiomeric forms by a chiral environment. Even so, the presence of aromatic side chains forming the cavity in which ThT is bound is predicted to induce substantial Cotton effect in ThT, of the magnitude comparable to the one predicted to originate from a 'chiral twist' mechanism. The predicted Cotton effect originates mostly from deformation of electron density of ThT by the presence of the aromatic rings, the contribution from crystallization water molecules being one order of magnitude smaller.

  11. Stability of some Cactaceae proteins based on fluorescence, circular dichroism, and differential scanning calorimetry measurements.

    PubMed

    Gorinstein, S; Zemser, M; Vargas-Albores, F; Ochoa, J L; Paredes-Lopez, O; Scheler, C; Aksu, S; Salnikow, J

    1999-02-01

    Characterization of three cactus proteins (native and denatured) from Machaerocereus gummosus (Pitahaya agria), Lophocereu schottii (Garambullo), and Cholla opuntia (Cholla), was based on electrophoretic, fluorescence, CD (circular dichroism), DSC (differential scanning calorimetry), and FT-IR (Fourier transform infrared) measurements. The obtained results of intrinsic fluorescence, DSC, and CD were dissimilar for the three species of cactus, providing evidence of differences in secondary and tertiary structures. Cactus proteins may be situated in the following order corresponding to their relative stability: Machaerocereus gummosus (Pitahaya agria) > Cholla opuntia (Cholla) > Lophocereu schottii (Garambullo). Thermodynamic properties of proteins and their changes upon denaturation (temperature of denaturation, enthalphy, and the number of ruptured hydrogen bonds) were correlated with the secondary structure of proteins and disappearance of alpha-helix.

  12. Classical Magnetic Dipole Moments for the Simulation of Vibrational Circular Dichroism by ab Initio Molecular Dynamics.

    PubMed

    Thomas, Martin; Kirchner, Barbara

    2016-02-01

    We present a new approach for calculating vibrational circular dichroism spectra by ab initio molecular dynamics. In the context of molecular dynamics, these spectra are given by the Fourier transform of the cross-correlation function of magnetic dipole moment and electric dipole moment. We obtain the magnetic dipole moment from the electric current density according to the classical definition. The electric current density is computed by solving a partial differential equation derived from the continuity equation and the condition that eddy currents should be absent. In combination with a radical Voronoi tessellation, this yields an individual magnetic dipole moment for each molecule in a bulk phase simulation. Using the chiral alcohol 2-butanol as an example, we show that experimental spectra are reproduced very well. Our approach requires knowing only the electron density in each simulation step, and it is not restricted to any particular electronic structure method. PMID:26771403

  13. Stability of some Cactaceae proteins based on fluorescence, circular dichroism, and differential scanning calorimetry measurements.

    PubMed

    Gorinstein, S; Zemser, M; Vargas-Albores, F; Ochoa, J L; Paredes-Lopez, O; Scheler, C; Aksu, S; Salnikow, J

    1999-02-01

    Characterization of three cactus proteins (native and denatured) from Machaerocereus gummosus (Pitahaya agria), Lophocereu schottii (Garambullo), and Cholla opuntia (Cholla), was based on electrophoretic, fluorescence, CD (circular dichroism), DSC (differential scanning calorimetry), and FT-IR (Fourier transform infrared) measurements. The obtained results of intrinsic fluorescence, DSC, and CD were dissimilar for the three species of cactus, providing evidence of differences in secondary and tertiary structures. Cactus proteins may be situated in the following order corresponding to their relative stability: Machaerocereus gummosus (Pitahaya agria) > Cholla opuntia (Cholla) > Lophocereu schottii (Garambullo). Thermodynamic properties of proteins and their changes upon denaturation (temperature of denaturation, enthalphy, and the number of ruptured hydrogen bonds) were correlated with the secondary structure of proteins and disappearance of alpha-helix. PMID:10333299

  14. Light flux density threshold at which protein denaturation is induced by synchrotron radiation circular dichroism beamlines.

    PubMed

    Miles, A J; Janes, Robert W; Brown, A; Clarke, D T; Sutherland, J C; Tao, Y; Wallace, B A; Hoffmann, S V

    2008-07-01

    New high-flux synchrotron radiation circular dichroism (SRCD) beamlines are providing important information for structural biology, but can potentially cause denaturation of the protein samples under investigation. This effect has been studied at the new CD1 dedicated SRCD beamline at ISA in Denmark, where radiation-induced thermal damage effects were observed, depending not only on the radiation flux but also on the focal spot size of the light. Comparisons with similar studies at other SRCD facilities worldwide has lead to the estimation of a flux density threshold under which SRCD beamlines should be operated when samples are to be exposed to low-wavelength vacuum ultraviolet radiation for extended periods of time.

  15. Reaction monitoring using mid-infrared laser-based vibrational circular dichroism.

    PubMed

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

    2014-09-01

    Changes in vibrational circular dichroism (VCD) were recorded on-line during a chemical reaction. The chiral complex nickel-(-)-sparteine chloride was hydrolyzed to free (-)-sparteine base in a biphasic system of sodium hydroxide solution and chloroform (CHCl(3)). Infrared (IR) and VCD spectra were iteratively recorded after pumping a sample from the CHCl(3) phase through a lab-built VCD spectrometer equipped with a tunable mid-IR quantum cascade laser light source, which allows for VCD measurements even in the presence of strongly absorbing backgrounds. Time-dependent VCD spectra were analyzed by singular value decomposition and global exponential fitting. Spectral features corresponding to the complex and free (-)-sparteine could be clearly identified in the fitted amplitude spectrum, which was associated with an exponential decay with an apparent time constant of 127 min (t(½) = 88 min).

  16. Achieving atomic resolution magnetic dichroism by controlling the phase symmetry of an electron probe

    DOE PAGES

    Rusz, Jan; Idrobo, Juan -Carlos; Bhowmick, Somnath

    2014-09-30

    The calculations presented here reveal that an electron probe carrying orbital angular momentum is just a particular case of a wider class of electron beams that can be used to measure electron magnetic circular dichroism (EMCD) with atomic resolution. It is possible to obtain an EMCD signal with atomic resolution by simply breaking the symmetry of the electron probe phase front using the aberration-corrected optics of a scanning transmission electron microscope. The probe’s required phase distribution depends on the sample’s magnetic symmetry and crystal structure. The calculations indicate that EMCD signals that use the electron probe’s phase are as strongmore » as those obtained by nanodiffraction methods.« less

  17. Spin polarization and magnetic dichroism in core-level photoemission from ferromagnets

    SciTech Connect

    Menchero, J G

    1997-05-01

    In this thesis we present a theoretical investigation of angle- and spin-resolved core-level photoemission from ferromagnetic Fe and Ni. We also consider magneto-dichroic effects due to reversal of the photon helicity or reversal of the sample magnetization direction. In chapter 1, we provide a brief outline of the history of photoemission, and show how it has played an important role in the development of modern physics. We then review the basic elements of the theory of core-level photoemission, and discuss the validity of the some of the commonly-used approximations. In chapter 2, we present a one-electron theory to calculate spin- and angle-resolved photoemission spectra for an arbitrary photon polarization. The Hamiltonian includes both spin-orbit and exchange interactions. As test cases for the theory, we calculate the spin polarization and magnetic dichroism for the Fe 2p core level, and find that agreement with experiment is very good.

  18. Induced birefringence and dichroism in azo polymers. Comparison between amorphous and liquid crystalline polymers

    SciTech Connect

    Natansohn, A.; Brown, D.; Rochon, P.

    1993-12-31

    Macroscopic order can be induced in amorphous high-Tg azo polymers (usually containing electron-donor - electron-acceptor substituted azobenzene moieties) by exposure to polarized light. The phenomenon is based on a series of trans-cis-trans isomerization cycles and the induced birefringence is typically of 2x10{sup {minus}2}. The ordered domains can be returned to randomness ({open_quotes}erased{close_quotes}) using circularly polarized light. This paper will present a comparison between amorphous and liquid crystalline azo polymers. The most significant difference between these two types of polymers is that any other type of concert with the azo moiety. Consequently the dichroism and birefringence induced in the liquid crystalline polymers can be one order of magnitude higher than in the amorphous polymers. At the same time, however, the time required to achieve saturation also increases by at least one order of magnitude.

  19. Broadband femtosecond circular dichroism spectrometer with white-light polarization control.

    PubMed

    Trifonov, Anton; Buchvarov, Ivan; Lohr, Andreas; Würthner, Frank; Fiebig, Torsten

    2010-04-01

    A broadband, femtosecond transient circular dichroism (TRCD) spectrometer has been developed and tested in the wavelength range from 350 to 700 nm. The spectrometer uses a femtosecond probe white light with well-defined circular polarization. The latter is modulated by the polarization of a narrowband seed pulse. We have implemented a dual-beam probe geometry with phase-locked detection technique to increase the signal-to-noise ratio and to reduce optical artifacts. The spectrometer allows the acquisition of TRCD spectra with subpicosecond time resolution and typical noise levels of 10(-4) absorbance units. The performance of this instrument has been demonstrated on bis(merocyanine) nanorod aggregates in tetrahydrofurane/methylcyclohexane solution. The case study confirmed that this spectrometer is effective for the investigation of chiral properties in various molecular and nanostructural systems that have transient spectra in the UV-visible spectral range.

  20. Circular dichroism studies on intermolecular interactions of amphotericin B in ionic liquid-rich environments.

    PubMed

    Jameson, Laramie P; Dzyuba, Sergei V

    2013-07-01

    Aggregation of amphotericin B (AmB) in an ionic liquid-rich environment was investigated using circular dichroism (CD) spectroscopy. It was found that nature of the ionic liquids' anion had a strong impact not only on the aggregation of AmB, but more importantly on the nature of AmB aggregates, as observed in the asymmetry of the exciton couplet of the aggregate in CD spectra. Unique CD signals for AmB aggregates were observed in three different 1-butyl-3-methylimidazolium ionic liquid solutions: [C4 -mim]Br favored the formation of AmB aggregates that were similar to those found in water, whereas [C4 -mim]BF4 and [C4 -mim]NO3 produced AmB aggregates that were different from each other and those found in water. The obtained results suggest that the designer solvent ability of ionic liquids could be expanded to address numerous intermolecular processes.

  1. Detection of magnetic circular dichroism on the two-nanometer scale

    NASA Astrophysics Data System (ADS)

    Schattschneider, Peter; Stöger-Pollach, Michael; Rubino, Stefano; Sperl, Matthias; Hurm, Christian; Zweck, Josef; Rusz, Ján

    2008-09-01

    Magnetic circular dichroism (MCD) is a standard technique for the study of magnetic properties of materials in synchrotron beamlines. We present here a scattering geometry in the transmission electron microscope through which MCD can be observed with unprecedented spatial resolution. A convergent electron beam is used to scan a cross sectional preparation of a Fe/Au multilayer sample. Differences in the energy-loss spectra induced by the magnetic moments of the Fe atoms can be resolved with a resolution of better than 2 nm. This is a breakthrough achievement when compared both to the previous energy-loss MCD resolution (200 nm) or the best x-ray MCD experiments (approximately 20 nm).

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

    PubMed

    Hussain, Rohanah; Siligardi, Giuliano

    2016-01-01

    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. PMID:27553234

  3. Probing chiral solute-water hydrogen bonding networks by chirality transfer effects: a vibrational circular dichroism study of glycidol in water.

    PubMed

    Yang, Guochun; Xu, Yunjie

    2009-04-28

    Vibrational absorption (VA) and vibrational circular dichroism (VCD) spectra of (S)-(-)-glycidol were measured in water with a concentration of 6.0M in the 1000-1750 cm(-1) region. Prominent and complex VCD spectral features were detected at the water bending vibrational region. Our experimental results show that water molecules can become optically active through hydrogen bonding interactions with glycidol molecules. To model the glycidol-water hydrogen bonding network in the solution, molecular dynamics simulations using the AMBER9 suite of programs were carried out. Altogether, 34 conformers of the small glycidol-(water)(N) clusters with N=1, 2, 3, and 4 were considered. Geometry optimizations, harmonic frequency calculations, and the VA and VCD intensity predictions of these small glycidol-water clusters were performed at the B3LYP/6-311++G(d,p) level of theory using the GAUSSIAN 03 program package. Strong cooperative hydrogen bonding effects were detected in the larger glycidol-(water)(N) clusters. The population weighted VA and VCD spectra of each N group of glycidol (water)(N=1,2,3,4) were used to produce the simulated VA and VCD spectra, which are in good agreement with the experimental VA and VCD spectra. The study shows that all these clusters make important contributions to the observed spectra and are the most important species in the aqueous solution with complicated equilibriums among them.

  4. Probing chiral solute-water hydrogen bonding networks by chirality transfer effects: A vibrational circular dichroism study of glycidol in water

    NASA Astrophysics Data System (ADS)

    Yang, Guochun; Xu, Yunjie

    2009-04-01

    Vibrational absorption (VA) and vibrational circular dichroism (VCD) spectra of (S)-(-)-glycidol were measured in water with a concentration of 6.0M in the 1000-1750 cm-1 region. Prominent and complex VCD spectral features were detected at the water bending vibrational region. Our experimental results show that water molecules can become optically active through hydrogen bonding interactions with glycidol molecules. To model the glycidol-water hydrogen bonding network in the solution, molecular dynamics simulations using the AMBER9 suite of programs were carried out. Altogether, 34 conformers of the small glycidol-(water)N clusters with N =1, 2, 3, and 4 were considered. Geometry optimizations, harmonic frequency calculations, and the VA and VCD intensity predictions of these small glycidol-water clusters were performed at the B3LYP/6-311++G(d,p) level of theory using the GAUSSIAN 03 program package. Strong cooperative hydrogen bonding effects were detected in the larger glycidol-(water)N clusters. The population weighted VA and VCD spectra of each N group of glycidol (water)N=1,2,3,4 were used to produce the simulated VA and VCD spectra, which are in good agreement with the experimental VA and VCD spectra. The study shows that all these clusters make important contributions to the observed spectra and are the most important species in the aqueous solution with complicated equilibriums among them.

  5. Element and orbital-specific observation of two-step magnetic transition in NpNiGa5 : X-ray magnetic circular dichroism study

    NASA Astrophysics Data System (ADS)

    Okane, T.; Ohkochi, T.; Inami, T.; Takeda, Y.; Fujimori, S.-I.; Kawamura, N.; Suzuki, M.; Tsutsui, S.; Yamagami, H.; Fujimori, A.; Tanaka, A.; Aoki, D.; Homma, Y.; Shiokawa, Y.; Yamamoto, E.; Haga, Y.; Nakamura, A.; Ōnuki, Y.

    2009-09-01

    X-ray magnetic circular dichroism (XMCD) experiments were performed at the NpM4,5 and the GaK absorption edges of NpNiGa5 to investigate the temperature-dependent changes of magnetic properties of Np5f and Ga4p electron states. By the sum-rule analysis of the NpM4,5 XMCD data, the orbital magnetic moment μL and the spin magnetic moment μS were estimated for the Np5f3 and 5f4 electronic configurations and their comparison to the previous magnetization and neutron-scattering experiments suggests that the 5f4 configuration is more likely than the 5f3 configuration in NpNiGa5 . It was found that |μL/μS| tends to increase from the high-temperature low-moment ordered state to the low-temperature high-moment ordered state. The result of the GaK XMCD indicates that the Ga4p electrons are magnetically polarized and the temperature and magnetic-field dependences of the Ga4p orbital moment are proportional to those of the magnetization measurements.

  6. Conformational study of an axially chiral Salen ligand in solution using two-photon circular dichroism and the fragment-recombination approach.

    PubMed

    Díaz, Carlos; Echevarria, Lorenzo; Hernández, Florencio E

    2013-09-01

    Herein we report on the conformational study of a chiral Salen ligand, AFX-155, in THF solution using two-photon absorption (TPA) and, even more importantly, two-photon circular dichroism (TPCD). The fragment-recombination approach (FRA), employed to perform computations on half-AXF-155 (AXF-169') and the center (C-AXF-155), allowed us to overcome the current computational limitations found in calculations of the TPCD spectra of large molecules. The comparative experimental-theoretical analysis of AXF-155 showed that its TPA is mainly determined by AXF-169' and validated, through TPCD, the presence of the two dominant Trans_R-Intra(NHB)//Trans_R-Extra(HB) and Trans_R-Intra(NHB)//Trans_R-Extra(NHB) structure in THF with a ΔΔ propeller chirality on the diphenylamine moieties at the end of each AXF-169'. The application of FRA for the analysis of the TPCD spectra of large chiral molecules has been proven to be effective. PMID:23937607

  7. Proteolytically-induced changes of secondary structural protein conformation of bovine serum albumin monitored by Fourier transform infrared (FT-IR) and UV-circular dichroism spectroscopy

    NASA Astrophysics Data System (ADS)

    Güler, Günnur; Vorob'ev, Mikhail M.; Vogel, Vitali; Mäntele, Werner

    2016-05-01

    Enzymatically-induced degradation of bovine serum albumin (BSA) by serine proteases (trypsin and α-chymotrypsin) in various concentrations was monitored by means of Fourier transform infrared (FT-IR) and ultraviolet circular dichroism (UV-CD) spectroscopy. In this study, the applicability of both spectroscopies to monitor the proteolysis process in real time has been proven, by tracking the spectral changes together with secondary structure analysis of BSA as proteolysis proceeds. On the basis of the FTIR spectra and the changes in the amide I band region, we suggest the progression of proteolysis process via conversion of α-helices (1654 cm- 1) into unordered structures and an increase in the concentration of free carboxylates (absorption of 1593 and 1402 cm- 1). For the first time, the correlation between the degree of hydrolysis and the concentration of carboxylic groups measured by FTIR spectroscopy was revealed as well. The far UV-CD spectra together with their secondary structure analysis suggest that the α-helical content decreases concomitant with an increase in the unordered structure. Both spectroscopic techniques also demonstrate that there are similar but less spectral changes of BSA for the trypsin attack than for α-chymotrypsin although the substrate/enzyme ratio is taken the same.

  8. First-principles approach to the dynamic magnetoelectric couplings for the non-reciprocal directional dichroism in BiFeO3

    DOE PAGES

    Kezsmarki, I.; Fishman, Randy Scott

    2016-04-18

    Due to the complicated magnetic and crystallographic structures of BiFeO3, its magnetoelectric (ME) couplings and microscopic model Hamiltonian remain poorly understood. By employing a firstprinciples approach, we uncover all possibleMEcouplings associated with the spin-current (SC) and exchange-striction (ES) polarizations, and construct an appropriate Hamiltonian for the long-range spin-cycloid in BiFeO3. First-principles calculations are used to understand the microscopic origins of theMEcouplings.Wefind that inversion symmetries broken by ferroelectric and antiferroelectric distortions induce the SC and the ES polarizations, which cooperatively produce the dynamicME effects in BiFeO3. A model motivated by first principles reproduces the absorption difference of counter-propagating light beams calledmore » non-reciprocal directional dichroism. The current paper focuses on the spin-driven (SD) polarizations produced by a dynamic electric field, i.e. the dynamic MEcouplings. Due to the inertial properties of Fe, the dynamic SD polarizations differ significantly from the static SD polarizations. Our systematic approach can be generally applied to any multiferroic material, laying the foundation for revealing hiddenMEcouplings on the atomic scale and for exploiting opticalMEeffects in the next generation of technological devices such as optical diodes.« less

  9. Ab initio ground state and L{sub 2,3} x-ray magnetic circular dichroism of Mn-based Heusler alloys

    SciTech Connect

    Galanakis, I.; Ostanin, S.; Alouani, M.; Dreysse, H.; Wills, J. M.

    2000-02-01

    Relativistic full-potential calculations within the generalized gradient approximation (GGA) for a series of Mn-based Heusler alloys are presented. Calculated equilibrium lattice parameters deviate less than 1.2% from the experimental values. The main features of a half metallic system are present in the density of states for the PtMnSb and NiMnSb. We predict that PdMnSb shows half metallic character under hydrostatic pressure. The substitution of Sb in PtMnSb by Sn or Te destroys the minority spin band gap. Spin and orbital magnetic moments for all the systems are in good agreement with previous calculations and experimental data. L{sub 2,3} x-ray absorption and x-ray magnetic circular dichroism (XMCD) spectra are calculated for all the five compounds. Pt spectra present big deviations from system to system in the PtMnY (Y=Sn,Sb,Te) compounds while Mn spectra show only small deviations. For all these spectra GGA underestimates the L{sub 3}/L{sub 2} integrated branching ratio and produces a much smaller L{sub 2} peak intensity for the Ni site in NiMnSb. The XMCD sum rules are used to compute the spin and orbital magnetic moments and the results are compared to the direct calculations. (c) 2000 The American Physical Society.

  10. Vibrational Circular Dichroism Absolute Configuration of 9,12-Cyclomulin-13-ol, a Diterpene from Azorella and Laretia Species.

    PubMed

    Muñoz, Marcelo A; San-Martín, Aurelio; Joseph-Nathan, Pedro

    2015-08-01

    The absolute configuration of the diterpenoid 9,12-cyclomulin-13-ol (1), a constituent of Azorella and Laretia species, has been established by vibrational circular dichroism spectroscopy in combination with density functional theory calculations. The obtained normal diterpene absolute configuration confirms that of azorellanol (2), which was determined by single crystal X-ray diffraction.

  11. Explaining the visible and near-infrared circular dichroism spectra of light-harvesting 1 complexes from purple bacteria: a modeling study.

    PubMed

    Georgakopoulou, Sofia; van Grondelle, Rienk; van der Zwan, Gert

    2006-02-23

    In this work, we investigate the origin and characteristics of the circular dichroism (CD) spectrum of various light-harvesting 1 (LH1) complexes. The near-infrared (NIR) CD signal of these core antennae is strongly nonconservative, and the nature of this nonconservativity is under examination in this paper. So far, on the basis of the high-resolution structures of LH2, we have been able to model the absorption and CD spectra in the bacteriochlorophyll (BChl) Q(Y) and Q(X) regions of LH2 (Georgakopoulou et al., Biophys. J. 2002, 82, 2184-2197), as well as in the carotenoid region (Georgakopoulou et al., Biophys. J. 2004, 87, 3010-3022). We proceed by applying the same modeling method in order to reproduce the LH1 spectra. We assume a ring of dimers in a perfect circular arrangement with 16-fold symmetry, and account for all excitonic interactions within the ring. Because LH1 complexes exhibit Q(Y) and Q(X) CD signals of very low intensity, higher transitions can easily affect these regions. Therefore, we expand the model and take into account also the Soret and carotenoid transitions. We can now understand the shape of the absorption and CD spectra and contemplate the structure of the LH1 complex. The latter is similar to LH2 in that it is a very symmetric ring dominated by excitonic interactions. The larger number of symmetry and the bigger diameter of LH1, combined with small rotations of the BChl transition dipole moments, are responsible for the display of CD signals that are very low in intensity. The interaction of the Q(Y) with the carotenoid transitions results in complete loss of the conservativity. Interaction energies between all the pigments in the ring are calculated, and their values are in good accordance with what is reported in the literature.

  12. Itinerant ferromagnetism in the As 4p conduction band of Ba0.6K0.4Mn2As2 identified by x-ray magnetic circular dichroism

    DOE PAGES

    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.; et al

    2015-05-27

    In this study, x-ray magnetic circular dichroism (XMCD) measurements on single-crystal and powder samples of Ba0.6K0.4Mn2As2 show that the ferromagnetism below TC ≈ 100 K arises in the As 4p conduction band. No XMCD signal is observed at the Mn x-ray absorption edges. Below TC, 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 themore » 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.« less

  13. Spin-lattice coupling across the singular magnetostructural transition in P r0.5S r0.5Co O3 by x-ray magnetic circular dichroism

    NASA Astrophysics Data System (ADS)

    Padilla-Pantoja, J.; Herrero-Martín, J.; Pellegrin, E.; Gargiani, P.; Valvidares, S. M.; Barla, A.; García-Muñoz, J. L.

    2015-12-01

    We have performed temperature-dependent x-ray magnetic circular dichroism on ferromagnetic P r0.5S r0.5Co O3 at the Co L2 ,3 edges to analyze the correlation of the spin and orbital angular components of the magnetization with the singular magnetostructural anomalies at ˜120 K. We found a sizable orbital angular momentum in Co atoms that follows a temperature dependence very similar to that of the spin momentum. Their sum agrees with the bulk magnetization. Taken together with recent x-ray absorption spectra showing the absence of changes in the electronic filling of Co 3 d states across the magnetostructural transition, our results demonstrate the relevance of the spin-orbit coupling for the stabilization of two distinct ferromagnetic phases in this metallic perovskite. The Co spin-state model is discussed on the basis of charge-transfer multiplet calculations of the dichroic spectral shape.

  14. UV-visible microscope spectrophotometric polarization and dichroism with increased discrimination power in forensic analysis

    NASA Astrophysics Data System (ADS)

    Purcell, Dale Kevin

    Microanalysis of transfer (Trace) evidence is the application of a microscope and microscopical techniques for the collection, observation, documentation, examination, identification, and discrimination of micrometer sized particles or domains. Microscope spectrophotometry is the union of microscopy and spectroscopy for microanalysis. Analytical microspectroscopy is the science of studying the emission, reflection, transmission, and absorption of electromagnetic radiation to determine the structure or chemical composition of microscopic-size materials. Microscope spectrophotometry instrument designs have evolved from monochromatic illumination which transmitted through the microscope and sample and then is detected by a photometer detector (photomultiplier tube) to systems in which broad-band (white light) illumination falls incident upon a sample followed by a non-scanning grating spectrometer equipped with a solid-state multi-element detector. Most of these small modern spectrometers are configured with either silicon based charged-couple device detectors (200-950 nm) or InGaAs based diode array detectors (850-2300 nm) with computerized data acquisition and signal processing being common. A focus of this research was to evaluate the performance characteristics of various modern forensic (UV-Vis) microscope photometer systems as well as review early model instrumental designs. An important focus of this research was to efficiently measure ultraviolet-visible spectra of microscopically small specimens for classification, differentiation, and possibly individualization. The first stage of the project consisted of the preparation of microscope slides containing neutral density filter reference materials, molecular fluorescence reference materials, and dichroic reference materials. Upon completion of these standard slide preparations analysis began with measurements in order to evaluate figures of merit for comparison of the instruments investigated. The figures of

  15. Part I. Molecular dichroism, optical and catalysis studies of several metalloporphyrins. Part II. Solid state studies

    SciTech Connect

    Sito, M.L.

    1993-01-01

    Part 1. Tetra(4-N-methylpyridyl)porphyrinatopalladium (II), [Pd-TMpyP][sup 4+], was prepared by a new technique, purified and intercalated with calf thymus DNA. The Soret and Q band regions were studied using Circular Dichroism (CD) and magnetic Circular Dichroism (MCD). The MCD measurements in Soret and Q band regions and CD of the Q band regions are reported for the first time. The known photocatalyst, tetra(4-pyridyl)porphyinato-zinc(II), was covalently bonded to the surfaces of both iodinated (Ia) and chlorinated (Ib) cross-linked poly(siloxane) materials. Thermal catalytic activity was found to be present, and it was quantitatively measured using olefin oxidation of styrene to acetophenone. The zinc porphyrin supported on iodinated poly(siloxane) showed an over 12-fold increase in catalytic activity, as measured by turnover numbers, compared to the chlorinated support material. Part II. The plasmas produced by ablation of YBa[sub 2]Cu[sub 3]O[sub 7] single-phase high T[sub C] bulk superconductors when exposed to XeCl excimer laser pulses have been studied. The luminescence of the laser-induced vapor plume have been analyzed using optical emission spectroscopy. Excited atomic neutral and single ionized species (Cu/Cu[sup +], Ba/Ba[sup +], Y/Y[sup +]) as well as some molecular emission bands (CuO, YO) were observed within the experimental resolution of an optical multichannel analyzer detection system. A liquid mediated pulse laser irradiation procedure was used in the attempt to form thin layers of carbides and nitrides of silicon. A boron doped single crystal (100) of silicon was irradiated while immersed in cyclohexane or liquid ammonia. Irradiation of the samples was carried out using a 308 nm excimer laser. The laser pulses had energy densities of 0.5 to 3.0 J cm[sup [minus]2] and the number of pulses used ranged from 1 to 50. The specimens were analyzed using specular reflectance and auger electron spectroscopies.

  16. Mulliken Population Analysis of X-ray Magnetic Circular Dichroism in Uranium Monochalcogenides: Examination of Sum Rules by Fully Relativistic Full-Potential LCAO Method

    NASA Astrophysics Data System (ADS)

    Suzuki, Shugo; Ariizumi, Toshihiro; Li, Ming-Fang

    2009-07-01

    We study the X-ray magnetic circular dichroism (XMCD) spectra at the U M4,5 and N4,5 edges of uranium monochalcogenides, UX where X=S, Se, and Te, examining the applicability of the XMCD sum rules to UX by the fully relativistic full-potential linear-combination-of-atomic-orbitals (LCAO) method based on the density functional theory. To extract the transitions relevant to the sum-rule analysis, we employ the Mulliken population analysis (MPA). Using the MPA, the orbital sum rule is found to be valid to 10-20% for the M4,5 edges and valid to 5-15% for the N4,5 edges. On the other hand, the spin sum rule is found to be valid to 10-20% for the M4,5 edges whereas valid to 30-35% for the N4,5 edges. Furthermore, it is found that the calculated XMCD spectra are consistent with a recent experimental observation that the intensity of the N4,5 XMCD signal is comparable to that of the M4,5 XMCD signal although contradicting a previous theoretical prediction that the XMCD intensity at the N4,5 edges is one order of magnitude smaller than that at the M4,5 edges.

  17. Light Scattering and Absorption Studies of Sickle Cell Hemoglobin

    NASA Astrophysics Data System (ADS)

    Kim-Shapiro, Daniel

    1997-11-01

    exponentially. The length of this delay time depends on the concentration of deoxy-HbS. The kinetics of polymerization was described by a novel double nucleation mechanism. These light scattering studies led to the understanding that many cells could travel through oxygen deficient tissue without sickling due to the delay time in polymerization. Some treatment strategies involve prolonging the delay time. Less work has been done in trying to understand polymer melting. Such investigations are important in order to determine whether polymers that reach the lungs melt before they enter the oxygen deficient tissues. I have initially addressed this problem by exploring the kinetics of oxygen binding to the polymers. These studies were conducted using time-resolved linear dichroism following laser photolysis. Preliminary studies in my laboratory indicate that polymer melting is slow enough to be an important consideration in understanding sickle cell disease. One of the most common therapies for sickle cell disease that is currently used involves administering the drug, hydroxyurea. The mechanism by which this drug benefits patients is not fully understood. One of its mechanisms (as determined by light scattering and absorption studies) involves increasing the delay time for polymerization.

  18. Chiral isothiocyanates - An approach to determination of the absolute configuration using circular dichroism measurement

    NASA Astrophysics Data System (ADS)

    Michalski, Oskar; Cież, Dariusz

    2013-04-01

    Chiral alkyl 2-isothiocyanates have been obtained from enantiopure, aliphatic amines. ECD measurements allowed us to correlate an absolute configuration at C-2 with a sign of the Cotton effect (CE) observed for n-π* transition at the longer-wavelength range of the spectrum. Chirooptical data calculated for all enantiomers were consistent with the measured CE values and indicated that the weak absorption band at 240 nm could give an important information concerning the stereochemistry of simple, chiral isothiocyanates. Optically active esters of 2-isothiocyanatocarboxylic acids, prepared from α-amino acids, showed two absorption bands located over 195 nm. The more intensive band near 200 nm and the weak absorption located at 250 nm were related to n-π* transitions in NCS group. TD DFT calculations carried out for methyl esters of 2-isothiocyanatocarboxylic acids showed the correlation between signs of CE determined for both absorption bands, and the absolute configuration on C-2.

  19. Room-temperature photomagnetism in the spinel ferrite (Mn,Zn,Fe)3O4 as seen via soft x-ray magnetic circular dichroism

    SciTech Connect

    Bettinger, J.S.; Piamonteze, C.; Chopdekar, R.V.; Liberati, M.; Arenholz, E.; Suzuki, Y.

    2009-08-01

    We have used X-ray magnetic circular dichroism (XMCD) in conjunction with multiplet simulations to directly probe the origin of photomagnetism in nanocrystalline (Mn,Zn,Fe){sub 3}O{sub 4}. A photomagnetic effect at room temperature has been observed in these films with HeNe illumination. We have verified an intervalence charge transfer among octahedral Fe cations to account for the increase in magnetization observed at and above room temperature in small magnetic fields. Using XMCD, we demonstrate that the dichroism of Fe in octahedral sites increases by 18% at room temperature while the dichroism of Fe in tetrahedral sites does not change.

  20. Detection of electron magnetic circular dichroism signals under zone axial diffraction geometry.

    PubMed

    Song, Dongsheng; Rusz, Jan; Cai, Jianwang; Zhu, Jing

    2016-10-01

    EMCD (electron magnetic circular dichroism) technique provides us a new opportunity to explore magnetic properties in the transmission electron microscope. However, specific diffraction geometry is the major limitation. Only the two-beam and three-beam case are demonstrated in the experiments until now. Here, we present the more general case of zone axial (ZA) diffraction geometry through which the EMCD signals can be detected even with the very strong sensitivity to dynamical diffraction conditions. Our detailed calculations and well-controlled diffraction conditions lead to experiments in agreement with theory. The effect of dynamical diffraction conditions on EMCD signals are discussed both in theory and experiments. Moreover, with the detailed analysis of dynamical diffraction effects, we experimentally obtain the separate EMCD signals for each crystallographic site in Y3Fe5O12, which is also applicable for other materials and cannot be achieved by site-specific EMCD and XMCD technique directly. Our work extends application of more general diffraction geometries and will further promote the development of EMCD technique. PMID:27448200

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

    PubMed Central

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

    2015-01-01

    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. PMID:26370961

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

    PubMed

    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. PMID:27587106

  3. Radiation damage to a DNA-binding protein. Combined circular dichroism and molecular dynamics simulation analysis.

    PubMed

    Mazier, S; Villette, S; Goffinont, S; Renouard, S; Maurizot, J C; Genest, D; Spotheim-Maurizot, M

    2008-11-01

    The E. coli lactose operon, the paradigm of gene expression regulation systems, is the best model for studying the effect of radiation on such systems. The operon function requires the binding of a protein, the repressor, to a specific DNA sequence, the operator. We have previously shown that upon irradiation the repressor loses its operator binding ability. The main radiation-induced lesions of the headpiece have been identified by mass spectrometry. All tyrosine residues are oxidized into 3,4-dihydroxyphenylalanine (DOPA). In the present study we report a detailed characterization of the headpiece radiation-induced modification. An original approach combining circular dichroism measurements and the analysis of molecular dynamics simulation of headpieces bearing DOPA-s instead of tyrosines has been applied. The CD measurements reveal an irreversible modification of the headpiece structure and stability. The molecular dynamics simulation shows a loss of stability shown by an increase in internal dynamics and allows the estimation of the modifications due to tyrosine oxidation for each structural element of the protein. The changes in headpiece structure and stability can explain at least in part the radiation-induced loss of binding ability of the repressor to the operator. This conclusion should hold for all proteins containing radiosensitive amino acids in their DNA-binding site. PMID:18959464

  4. Giant spin splitting, strong valley selective circular dichroism and valley-spin coupling induced in silicene

    NASA Astrophysics Data System (ADS)

    Qu, Jinfeng; Peng, Xiangyang; Xiao, Di; Zhong, Jianxin

    2016-08-01

    Silicene is a potential candidate for valleytronics. However, in comparison with the transition metal dichalcogenides (TMDs), silicene has a tiny energy gap and zero spin splitting at its Dirac valleys, being unfavorable for valleytronic applications. Based on first principles calculations, we find that by proximity with Bi(111) bilayer, the Dirac valleys of silicene acquire a sizable energy gap and giant spin splittings, which are even larger than the splittings of Mo S2 . Our calculations show that the silicene over Bi layer exhibits a strong valley-contrasting circular dichroism, enabling selective optical pumping of valley carriers. Due to the time reversal symmetry and the breaking of inversion symmetry, the Berry curvatures and the spin splittings are opposite at the K and K' valleys of silicene, and hence the valley and spin are locked and can be simultaneously polarized. In this way, silicene and likely other similar Dirac materials can be comparable to TMDs in valleytronics, which not only adds a new dimension to the properties of silicene but also expands the members of the valleytronic family.

  5. Numerical study of achiral phase-change metamaterials for ultrafast tuning of giant circular conversion dichroism

    PubMed Central

    Cao, Tun; Wei, Chenwei; Mao, Libang

    2015-01-01

    Control of the polarization of light is highly desirable for detection of material’s chirality since biomolecules have vibrational modes in the optical region. Here, we report an ultrafast tuning of pronounced circular conversion dichroism (CCD) in the mid-infrared (M-IR) region, using an achiral phase change metamaterial (PCMM). Our structure consists of an array of Au squares separated from a continuous Au film by a phase change material (Ge2Sb2Te5) dielectric layer, where the Au square patches occupy the sites of a rectangular lattice. The extrinsically giant 2D chirality appears provided that the rectangular array of the Au squares is illuminated at an oblique incidence, and accomplishes a wide tunable wavelength range between 2664 and 3912 nm in the M-IR regime by switching between the amorphous and crystalline states of the Ge2Sb2Te5. A photothermal model is investigated to study the temporal variation of the temperature of the Ge2Sb2Te5 layer, and shows the advantage of fast transiting the phase of Ge2Sb2Te5 of 3.2 ns under an ultralow incident light intensity of 1.9 μW/μm2. Our design is straightforward to fabricate and will be a promising candidate for controlling electromagnetic (EM) wave in the optical region. PMID:26423517

  6. Induced circular dichroism of the interaction between pinacyanol and algal alginates.

    PubMed

    Khouri, Sa'ib J; Knierim, Robert; Buss, Volker

    2009-09-01

    The interaction between pinacyanol chloride and sodium alginate or guluronate-rich alginate is found to effect profound changes in the visible absorbance and circular dichroism spectra. Two different types of aggregates are observed depending on the relative dye/alginate concentrations. With a dye/alginate ratio at 1:1, a complex is deduced based on an analysis of Job's method and conductometric titrations. Another complex forms at 1:10 dye/alginate ratio and only in the presence of alginate or guluronate-rich alginate. The two aggregates are in dynamic equilibrium according to the presence of isosbestic points in the visible spectra. The effects of pH and divalent cations on the spectra are studied. The 1:10 complex is damaged by addition of hydrochloric acid and divalent cations; however, at low concentration of these agents the spectra indicate conversion of the complex into the 1:1 aggregate. Models for the two complexes are proposed taking into account the preference of guluronate binding sites for chelating ions.

  7. Electrochemical titrations and reaction time courses monitored in situ by magnetic circular dichroism spectroscopy.

    PubMed

    Bradley, Justin M; Butt, Julea N; Cheesman, Myles R

    2011-12-15

    Magnetic circular dichroism (MCD) spectra, at ultraviolet-visible or near-infrared wavelengths (185-2000 nm), contain the same transitions observed in conventional absorbance spectroscopy, but their bisignate nature and more stringent selection rules provide greatly enhanced resolution. Thus, they have proved to be invaluable in the study of many transition metal-containing proteins. For mainly technical reasons, MCD has been limited almost exclusively to the measurement of static samples. But the ability to employ the resolving power of MCD to follow changes at transition metal sites would be a potentially significant advance. We describe here the development of a cuvette holder that allows reagent injection and sample mixing within the 50-mm-diameter ambient temperature bore of an energized superconducting solenoid. This has allowed us, for the first time, to monitor time-resolved MCD resulting from in situ chemical manipulation of a metalloprotein sample. Furthermore, we report the parallel development of an electrochemical cell using a three-electrode configuration with physically separated working and counter electrodes, allowing true potentiometric titration to be performed within the bore of the MCD solenoid.

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

    PubMed

    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. Magnetic properties of transition-metal multilayers studied with x-ray magnetic circular dichroism spectroscopy

    SciTech Connect

    Stoehr, J.; Nakajima, R.

    1998-01-01

    The detailed understanding of the magnetic properties of transition-metal multilayers requires the use of state-of-the-art experimental techniques. Over the last few years, the X-ray magnetic circular dichroism (XMCD) technique has evolved into an important magnetometry tool. This paper is an overview of the principles and unique strengths of the technique. Aspects covered include the quantitative determination of element-specific spin and orbital magnetic moments and their anisotropies through sumrule analyses of experimental spectra. A discussion is presented on how the spin and orbital magnetic moments in transition-metal thin films and sandwiches are modified relative to the bulk. The authors show that a thin film of a nonmagnetic metal such as Cu may become magnetically active when adjacent to a magnetic layer, and a thin film of a ferromagnetic metal such as Fe may become magnetically inactive. The orbital moment is found to become anisotropic in thin films; it can be regarded as the microscopic origin of the magnetocrystalline anisotropy.

  10. Insoluble protein characterization by circular dichroism (CD) spectroscopy and nuclear magnetic resonance (NMR).

    PubMed

    Goyal, Shaveta; Qin, Haina; Lim, Liangzhong; Song, Jianxing

    2015-01-01

    Besides misfolded proteins, which still retain the capacity to fold into uniquely defined structures but are misled to "off-pathway" aggregation, there exists a group of proteins which are unrefoldable and insoluble in buffers. Previously no general method was available to solubilize them and consequently their solution conformations could not be characterized. Recently, we discovered that these insoluble proteins could in fact be solubilized in pure water. Circular dichroism (CD) spectroscopy and nuclear magnetic resonance (NMR) characterization led to their classification into three groups, all of which lack the tight tertiary packing and consequently anticipated to unavoidably aggregate in vivo with ~150 mM ions, thus designated as "intrinsically insoluble proteins (IIPs)." It appears that eukaryotic genomes contain many "IIP," which also have a potential to interact with membranes to trigger neurodegenerative diseases. In this chapter, we provide a detailed procedure to express and purify these proteins, followed by CD and NMR spectroscopy characterization of their conformation and interaction with dodecylphosphocholine (DPC).

  11. Circular Dichroism Observed by Photoemission from Ultrathin Bi2Te3 Films

    NASA Astrophysics Data System (ADS)

    Xu, Cai-Zhi; Liu, Yang; Yukawa, Ryu; Zhang, Long-Xiang; Miller, Tom; Chiang, Tai-Chang

    2015-03-01

    Circular dichroism (CD) observed by photoemission from the surface states of topological insulators has drawn much interest. It was initially attributed to the spin polarization or chiral orbital momentum of the initial states, but later proven to also involve the final states. The detailed mechanism remains controversial. To address this question, we have performed measurements of ultrathin films of the prototypical topological insulator Bi2Te3 over a wide range of film thickness and photon energy. The results show that the CD depends not only on the photon energy, but also on the film thickness in a nontrivial manner. A theoretical model has been developed that involves dipole transition, surface photoemission, and spin-orbit coupling. The computed results are in good agreement with the general trends of the data including sign reversals as a function of photon energy and film thickness. The complex behavior of the measured CD function is partially caused by modifications of both the initial and final states in the thin film geometry.

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

    PubMed

    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. PMID:24655319

  13. Circular dichroism in valence photoelectron spectroscopy of free unoriented chiral molecules: Camphor and bromocamphor

    SciTech Connect

    Lischke, T.; Boewering, N.; Schmidtke, B.; Mueller, N.; Khalil, T.; Heinzmann, U.

    2004-08-01

    The circular dichroism in the photoelectron angular distribution was investigated for valence photoionization of randomly oriented pure enantiomers of camphor and bromocamphor molecules using circularly polarized light in the vacuum ultraviolet. The forward-backward electron emission spectra were recorded simultaneously with two spectrometers at several opposite angles relative to the propagation direction of the photon beam and compared for each of the two substances. Measurements were also carried out for reversed light helicity and opposite molecular handedness. For the left- and right-handed enantiomers of both molecules we observed asymmetries of comparable magnitude up to several percent. The measured asymmetry parameters vary strongly for different orbital binding energies and also for the selected photon energies in the valence region. The results for both molecules are compared. They suggest a strong influence of the final states on the asymmetry, depending on the chiral geometry of the molecular electronic structure, as well as a significant dependence on the initial states involved. They also confirm theoretical predictions describing the effect in pure electric-dipole approximation.

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

    PubMed Central

    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

  15. Ligand induced circular dichroism and circularly polarized luminescence in CdSe quantum dots.

    PubMed

    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

    2013-12-23

    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 postsynthetic 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. Time Dependent Density Functional Theory (TDDFT) 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 origin of the induced chirality is consistent with the hybridization of highest occupied CdSe molecular orbitals with those of the chiral ligand.

  16. Magnetic Circular Dichroism Spectroscopy of meso-Tetraphenylporphyrin-Derived Hydroporphyrins and Pyrrole-Modified Porphyrins.

    PubMed

    Rhoda, Hannah M; Akhigbe, Joshua; Ogikubo, Junichi; Sabin, Jared R; Ziegler, Christopher J; Brückner, Christian; Nemykin, Victor N

    2016-07-28

    A large set of free-base and transition-metal 5,10,15,20-tetraphenyl-substituted chlorins, bacteriochlorins, and isobacteriochlorins and their pyrrole-modified analogues were investigated by combined UV-visible spectroscopy, magnetic circular dichroism (MCD), density functional theory (DFT), and time-dependent DFT (TDDFT) approaches and their spectral characteristics were compared to those of the parent compounds, free-base tetraphenylporphyrin 1H2 and chlorin 2H2. It was shown that the nature of the pyrroline substituents in the chlorin derivatives dictates their specific UV-vis and MCD spectroscopic signatures. In all hydroporphyrin-like cases, MCD spectroscopy suggests that the ΔHOMO is smaller than the ΔLUMO for the macrocycle-centered frontier molecular orbitals. DFT and TDDFT calculations were able to explain the large broadening of the UV-vis and MCD spectra of the chlorin diones and their derivatives compared to the other hydroporphyrins and hydroporphyrin analogues. This study contributes to the further understanding of the electronic effects of replacing a pyrrole in porphyrins by pyrrolines or other five-membered heterocycles (oxazoles and imidazoles). PMID:27400337

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

    PubMed

    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.

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

    NASA Astrophysics Data System (ADS)

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

    PubMed

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

    2015-01-01

    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. PMID:26370961

  20. Circular dichroism spectroscopy of complexes of semiconductor quantum dots with chlorin e6

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

    Experimental investigation of circular dichroism (CD) spectra of complexes based on ZnS:Mn/ZnS and CdSe/ZnS QDs and chlorin e6 (Ce6) molecules in aqua solutions at different pH level, in methanol and in DMSO were carried out. The changes in CD spectra of Ce6 upon its bonding in complex with semiconductor QDs were analyzed. Application of CD spectroscopy allowed to obtain the CD spectrum of luminescent Ce6 dimer for the first time, and to discover a nonluminescent Ce6 aggregate, preliminary identified as a "tetramer", dissymmetry factor of which is 40 times larger than that for its monomer. The analysis of obtained data showed that in complexes with QDs Ce6 can be either in the monomeric form or in the form of non-luminescent tetramer. The interaction of relatively unstable luminescent Ce6 dimerwith QDs leads to its partial monomerization and formation complexes with chlorin e6 in monomeric form.

  1. [Study on the effect of electric field on the secondary structure of lipase by circular dichroism].

    PubMed

    Yao, Zhan-quan; Ao, Dun-ge-ri-le; Xu, Qiang; Yang, Ti-qiang

    2006-12-01

    After the lipase was treated with electric field for five minutes, the effect of electric field on the secondary structure of lipase was studied by circular dichroism (CD). The results showed that different electric field strength in the range from 0. 5 to 6. 0 kV x cm(-1) has a different effect on the relative contents of alpha-helix, beta-sheet, beta-turn and random coil of the lipase, and whose changes were non-monotonous with the raising of electric field. In general, the electric treatment tends to transform the alpha-helix and beta-sheet into beta-turn and random coil. The decrease in alpha-helix and beta-sheet ranged respectively from 4. 6% to 48. 0% and from 13. 2% to 35. 1%, and the increase in beta-turn and random coil ranged respectively from 2. 8% to 33. 3% and from 0. 9% to 48. 1%. The result of this study has important meaning to explain the biological effect of electric treatment seeds.

  2. High Field Magnetic Circular Dichroism in Ferromagnetic InMnSb and InMnAs

    NASA Astrophysics Data System (ADS)

    Meeker, M. A.; Magill, B. A.; Khodaparast, G. A.; Saha, D.; Stanton, C. J.; McGill, S.; Wessels, B. W.

    An understanding of the fundamental interactions in narrow gap ferromagnetic semiconductors such as InMnAs and InMnSb has been developed primarily from static magnetization and electrical transport measurements. In this study, to provide a better understanding of the coupling of the Mn impurities to the conduction and valence bands through the sp-d exchange interactions, we have performed magnetic circular dichroism measurements (MCD) on MOVPE grown InMnAs and InMnSb. In our samples, the Mn content varies from 2% to 10.7% and all the samples have Curie temperatures above 300 K. The samples were photo-excited using a Quartz Tungsten Halogen lamp with energies ranging between 0.92-1.45 eV, and in magnetic fields up to 31 T. The temperatures ranged from 15-190 K. Comparison of the observed MCD with theoretical calculations provides a direct method to probe the band structure including the temperature dependence of the spin-orbit split-off bandgap and g-factors, as well as a means to estimate the sp-d coupling constants. Supported by the AFOSR through grant FA9550-14-1-0376, NSF-Career Award DMR-0846834 , NSF-DMR-60035274 , NSF-DMR-1305666, NSF MRI program (DMR-1229217).

  3. Sexual dichroism and pigment localization in the wing scales of Pieris rapae butterflies.

    PubMed

    Giraldo, M A; Stavenga, D G

    2007-01-01

    The beads in the wing scales of pierid butterflies play a crucially important role in wing coloration as shown by spectrophotometry and scanning electron microscopy (SEM). The beads contain pterin pigments, which in Pieris rapae absorb predominantly in the ultraviolet (UV). SEM demonstrates that in the European subspecies Pieris rapae rapae, both males and females have dorsal wing scales with a high concentration of beads. In the Japanese subspecies Pieris rapae crucivora, however, only the males have dorsal wing scales studded with beads, and the dorsal scales of females lack beads. Microspectrophotometry of single scales without beads yields reflectance spectra that increase slightly and monotonically with wavelength. With beads, the reflectance is strongly reduced in the UV and enhanced at the longer wavelengths. By stacking several layers of beaded scales, pierid butterflies achieve strong colour contrasts, which are not realized in the dorsal wings of female P. r. crucivora. Consequently, P. r. crucivora exhibits a strong sexual dichroism that is absent in P. r. rapae. PMID:17018427

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

    PubMed

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

    PubMed

    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. PMID:27419590

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

    PubMed

    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.

  7. Photoelectron circular dichroism of chiral molecules studied with a continuum-state-corrected strong-field approximation

    NASA Astrophysics Data System (ADS)

    Dreissigacker, Ingo; Lein, Manfred

    2014-05-01

    Motivated by recent experiments on circular dichroism in the photoelectron momentum distributions from strong-field ionization of chiral molecules [C. Lux et al., Angew. Chem. Int. Ed. 51, 5001 (2012), 10.1002/anie.201109035; C. S. Lehmann et al., J. Chem. Phys. 139, 234307 (2013), 10.1063/1.4844295], we investigate the origin of this effect theoretically. We show that it is not possible to describe photoelectron circular dichroism with the commonly used strong-field approximation due to its plane-wave nature. We therefore apply the Born approximation to the scattering state and use this as a continuum-state correction in the strong-field approximation. We obtain electron distributions for the molecules camphor and fenchone. In order to gain physical insight into the process, we study the contributions of individual molecular orientations.

  8. Simulations of circular dichroism spectra of a pair of diterpene enantiomers by time-dependent density functional theory

    NASA Astrophysics Data System (ADS)

    Liaw, Chih-Chuang; Chang, Jia-Lin; Chen, Shou-Fong; Huang, Jhih-Hong; Sie, Jyun-Fu; Cheng, Yung-Yi

    2011-11-01

    We present the first theoretical study on a pair of diterpene enantiomers of formula C 21H 34O 5, which were newly isolated from plants and identified as 3β,5β-dihydroxy-16 α/ β-methoxyhalima-13(14)-en-15,16-olide. The equilibrium geometries and harmonic vibrational frequencies of their low-lying conformers were obtained by using the AM1 and B3LYP/6-31+G(d) methods. At the optimized geometries, rotatory strengths of six excited states of each conformer were computed by the time-dependent density functional theory. The electronic circular dichroism spectra were simulated by taking Boltzmann averaging and considering the solvent effect, from which the absolute configurations of the enantiomers were determined. Their vibrational circular dichroism spectra were also predicted.

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

    PubMed

    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.

  10. Synchrotron radiation circular dichroism (SRCD) spectroscopy: An emerging method in structural biology for examining protein conformations and protein interactions

    NASA Astrophysics Data System (ADS)

    Wallace, B. A.; Gekko, Kunihiko; Vrønning Hoffmann, Søren; Lin, Yi-Hung; Sutherland, John C.; Tao, Ye; Wien, Frank; Janes, Robert W.

    2011-09-01

    Circular dichroism (CD) spectroscopy is a well-established technique in structural biology. The use of synchrotron radiation as an intense light source for these measurements extends the applications possible using lab-based instruments. In recent years, there has been a major growth in synchrotron radiation circular dichroism (SRCD) beamlines worldwide, including ones at the NSLS, ISA, SRS, HiSOR, BSRF, NSRRC, SOLEIL, Diamond, TERAS, BESSYII, and ANKA synchrotrons. Through the coordinated efforts of beamline scientists and users at these sites, important proof-of-principle studies have been done enabling the method to be developed for novel and productive studies on biological systems. This paper describes the characteristics of SRCD beamlines and some of the new types of applications that have been undertaken using these beamlines.

  11. Computational Study of the Structure, the Flexibility, and the Electronic Circular Dichroism of Staurosporine - a Powerful Protein Kinase Inhibitor

    NASA Astrophysics Data System (ADS)

    Karabencheva-Christova, Tatyana G.; Singh, Warispreet; Christov, Christo Z.

    2014-07-01

    Staurosporine (STU) is a microbial alkaloid which is an universal kinase inhibitor. In order to understand its mechanism of action it is important to explore its structure-properties relationships. In this paper we provide the results of a computational study of the structure, the chiroptical properties, the conformational flexibility of STU as well as the correlation between the electronic circular dichroism (ECD) spectra and the structure of its complex with anaplastic lymphoma kinase.

  12. Microscopic Theory and Simulation of Quantum-Well Intersubband Absorption

    NASA Technical Reports Server (NTRS)

    Li, Jianzhong; Ning, C. Z.

    2004-01-01

    We study the linear intersubband absorption spectra of a 15 nm InAs quantum well using the intersubband semiconductor Bloch equations with a three-subband model and a constant dephasing rate. We demonstrate the evolution of intersubband absorption spectral line shape as a function of temperature and electron density. Through a detailed examination of various contributions, such as the phase space filling effects, the Coulomb many-body effects and the non-parabolicity effect, we illuminate the underlying physics that shapes the spectra. Keywords: Intersubband transition, linear absorption, semiconductor heterostructure, InAs quantum well

  13. Solar absorption surface panel

    DOEpatents

    Santala, Teuvo J.

    1978-01-01

    A composite metal of aluminum and nickel is used to form an economical solar absorption surface for a collector plate wherein an intermetallic compound of the aluminum and nickel provides a surface morphology with high absorptance and relatively low infrared emittance along with good durability.

  14. Oriented Circular Dichroism: A Method to Characterize Membrane-Active Peptides in Oriented Lipid Bilayers.

    PubMed

    Bürck, Jochen; Wadhwani, Parvesh; Fanghänel, Susanne; Ulrich, Anne S

    2016-02-16

    The structures of membrane-bound polypeptides are intimately related to their functions and may change dramatically with the lipid environment. Circular dichroism (CD) is a rapid analytical method that requires relatively low amounts of material and no labeling. Conventional CD is routinely used to monitor the secondary structure of peptides and proteins in solution, for example, in the presence of ligands and other binding partners. In the case of membrane-active peptides and transmembrane proteins, these measurements can be applied to, and remain limited to, samples containing detergent micelles or small sonicated lipid vesicles. Such traditional CD analysis reveals only secondary structures. With the help of an oriented circular dichroism (OCD) setup, however, based on the preparation of macroscopically oriented lipid bilayers, it is possible to address the membrane alignment of a peptide in addition to its conformation. This approach has been mostly used for α-helical peptides so far, but other structural elements are conceivable as well. OCD analysis relies on Moffitt's theory, which predicts that the electronic transition dipole moments of the backbone amide bonds in helical polypeptides are polarized either parallel or perpendicular to the helix axis. The interaction of the electric field vector of the circularly polarized light with these transitions results in an OCD spectrum of a membrane-bound α-helical peptide, which exhibits a characteristic line shape and reflects the angle between the helix axis and the bilayer normal. For parallel alignment of a peptide helix with respect to the membrane surface (S-state), the corresponding "fingerprint" CD band around 208 nm will exhibit maximum negative amplitude. If the helix changes its alignment via an obliquely tilted (T-state) to a fully inserted transmembrane orientation (I-state), the ellipticity at 208 nm decreases and the value approaches zero due to the decreased interactions between the field and the

  15. First-principles approach to the dynamic magnetoelectric couplings for the non-reciprocal directional dichroism in BiFeO3

    NASA Astrophysics Data System (ADS)

    Lee, Jun Hee; Kézsmáki, István; Fishman, Randy S.

    2016-04-01

    Due to the complicated magnetic and crystallographic structures of BiFeO3, its magnetoelectric (ME) couplings and microscopic model Hamiltonian remain poorly understood. By employing a first-principles approach, we uncover all possible ME couplings associated with the spin-current (SC) and exchange-striction (ES) polarizations, and construct an appropriate Hamiltonian for the long-range spin-cycloid in BiFeO3. First-principles calculations are used to understand the microscopic origins of the ME couplings. We find that inversion symmetries broken by ferroelectric and antiferroelectric distortions induce the SC and the ES polarizations, which cooperatively produce the dynamic ME effects in BiFeO3. A model motivated by first principles reproduces the absorption difference of counter-propagating light beams called non-reciprocal directional dichroism. The current paper focuses on the spin-driven (SD) polarizations produced by a dynamic electric field, i.e. the dynamic ME couplings. Due to the inertial properties of Fe, the dynamic SD polarizations differ significantly from the static SD polarizations. Our systematic approach can be generally applied to any multiferroic material, laying the foundation for revealing hidden ME couplings on the atomic scale and for exploiting optical ME effects in the next generation of technological devices such as optical diodes. This manuscript has been written by UT-Battelle, LLC under Contract No. DE-AC05-00OR22725 with the US Department of Energy. The United States Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a non-exclusive, paid-up, irrevocable, world-wide license to publish or reproduce the published form of this manuscript, or allow others to do so, for United States Government purposes. The Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan.

  16. Magnetic circular dichroism studies of matrix-isolated atoms: Excited state spin-orbit coupling constant reduction of copper in the noble gases

    NASA Astrophysics Data System (ADS)

    Vala, Martin; Zeringue, Kyle; ShakhsEmampour, Jalal; Rivoal, Jean-Claude; Pyzalski, Robert

    1984-03-01

    The absorption and magnetic circular dichroism spectra of the 2P←2S transition of matrix-isolated copper atoms have been measured in krypton and xenon matrices. A dramatic reversal in the MCD C term pattern is observed. From a spectral band moment analysis it is shown that: (1) noncubic lattice cage vibrational motions are more important than cubic ones in contributing to the observed bandwidths and (2) the Cu excited state spin-orbit coupling constant (λ) in krypton is reduced to 57% of its gas phase value, whereas in xenon it is reduced to -14% of its gas phase value. Calculations using the Moran model show that the excited state geometry of the metal/rare gas cage is distorted via the Jahn-Teller effect in opposite ways in krypton and xenon matrices. The negative sign of λ in xenon reveals a reversal in the order of the 2P state spin-orbit multiplets. Neither this reversal nor the reduction of λ in krypton can be accounted for by the Jahn-Teller effect. We attribute the spin-orbit constant reduction to the overlap of the Cu 4p orbital with the np of the rare gas matrix cage atoms. The calculated spin-orbit reduction factors (in Ar, Kr, and Xe) agree well with the experimental ones if a contracted Cu 4p orbital is used. In the same way the ground state g factor shift with matrix atom type, observed by Kasai and McLeod, is semiquantitatively accounted for by calculation of the overlaps between the Cu 4s orbital and the np orbitals of the rare gas cage atoms.

  17. Direct observation of depth profile of magnetic moment by magnetic circular dichroism

    NASA Astrophysics Data System (ADS)

    Mun, Bongjin Simon; Yang, See-Hun; Mannella, Norman; Kay, Alex W.; Kim, Sang-Koog; Kortright, Jeffrey B.; Underwood, Jim H.; Hussain, Zahid; Fadley, Charles S.

    2001-03-01

    The magnetic properties at the interface between Fe and Cr wedge layers are investigated with a new depth-resolved soft x-ray photoemission spectroscopy (SXPS)[1], combined with magnetic circular dichroism (MCD). The layers of Fe (10 A)/ Cr (50 A wedge- shaped) are grown on a periodic multilayer (B 4 C(22.5A)/W(17.1 A)) _40, which provides the strong standing wave effects of 40 The unique angular dependence of photoelectron intensity of Fe and Cr has been observed at each different Cr wedge thickness and show excellent agreement with the theoretical calculation. To maximize the enhancement and contrast of standing wave effect inside of sample, the sample position is tuned to the Bragg angle position, at which the MCD measurement with SXPS along the different thickness of Cr wedge layer provides the depth profile of the magnetic moment of Fe and Cr. A strong antiparallel coupling across the interface of Cr magnetic moment is clearly resolved while the apparent reduction of Fe magnetic moment is observed near the interface. This observation is consistent with the other works on the same system [2] and even describes how the magnetic moment behaves inside of the sample from the top surface to the interface in one single sample preparation. In this experiment, a new depth-resolved SXPS has been successfully implemented to magnetic multilayer system and prove to be powerful technique to study the buried interface of magnetic system, as proposed by our former work [1]. [1] S.-H. Yang, B. S. Mun, A.W. Kay, S.-K. Kim, J. B. Kortright , J.H. Underwood, Z. Hussain, C. S. Fadley, Surf. Sci. 461 L557-L564 (2000) [2] G. Panaccione, F. Sirotti, E. Narducci, and G. Rossi, Phys. Rev. B 55, 389 (1997)

  18. Circular Dichroism Reveals Evidence of Coupling Between Immunoglobulin Constant and Variable Region Secondary Structure†

    PubMed Central

    Janda, Alena; Casadevall, Arturo

    2010-01-01

    Antibodies (Ab) are bifunctional molecules with two domains, a constant region (C) that confers effector properties and a variable (V) region responsible of antigen (Ag) binding. Historically the C and V regions were considered to be functionally independent, with Ag specificity being solely determined by the V region. However, recent studies suggest that the C region can affect Ab fine specificity. This has led to the proposal that the CH domain influences the structure of the V region, thus affecting Ab affinity and fine specificity. An inference from this proposal is that V region identical monoclonal Abs (mAbs) differing in C region (eg isotype) would manifest different secondary structures arising from isotype-induced variation in the V-C region after Ag binding. We hypothesized that such effects could translate into differences in Circular Dichroism (CD) upon Ag-Ab complex formation. Consequently we studied the interaction of a set of V region identical IgG1, IgG2a, IgG2b, and IgG3 mAbs with glucuronoxylomannan (GXM). The native CD spectra of the pairs IgG1/IgG2a and IgG3/IgG2b were strikingly similar, implying similar secondary structure content. GXM binding by IgG1, IgG2a, IgG2b and IgG3 produced different CD changes, with the pairs IgG1/IgG2a and IgG3/IgG2b again manifesting qualitatively similar trends in secondary structure changes. The magnitude of the changes differed among the isotypes with IgG2a > IgG3> IgG2b> IgG1. These differences in CD changes were interpreted to reflect differences in V-C secondary structure. PMID:20299100

  19. Synchrotron radiation circular dichroism spectroscopy study of recombinant T β4 folding

    NASA Astrophysics Data System (ADS)

    Huang, Yung-Chin; Chu, Hsueh-Liang; Chen, Peng-Jen; Chang, Chia-Ching

    Thymosin beta 4 (T β4) is a 43-amino acid small peptide, has been demonstrated that it can promote cardiac repair, wound repair, tissue protection, and involve in the proliferation of blood cell precursor stem cells of bone marrow. Moreover, T β4 has been identified as a multifunction intrinsically disordered protein, which is lacking the stable tertiary structure. Owing to the small size and disordered character, the T β4 protein degrades rapidly and the storage condition is critical. Therefore, it is not easy to reveal its folding mechanism of native T β4. However, recombinant T β4 protein (rT β4), which fused with a 5-kDa peptide in its amino-terminal, is stable and possesses identical function of T β4. Therefore, rT β4 can be used to study its folding mechanism. By using over-critical folding process, stable folding intermediates of rT β4 can be obtained. Structure analysis of folding intermediates by synchrotron radiation circular dichroism (SRCD) and fluorescence spectroscopies indicate that rT β4 is a random coli major protein and its hydrophobic region becomes compact gradually. Moreover, the rT β4 folding is a two state transition. Thermal denaturation analysis indicates that rT β4 lacks stable tertiary structure. These results indicated that rT β4, similar to T β4, is an intrinsically disordered protein. Research is supported by MOST, Taiwan. MOST 103-2112-M-009-011-MY3. Corresponding author: Chia-Ching Chang; ccchang01@faculty.nctu.edu.tw.

  20. Conformational analysis and vibrational circular dichroism of tris(ethylenediamine)ruthenium(II) complex: a theoretical study.

    PubMed

    Pandith, Altaf Hussain; Pati, Swapan K

    2010-01-14

    The conformational preferences and vibrational circular dichroism of tris(ethylenediamine)ruthenium complex in two main configurations (Lambda) and (Delta), have been performed using density functional theory. We find that for the free [Ru(en)(3)](2+) ion in the Delta-configuration, the conformational stability order is Delta(deltadeltadelta) > Delta(lambdadeltadelta) > Delta(lambdalambdadelta) > Delta(lambdalambdalambda) and that for the Lambda-configuration it is Lambda(deltadeltadelta) < Lambda(lambdadeltadelta) < Lambda(lambdalambdadelta) < Lambda(lambdalambdalambda). The energy differences between the four conformers for both the configurations Delta and Lambda are relatively small, but the activation barriers for ring inversion from one conformation to another are significant, as compared to other such systems. We trace the origin of these results to the lower oxidation state of Ru and relatively larger Ru-N bond length. We have also studied the effect of counterions on the conformational stability for Ru(en)(3)Cl(2.) Our results indicate a reverse stability order for the associated complex, Ru(en)(3) Cl(2) and higher activation barriers for ring inversion as compared to the free complex ion Ru(en)(3)(2+). It is because of larger hydrogen bonding interactions between the three N-H bonds and the chloride ion in these two conformers as compared to other conformations, which is also evident from the VCD spectra of N-H stretching modes. We also investigate IR spectra for all conformations in Delta- and Lambda-configurations and together with energetics and VCD spectra elucidate the spectroscopic characteristics of Ru(en)(3)(2+) complexes with and without the associated counterions.

  1. X-ray magnetic-circular-dichroism study of Ni/Fe (001) multilayers

    SciTech Connect

    Lin, T.; Schwickert, M.M.; Tomaz, M.A.; Chen, H.; Harp, G.R.

    1999-06-01

    The structure and magnetic properties of Fe/Ni(001) multilayers are studied using x-ray diffraction, magneto-optical Kerr effect magnetometry, and x-ray magnetic circular dichroism. Multilayers are deposited with constant Fe layers (12 {Angstrom}) and wedged Ni layers (0{endash}30 {Angstrom}), repeated 20 times, to explore the magnetic moment and the structure dependence upon thickness of Ni (t{sub Ni}). Up to t{sub Ni}{approx}16 {Angstrom} (11 ML), both the Fe and the Ni have a bct structure, similar to the bulk structure of bcc Fe. The magnetic moments of Ni in the bct region are nearly constant at 0.85{mu}{sub B} for a Ni thickness t{sub Ni} in the range 3 {Angstrom}{lt}t{sub Ni}{lt}16 {Angstrom}. This represents a significant enhancement over the moment in bulk fcc Ni (0.59{mu}B). The Fe/Ni multilayer undergoes a crystalline phase transition between 16 {Angstrom}{lt}t{sub Ni}{lt}23 {Angstrom}, beyond which both the Fe and Ni have an fct structure. In the fct region, the Ni magnetic moment is close to its bulk value and the Fe magnetic moment drops to 1.5{mu}{sub B}, which is {approximately}70{percent} of its bulk value. The crystalline phase transition is also accompanied by a rotation of the magnetic easy axis by 45{degree} in the plane of the film. {copyright} {ital 1999} {ital The American Physical Society}

  2. The secondary structure of echistatin from 1H-NMR, circular-dichroism and Raman spectroscopy.

    PubMed

    Saudek, V; Atkinson, R A; Lepage, P; Pelton, J T

    1991-12-01

    Detailed biophysical studies have been carried out on echistatin, a member of the disintegrin family of small, cysteine-rich, RGD-containing proteins, isolated from the venom of the saw-scaled viper Echis carinatus. Analysis of circular-dichroism spectra indicates that, at 20 degrees C, echistatin contains no alpha-helix but contains mostly beta-turns and beta-sheet. Two isobestic points are observed as the temperature is raised, the conformational changes associated with that observed between 40 degrees C and 72 degrees C being irreversible. Raman spectra also indicate considerable beta-turn and beta-sheet (20%) structure and an absence of alpha-helical structure. Three of the four disulphide bridges are shown to be in an all-gauche conformation, while the fourth adopts a trans-gauche-gauche conformation. The 1H-NMR spectrum of echistatin has been almost fully assigned. A single conformation was observed at 27 degrees C with the four proline residues adopting only the trans conformation. A large number of backbone amide protons were found to exchange slowly, but no segments of the backbone were found to be in either alpha-helical or beta-sheet conformation. A number of turns could be characterised. An irregular beta-hairpin contains the RGD sequence in a mobile loop at its tip. Two of the four disulphide cross-links have been identified from the NMR spectra. The data presented in this paper will serve to define the structure of echistatin more closely in subsequent studies. PMID:1761037

  3. Quasar Absorption Studies

    NASA Technical Reports Server (NTRS)

    Mushotzky, Richard (Technical Monitor); Elvis, Martin

    2004-01-01

    The aim of the proposal is to investigate the absorption properties of a sample of inter-mediate redshift quasars. The main goals of the project are: Measure the redshift and the column density of the X-ray absorbers; test the correlation between absorption and redshift suggested by ROSAT and ASCA data; constrain the absorber ionization status and metallicity; constrain the absorber dust content and composition through the comparison between the amount of X-ray absorption and optical dust extinction. Unanticipated low energy cut-offs where discovered in ROSAT spectra of quasars and confirmed by ASCA, BeppoSAX and Chandra. In most cases it was not possible to constrain adequately the redshift of the absorber from the X-ray data alone. Two possibilities remain open: a) absorption at the quasar redshift; and b) intervening absorption. The evidences in favour of intrinsic absorption are all indirect. Sensitive XMM observations can discriminate between these different scenarios. If the absorption is at the quasar redshift we can study whether the quasar environment evolves with the Cosmic time.

  4. Excited electronic states of limonene: A circular dichroism and photoelectron spectroscopy study of d-limonene

    NASA Astrophysics Data System (ADS)

    Brint, P.; Meshulam, Edna; Gedanken, Aharon

    1984-08-01

    The excited states of limonene are discussed in the light of vacuum-UV absorption, VUVCD and photoelectron spectroscopy measurements. Only one π → π* transition arising from the double bond of the ring is observed. The CD sign of the π → π* transition does not obey the octant rule formulated for chiral olefins.

  5. Rotational averaging of multiphoton absorption cross sections

    SciTech Connect

    Friese, Daniel H. Beerepoot, Maarten T. P.; Ruud, Kenneth

    2014-11-28

    Rotational averaging of tensors is a crucial step in the calculation of molecular properties in isotropic media. We present a scheme for the rotational averaging of multiphoton absorption cross sections. We extend existing literature on rotational averaging to even-rank tensors of arbitrary order and derive equations that require only the number of photons as input. In particular, we derive the first explicit expressions for the rotational average of five-, six-, and seven-photon absorption cross sections. This work is one of the required steps in making the calculation of these higher-order absorption properties possible. The results can be applied to any even-rank tensor provided linearly polarized light is used.

  6. Absorption heat pump system

    DOEpatents

    Grossman, G.

    1982-06-16

    The efficiency of an absorption heat pump system is improved by conducting liquid from a second stage evaporator thereof to an auxiliary heat exchanger positioned downstream of a primary heat exchanger in the desorber of the system.

  7. Absorption heat pump system

    DOEpatents

    Grossman, Gershon

    1984-01-01

    The efficiency of an absorption heat pump system is improved by conducting liquid from a second stage evaporator thereof to an auxiliary heat exchanger positioned downstream of a primary heat exchanger in the desorber of the system.

  8. Compounds affecting cholesterol absorption

    NASA Technical Reports Server (NTRS)

    Hua, Duy H. (Inventor); Koo, Sung I. (Inventor); Noh, Sang K. (Inventor)

    2004-01-01

    A class of novel compounds is described for use in affecting lymphatic absorption of cholesterol. Compounds of particular interest are defined by Formula I: ##STR1## or a pharmaceutically acceptable salt thereof.

  9. DESIRS: a state-of-the-art VUV beamline featuring high resolution and variable polarization for spectroscopy and dichroism at SOLEIL.

    PubMed

    Nahon, Laurent; de Oliveira, Nelson; Garcia, Gustavo A; Gil, Jean-François; Pilette, Bertrand; Marcouillé, Olivier; Lagarde, Bruno; Polack, François

    2012-07-01

    DESIRS is a new undulator-based VUV beamline on the 2.75 GeV storage ring SOLEIL (France) optimized for gas-phase studies of molecular and electronic structures, reactivity and polarization-dependent photodynamics on model or actual systems encountered in the universe, atmosphere and biosphere. It is equipped with two dedicated endstations: a VUV Fourier-transform spectrometer (FTS) for ultra-high-resolution absorption spectroscopy (resolving power up to 10(6)) and an electron/ion imaging coincidence spectrometer. The photon characteristics necessary to fulfill its scientific mission are: high flux in the 5-40 eV range, high spectral purity, high resolution, and variable and well calibrated polarizations. The photon source is a 10 m-long pure electromagnetic variable-polarization undulator producing light from the very near UV up to 40 eV on the fundamental emission with tailored elliptical polarization allowing fully calibrated quasi-perfect horizontal, vertical and circular polarizations, as measured with an in situ VUV polarimeter with absolute polarization rates close to unity, to be obtained at the sample location. The optical design includes a beam waist allowing the implementation of a gas filter to suppress the undulator high harmonics. This harmonic-free radiation can be steered toward the FTS for absorption experiments, or go through a highly efficient pre-focusing optical system, based on a toroidal mirror and a reflective corrector plate similar to a Schmidt plate. The synchrotron radiation then enters a 6.65 m Eagle off-plane normal-incidence monochromator equipped with four gratings with different groove densities, from 200 to 4300 lines mm(-1), allowing the flux-to-resolution trade-off to be smoothly adjusted. The measured ultimate instrumental resolving powers are 124000 (174 µeV) around 21 eV and 250000 (54 µeV) around 13 eV, while the typical measured flux is in the 10(10)-10(11) photons s(-1) range in a 1

  10. Solar selective absorption coatings

    DOEpatents

    Mahoney, Alan R.; Reed, Scott T.; Ashley, Carol S.; Martinez, F. Edward

    2004-08-31

    A new class of solar selective absorption coatings are disclosed. These coatings comprise a structured metallic overlayer such that the overlayer has a sub-micron structure designed to efficiently absorb solar radiation, while retaining low thermal emissivity for infrared thermal radiation. A sol-gel layer protects the structured metallic overlayer from mechanical, thermal, and environmental degradation. Processes for producing such solar selective absorption coatings are also disclosed.

  11. Solar selective absorption coatings

    DOEpatents

    Mahoney, Alan R.; Reed, Scott T.; Ashley, Carol S.; Martinez, F. Edward

    2003-10-14

    A new class of solar selective absorption coatings are disclosed. These coatings comprise a structured metallic overlayer such that the overlayer has a sub-micron structure designed to efficiently absorb solar radiation, while retaining low thermal emissivity for infrared thermal radiation. A sol-gel layer protects the structured metallic overlayer from mechanical, thermal, and environmental degradation. Processes for producing such solar selective absorption coatings are also disclosed.

  12. Optical absorption measurement system

    DOEpatents

    Draggoo, Vaughn G.; Morton, Richard G.; Sawicki, Richard H.; Bissinger, Horst D.

    1989-01-01

    The system of the present invention contemplates a non-intrusive method for measuring the temperature rise of optical elements under high laser power optical loading to determine the absorption coefficient. The method comprises irradiating the optical element with a high average power laser beam, viewing the optical element with an infrared camera to determine the temperature across the optical element and calculating the absorption of the optical element from the temperature.

  13. Scanning imaging absorption spectrometer for atmospheric chartography

    NASA Technical Reports Server (NTRS)

    Burrows, John P.; Chance, Kelly V.

    1991-01-01

    The SCanning Imaging Absorption SpectroMeter for Atmospheric CHartographY is an instrument which measures backscattered, reflected, and transmitted light from the earth's atmosphere and surface. SCIAMACHY has eight spectral channels which observe simultaneously the spectral region between 240 and 1700 nm and selected windows between 1940 and 2400 nm. Each spectral channel contains a grating and linear diode array detector. SCIAMACHY observes the atmosphere in nadir, limb, and solar and lunar occultation viewing geometries.

  14. The Role of Heme Chirality in the Circular Dichroism of Heme Proteins

    NASA Astrophysics Data System (ADS)

    Woody, Robert W.; Pescitelli, Gennaro

    2014-07-01

    The rotational strength (R) of the Soret transition in sperm-whale myoglobin (SW Mb), the hemoglobin from Chironomus thummi thummi (CTT Hb), and human hemoglobin (hHb) has been calculated using 20 high-resolution (< 1:5 Å) crystal structures. The intrinsic rotational strength due to heme non-planarity was calculated using π-electron theory and time-dependent density functional theory (TDDFT). Calculations on model protoporphyrins with a planar nucleus and with various torsional angles for the 2- and 4-vinyl substituents showed maximum R of ±0.70 Debye-Bohr magneton (1 DBM = 0.9273 · 10-38 cgs units). Viewing the heme so that the 2- and 4-vinyls are in a counterclockwise relationship, if a vinyl points toward the viewer, it contributes positively to R. Calculations of the intrinsic R for explicit heme geometries of SW Mb, CTT Hb, and hHb gave averages of 0.40±0.09, ±0:44±0.04, and +0.32±0.11 DBM, respectively. Coupling of the Soret transition with aromatic side-chain and peptide backbone transitions was also considered. For SW Mb, the magnitudes of the contributions decreased in the order Rint > Raro > Rpep. For CTT Hb and hHB, the orders were, respectively, Rint > Rpep > Raro and Rint > Raro ≈ Rpep. Human Hb ɑ chains showed the same trend as CTT Hb. Only in the hHb β chains did Raro predominate, with the order Raro > Rint > Rpep. The total predicted Rtot for SW Mb, CTT Hb, and hHb averaged +0.77±0.10 (0.56 - 0.80), -0.37±0.12 (-0.5), and +0.31±0.17 DBM (0.23 - 0.50), respectively. (Values in parentheses are experimental values.) Thus, contrary to the currently accepted view, coupling with aromatic side-chain or peptide transitions is not the dominant factor in the Soret circular dichroism (CD) of these proteins. The Soret CD is dominated by intrinsic CD of the heme chromophore, of which vinyl torsion is the major determinant. This result suggests an explanation for the large effect of heme isomerism on the Soret CD of Mb and Hb. Rotation about the

  15. Circular dichroism study of stacking properties of oligodeoxyadenylates and polydeoxyadenylate. A three-state conformational model.

    PubMed

    Olsthoorn, C S; Bostelaar, L J; De Rooij, J F; Van Boom, J H; Altona, C

    1981-04-01

    The temperature dependence of the circular dichroism (CD) spectra of a series of deoxyadenylates (dA)n, n = 2, 3, 6, 9, 12, infinity, in aqueous solution was studied. The data were interpreted on the basis of a new conformational model for the stacked state suggested by our previous proton NMR studies on (dA)2 and (dA)3 [C. S. M. Olsthoorn, L. J. Bostelaar, J. H. van Boom & C. Altona (1980) Eur. J. biochem. 112, 95-110]. In this model the stacked regions of the single-stranded oligomers consist of residues taking up a geometry resembling that of the B-DNA genus of structures (all sugars S or C2'-endo) except those residues at the 3' end that do not 'feel' a following stacking interaction. The deoxyribose rings in the latter residues retain (or regain when melting out removes a stacking interaction somewhere along the chain) the conformational freedom (S in equilibrium N, N = C3'-endo) that these rings possess in the monomers 2'-deoxyadenosine 5'-methylphosphate or in 2'-deoxyadenosine 3',5'-bis(methylphosphate), as the case may be. It is shown that this model allows (a) construction of the CD spectra of (dA)n, n = 3, 6, 9, 12, from those of the dimer and the polymer; (b) the separation of the weak CD displayed by the regular S-S stacking mode and the far stronger CD exhibited by the 3'-end S-N stacking (the latter CD resembles that of the A-DNA genus of structures); (c) delineation of the thermodynamics of stacking. The melting temperature remains constant and independent of chain length (about 50 degrees C) whereas delta H degrees and delta S degrees show a slight increase in absolute values on increasing n from 2 to infinity owing to small cooperativity effects. Near 0 degrees C the dimer occurs for about 90% in the stacked form, the oligomers attain even higher conformational purities. It is suggested that premelting phenomena observed in the CD spectra of double-helical DNAs may also involve local transitions from the normal B-like ----S-S-s---- stacking mode

  16. The circular dichroism properties of phi W-14 DNA containing alpha-putrescinylthymine.

    PubMed

    Spetter, S; Chen, C; Warren, R A; Hanlon, S

    1985-03-01

    The circular dichroism properties of phi W-14 DNA containing alpha-putrescinylthymine and its acetylated derivative have been examined in a number of aqueous solvents. Native phi W-14 DNA exhibits a B-type CD spectrum whose characteristics do not entirely conform to what would be expected for its GC content (51%). The conformationally sensitive positive band above 260 nm has a rotational strength greater than that normally found in prokaryotic DNAs of comparable GC content, such as Escherichia coli DNA. The rotational strength of this band in the spectrum of the heat-denatured form of phi W-14 DNA, however, is similar to that of heat denatured E. coli DNA. Abolition of the positive charge on the putrescine residues of native phi W-14 DNA by reaction with CH2O or by acetylation reduces the rotational strength to a level appropriate for its GC content. Increases in the electrolyte content of the solvent have the same effect, although the rotational strength of this band in phi W-14 DNA does not become comparable to that of E. coli DNA until 6-7 M LiCl. Titration to pH 10.6 in solvents of modest electrolyte content, however, fails to appreciably affect the CD spectral properties of either native phi W-14 DNA or the derivative in which half of the secondary and all of the primary amino groups have been acetylated. On the basis of these results we have concluded that the enhanced rotational strength of the positive band above 260 nm in the CD spectrum of phi W-14 DNA is due to a conformational difference caused by an ion-pair interaction of the positively charged primary amino groups of putrescine with the phosphate backbone. The CD spectral properties, however, reveal that these differences, averaged over the entire basepair population, appear to be relatively small. The average conformation, at least in dilute aqueous solutions, seems to be an unexceptional B variant with conformational properties which would be more appropriate for a DNA of higher CG content.

  17. Seven-effect absorption refrigeration

    DOEpatents

    DeVault, R.C.; Biermann, W.J.

    1989-05-09

    A seven-effect absorption refrigeration cycle is disclosed utilizing three absorption circuits. In addition, a heat exchanger is used for heating the generator of the low absorption circuit with heat rejected from the condenser and absorber of the medium absorption circuit. A heat exchanger is also provided for heating the generator of the medium absorption circuit with heat rejected from the condenser and absorber of the high absorption circuit. If desired, another heat exchanger can also be provided for heating the evaporator of the high absorption circuit with rejected heat from either the condenser or absorber of the low absorption circuit. 1 fig.

  18. Seven-effect absorption refrigeration

    DOEpatents

    DeVault, Robert C.; Biermann, Wendell J.

    1989-01-01

    A seven-effect absorption refrigeration cycle is disclosed utilizing three absorption circuits. In addition, a heat exchanger is used for heating the generator of the low absorption circuit with heat rejected from the condenser and absorber of the medium absorption circuit. A heat exchanger is also provided for heating the generator of the medium absorption circuit with heat rejected from the condenser and absorber of the high absorption circuit. If desired, another heat exchanger can also be provided for heating the evaporator of the high absorption circuit with rejected heat from either the condenser or absorber of the low absorption circuit.

  19. Harnessing the electromagnetic absorptions of metamaterials for positive applications

    NASA Astrophysics Data System (ADS)

    Xiang, Yuanjiang; Zou, Yanhong; Luo, Hailu; Dai, Xiaoyu; Wen, Shuangchun; Fan, Dianyuan

    2010-08-01

    Absorption or loss is inevitable for the metal-based metamaterials (MMs) due to the intrinsic loss of the metal, and constitutes a major hurdle to the practical realization of most applications such as a sub-wavelength lens. Thus, to reduce the losses becomes one of the major challenges in the MM field. However, the inevitable loss can also be harnessed to take a positive role in the applications of MMs such as stealth technology or other types of cloaking devices. In this presentation, after a brief review of the advances in MMs-based absorbers, we present several schemes to fulfill the desired electromagnetic absorption properties, both linear and nonlinear. For linear absorption, we have experimentally demonstrated that the absorption performance of an ordinary microwave absorbing material can be evidently improved by using the electric resonance resulting from an array of subwavelength metallic circuit elements. For nonlinear absorption, we show theoretically that the active linear magnetic permeability induces a nonlinear absorption, similar to the two-photon absorption (TPA), of electric field in a lossy MM with a Kerr-type nonlinear polarization.

  20. Absolute measurements of nonlinear absorption near LIDT at 193 nm

    NASA Astrophysics Data System (ADS)

    Blaschke, Holger; Ristau, Detlev; Welsch, Eberhard; Apel, Oliver

    2001-04-01

    Previous investigations indicate that oxide coatings exhibit non-linear absorption phenomena below 200 nm. Hereby, absorption data of Al2O3 thin film coatings has been determined absolutely by laser calorimetry (LCA) at 193 nm in the low fluence regime. As an alternative, on the basis of the pulsed surface thermal lens technique (STL), photothermal measurements allow to determine the absorption relatively at fluence levels both in the subdamage fluence range far from the damage onset and close to the LIDT. By combining the two measurement techniques, the absolute determination of linear as well as multiphoton absorption can be achieved also in the vicinity of the laser damage fluences. This is of crucial interest because the initiation of damage onset can be observed immediately. Absolute absorption data of Al2O3 coatings at different laser fluences stating of some mJoule/cm2 will be presented for the wavelength 193 nm. Thus, the correlation between the increase of absorption and the onset of breakdown can be illustrated impressively. The evaluation and discussion of the experimental results are focused on the degree of non-linearity of the investigated absorption behavior of oxide single layers initiating the optical breakdown of UV oxide coatings.

  1. Effects of dispersion and absorption in resonant Bragg diffraction of x-rays.

    PubMed

    Lovesey, S W; Scagnoli, V; Dobrynin, A N; Joly, Y; Collins, S P

    2014-03-26

    Resonant diffraction of x-rays by crystals with anisotropic optical properties is investigated theoretically, to assess how the intensity of a Bragg spot is influenced by effects related to dispersion (birefringence) and absorption (dichroism). Starting from an exact but opaque expression, simple analytic results are found to expose how intensity depends on dispersion and absorption in the primary and secondary beams and, also, the azimuthal angle (rotation of the crystal about the Bragg wavevector). If not the full story for a given application, our results are more than adequate to explore consequences of dispersion and absorption in the intensity of a Bragg spot. Results are evaluated for antiferromagnetic copper oxide, and low quartz. For CuO, one of our results reproduces all salient features of a previously published simulation of the azimuthal-angle dependence of a magnetic Bragg peak. It is transparent in our analytic result that dispersion and absorption effects alone cannot reproduce published experimental data. Available data for the azimuthal-angle dependence of space-group forbidden reflections (0,0, l), with l ≠ 3n, of low quartz depart from symmetry imposed by the triad axis of rotation symmetry. The observed asymmetry can be induced by dispersion and absorption even though absorption coefficients are constant, independent of the azimuthal angle, in this class of reflections.

  2. Effects of dispersion and absorption in resonant Bragg diffraction of x-rays.

    PubMed

    Lovesey, S W; Scagnoli, V; Dobrynin, A N; Joly, Y; Collins, S P

    2014-03-26

    Resonant diffraction of x-rays by crystals with anisotropic optical properties is investigated theoretically, to assess how the intensity of a Bragg spot is influenced by effects related to dispersion (birefringence) and absorption (dichroism). Starting from an exact but opaque expression, simple analytic results are found to expose how intensity depends on dispersion and absorption in the primary and secondary beams and, also, the azimuthal angle (rotation of the crystal about the Bragg wavevector). If not the full story for a given application, our results are more than adequate to explore consequences of dispersion and absorption in the intensity of a Bragg spot. Results are evaluated for antiferromagnetic copper oxide, and low quartz. For CuO, one of our results reproduces all salient features of a previously published simulation of the azimuthal-angle dependence of a magnetic Bragg peak. It is transparent in our analytic result that dispersion and absorption effects alone cannot reproduce published experimental data. Available data for the azimuthal-angle dependence of space-group forbidden reflections (0,0, l), with l ≠ 3n, of low quartz depart from symmetry imposed by the triad axis of rotation symmetry. The observed asymmetry can be induced by dispersion and absorption even though absorption coefficients are constant, independent of the azimuthal angle, in this class of reflections. PMID:24599265

  3. All-optical switching in granular ferromagnets caused by magnetic circular dichroism

    NASA Astrophysics Data System (ADS)

    Ellis, Matthew O. A.; Fullerton, Eric E.; Chantrell, Roy W.

    2016-07-01

    Magnetic recording using circularly polarised femto-second laser pulses is an emerging technology that would allow write speeds much faster than existing field driven methods. However, the mechanism that drives the magnetisation switching in ferromagnets is unclear. Recent theories suggest that the interaction of the light with the magnetised media induces an opto-magnetic field within the media, known as the inverse Faraday effect. Here we show that an alternative mechanism, driven by thermal excitation over the anisotropy energy barrier and a difference in the energy absorption depending on polarisation, can create a net magnetisation over a series of laser pulses in an ensemble of single domain grains. Only a small difference in the absorption is required to reach magnetisation levels observed experimentally and the model does not preclude the role of the inverse Faraday effect but removes the necessity that the opto-magnetic field is 10 s of Tesla in strength.

  4. All-optical switching in granular ferromagnets caused by magnetic circular dichroism.

    PubMed

    Ellis, Matthew O A; Fullerton, Eric E; Chantrell, Roy W

    2016-01-01

    Magnetic recording using circularly polarised femto-second laser pulses is an emerging technology that would allow write speeds much faster than existing field driven methods. However, the mechanism that drives the magnetisation switching in ferromagnets is unclear. Recent theories suggest that the interaction of the light with the magnetised media induces an opto-magnetic field within the media, known as the inverse Faraday effect. Here we show that an alternative mechanism, driven by thermal excitation over the anisotropy energy barrier and a difference in the energy absorption depending on polarisation, can create a net magnetisation over a series of laser pulses in an ensemble of single domain grains. Only a small difference in the absorption is required to reach magnetisation levels observed experimentally and the model does not preclude the role of the inverse Faraday effect but removes the necessity that the opto-magnetic field is 10 s of Tesla in strength. PMID:27466066

  5. All-optical switching in granular ferromagnets caused by magnetic circular dichroism

    PubMed Central

    Ellis, Matthew O. A.; Fullerton, Eric E.; Chantrell, Roy W.

    2016-01-01

    Magnetic recording using circularly polarised femto-second laser pulses is an emerging technology that would allow write speeds much faster than existing field driven methods. However, the mechanism that drives the magnetisation switching in ferromagnets is unclear. Recent theories suggest that the interaction of the light with the magnetised media induces an opto-magnetic field within the media, known as the inverse Faraday effect. Here we show that an alternative mechanism, driven by thermal excitation over the anisotropy energy barrier and a difference in the energy absorption depending on polarisation, can create a net magnetisation over a series of laser pulses in an ensemble of single domain grains. Only a small difference in the absorption is required to reach magnetisation levels observed experimentally and the model does not preclude the role of the inverse Faraday effect but removes the necessity that the opto-magnetic field is 10 s of Tesla in strength. PMID:27466066

  6. Atomic moments in Mn2CoAl thin films analyzed by X-ray magnetic circular dichroism

    DOE PAGES

    Jamer, M. E.; Assaf, B. A.; Sterbinsky, G. E.; Arena, D. A.; Heiman, D.

    2014-12-05

    Spin gapless semiconductors are known to be strongly affected by structural disorder when grown epitaxially as thin films. The magnetic properties of Mn2CoAl thin films grown on GaAs (001) substrates are investigated here as a function of annealing. This study investigates the atomic-specific magnetic moments of Mn and Co atoms measured through X-ray magnetic circular dichroism as a function of annealing and the consequent structural ordering. Results indicate that the structural distortion mainly affects the Mn atoms as seen by the reduction of the magnetic moment from its predicted value.

  7. Picosecond transient circular dichroism of the photoreceptor protein of the light-adapted form of Blepharisma japonicum

    NASA Astrophysics Data System (ADS)

    Hache, François; Khuc, Mai-Thu; Brazard, Johanna; Plaza, Pascal; Martin, Monique M.; Checcucci, Giovanni; Lenci, Francesco

    2009-11-01

    We present a picosecond transient circular dichroism study of OBIP, the putative photoreceptor protein involved in the photophobic response of Blepharisma japonicum. The probe wavelength was chosen at 230 nm. The results are compared to those of the isolated chromophore, OxyBP, in solution. The CD changes in OBIP and OxyBP do not show the same dynamics: OBIP's signal relaxes in a few ps whereas no such decay is obtained for OxyBP. This observation brings support to the formerly evoked existence of a fast photoinduced reaction in the chromoprotein, and demonstrates the implication of local geometrical changes that accompany this process.

  8. Intestinal absorption of magnesium from food and supplements.

    PubMed Central

    Fine, K D; Santa Ana, C A; Porter, J L; Fordtran, J S

    1991-01-01

    The purpose of this study was to measure magnesium absorption over the wide range of intakes to which the intestine may be exposed from food and/or magnesium-containing medications. Net magnesium absorption was measured in normal subjects after they ingested a standard meal supplemented with 0, 10, 20, 40, and 80 mEq of magnesium acetate. Although absorption increased with each increment in intake, fractional magnesium absorption fell progressively (from 65% at the lowest to 11% at the highest intake) so that absorption as a function of intake was curvilinear. This absorption-intake relationship was almost perfectly represented by an equation containing a hyperbolic function plus a linear function. Our results are statistically compatible with a magnesium absorption process that simultaneously uses a mechanism that reaches an absorptive maximum, plus a mechanism that endlessly absorbs a defined fraction (7%) of ingested magnesium. Compared to previous studies of calcium absorption, much less magnesium that calcium was absorbed at intakes above 8 mEq/meal, apparently due to greater restriction of intestinal permeability to magnesium. We also found that magnesium from a high magnesium-containing food source, almonds, was just as bioavailable as from soluble magnesium acetate. In contrast, magnesium absorption from commercially available enteric-coated magnesium chloride was much less than from magnesium acetate, suggesting that enteric coating can impair magnesium bioavailability. PMID:1864954

  9. Absorption heat pump system

    DOEpatents

    Grossman, Gershon; Perez-Blanco, Horacio

    1984-01-01

    An improvement in an absorption heat pump cycle is obtained by adding adiabatic absorption and desorption steps to the absorber and desorber of the system. The adiabatic processes make it possible to obtain the highest temperature in the absorber before any heat is removed from it and the lowest temperature in the desorber before heat is added to it, allowing for efficient utilization of the thermodynamic availability of the heat supply stream. The improved system can operate with a larger difference between high and low working fluid concentrations, less circulation losses, and more efficient heat exchange than a conventional system.

  10. Surface characterization of human serum albumin and sodium perfluorooctanoate mixed solutions by pendant drop tensiometry and circular dichroism.

    PubMed

    Messina, Paula; Prieto, Gerardo; Dodero, Verónica; Cabrerizo-Vílchez, M A; Maldonado-Valderrama, J; Ruso, Juan M; Sarmiento, Félix

    2006-06-15

    The interfacial behavior of mixed human serum albumin (HSA)/sodium perfluorooctanoate (C8FONa) solutions is examined by using two experimental techniques, pendant drop tensiometry and circular dichroism spectroscopy. Through the analysis of the surface tension of the mixed solutions, surface competitive adsorption at the air-water interface between C8FONa and HSA is detected. The dynamic adsorption curves exhibit the distinct regimes in their time-dependent surface tension. The nature of these regimes is further analyzed in terms of the variation of the molecules surface areas. As a consequence, a compact and dense structure was formed where protein molecules were interconnected and overlapped. Thus, a reduction of the area occupied per molecule from 100 to 0.2 nm(2) is interpreted as a gel-like structure at the surface. The presence of the surfactant seems to favor the formation of this interfacial structure. Finally, measurements of circular dichroism suggests a compaction of the protein due to the association with the surfactant given by an increase of alpha-helix structure in the complexes as compared to that of pure protein.

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

    PubMed

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

    2016-01-01

    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. PMID:27220650

  12. Structural alterations of human serum albumin caused by glycative and oxidative stressors revealed by circular dichroism analysis.

    PubMed

    Monacelli, Fiammetta; Storace, Daniela; D'Arrigo, Cristina; Sanguineti, Roberta; Borghi, Roberta; Pacini, Davide; Furfaro, Anna L; Pronzato, Maria A; Odetti, Patrizio; Traverso, Nicola

    2013-01-01

    The aim of this work was to evaluate the ability of oxidative and glycative stressors to modify properties of human serum albumin (HSA) by analyzing markers of glycation (pentosidine) and oxidation (advanced oxidative protein products (AOPPs)) and assessing fluorescence and circular dichroism. HSA was incubated for up to 21 days with ribose, ascorbic acid (AA) and diethylenetriamine pentacetate (DTPA) in various combinations in order to evaluate influences of these substances on the structure of HSA. Ribose was included as a strong glycative molecule, AA as a modulator of oxidative stress, and DTPA as an inhibitor of metal-catalyzed oxidation. Ribose induced a significant increase in pentosidine levels. AA and DTPA prevented the accumulation of pentosidine, especially at later time points. Ribose induced a mild increase in AOPP formation, while AA was a strong inducer of AOPP formation. Ribose, in combination with AA, further increased the formation of AOPP. DTPA prevented the AA-induced generation of AOPP. Ribose was also a potent inducer of fluorescence at 335nm ex/385nm em, which is typical of pentosidine. AA and DTPA prevented this fluorescence. Circular dichroism showed complex results, in which AA and DTPA were strong modifiers of the percentages of the alpha-helical structure of HSA, while ribose affected the structure of HSA only at later time points. PMID:23702842

  13. PILOT STUDY International comparability in spectroscopic measurements of protein structure by circular dichroism: CCQM-P59

    NASA Astrophysics Data System (ADS)

    Ravi, Jascindra; Schiffmann, David; Tantra, Ratna; Cox, Simon; Eady, Jonathan; Jones, Christopher; Vrettos, John S.; Affleck, Richard P.; DeSa Lorenz, Julie; Shigeri, Yasushi; Linghui, Sheng; Jun, Liu; Willows, Robert; Charlet, Philippe; Dupont, Yves; Meuse, Curtis W.; Bailey, Marc J. A.; Knight, Alex E.

    2010-01-01

    Circular dichroism is a spectroscopic technique that is widely used to obtain information about protein structure, and hence is an important tool with many applications, including the characterization of biopharmaceuticals. However, there is a lack of confidence in the technique, arising from an observed lack of comparability in the data obtained by different laboratories, or even different operators. In this study, we set out to determine the extent of comparability in the technique, by comparing the results obtained from identical protein samples by a panel of worldwide laboratories. The laboratories chosen were either national measurement institutes (NMIs) or expert laboratories nominated by an NMI. We also aimed to identify the main factors contributing to any lack of measurement comparability. Data were analysed using PCA and SIMCA methods, and we show these statistical techniques are ideal for analysing large amounts of this type of spectroscopic data. We found a startling lack of comparability among laboratories, but we also found that most of the variability arose from relatively simple problems, which can be avoided by following simple guidelines. We believe that the lack of an absolute reference or measurement traceability in circular dichroism contributes to a lack of confidence in the technique. Main text. To reach the main text of this paper, click on Final Report. The final report has been peer-reviewed and approved for publication by the CCQM Working Group on Bioanalysis (BAWG).

  14. Structural alterations of human serum albumin caused by glycative and oxidative stressors revealed by circular dichroism analysis.

    PubMed

    Monacelli, Fiammetta; Storace, Daniela; D'Arrigo, Cristina; Sanguineti, Roberta; Borghi, Roberta; Pacini, Davide; Furfaro, Anna L; Pronzato, Maria A; Odetti, Patrizio; Traverso, Nicola

    2013-01-01

    The aim of this work was to evaluate the ability of oxidative and glycative stressors to modify properties of human serum albumin (HSA) by analyzing markers of glycation (pentosidine) and oxidation (advanced oxidative protein products (AOPPs)) and assessing fluorescence and circular dichroism. HSA was incubated for up to 21 days with ribose, ascorbic acid (AA) and diethylenetriamine pentacetate (DTPA) in various combinations in order to evaluate influences of these substances on the structure of HSA. Ribose was included as a strong glycative molecule, AA as a modulator of oxidative stress, and DTPA as an inhibitor of metal-catalyzed oxidation. Ribose induced a significant increase in pentosidine levels. AA and DTPA prevented the accumulation of pentosidine, especially at later time points. Ribose induced a mild increase in AOPP formation, while AA was a strong inducer of AOPP formation. Ribose, in combination with AA, further increased the formation of AOPP. DTPA prevented the AA-induced generation of AOPP. Ribose was also a potent inducer of fluorescence at 335nm ex/385nm em, which is typical of pentosidine. AA and DTPA prevented this fluorescence. Circular dichroism showed complex results, in which AA and DTPA were strong modifiers of the percentages of the alpha-helical structure of HSA, while ribose affected the structure of HSA only at later time points.

  15. Structural Alterations of Human Serum Albumin Caused by Glycative and Oxidative Stressors Revealed by Circular Dichroism Analysis

    PubMed Central

    Monacelli, Fiammetta; Storace, Daniela; D’Arrigo, Cristina; Sanguineti, Roberta; Borghi, Roberta; Pacini, Davide; Furfaro, Anna L.; Pronzato, Maria A.; Odetti, Patrizio; Traverso, Nicola

    2013-01-01

    The aim of this work was to evaluate the ability of oxidative and glycative stressors to modify properties of human serum albumin (HSA) by analyzing markers of glycation (pentosidine) and oxidation (advanced oxidative protein products (AOPPs)) and assessing fluorescence and circular dichroism. HSA was incubated for up to 21 days with ribose, ascorbic acid (AA) and diethylenetriamine pentacetate (DTPA) in various combinations in order to evaluate influences of these substances on the structure of HSA. Ribose was included as a strong glycative molecule, AA as a modulator of oxidative stress, and DTPA as an inhibitor of metal-catalyzed oxidation. Ribose induced a significant increase in pentosidine levels. AA and DTPA prevented the accumulation of pentosidine, especially at later time points. Ribose induced a mild increase in AOPP formation, while AA was a strong inducer of AOPP formation. Ribose, in combination with AA, further increased the formation of AOPP. DTPA prevented the AA-induced generation of AOPP. Ribose was also a potent inducer of fluorescence at 335nm ex/385nm em, which is typical of pentosidine. AA and DTPA prevented this fluorescence. Circular dichroism showed complex results, in which AA and DTPA were strong modifiers of the percentages of the alpha-helical structure of HSA, while ribose affected the structure of HSA only at later time points. PMID:23702842

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

    PubMed Central

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

    2016-01-01

    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. PMID:27220650

  17. Lipid membrane association of myelin proteins and peptide segments studied by oriented and synchrotron radiation circular dichroism spectroscopy.

    PubMed

    Muruganandam, Gopinath; Bürck, Jochen; Ulrich, Anne S; Kursula, Inari; Kursula, Petri

    2013-12-01

    Myelin-specific proteins are either integral or peripheral membrane proteins that, in complex with lipids, constitute a multilayered proteolipid membrane system, the myelin sheath. The myelin sheath surrounds the axons of nerves and enables rapid conduction of axonal impulses. Myelin proteins interact intimately with the lipid bilayer and play crucial roles in the assembly, function, and stability of the myelin sheath. Although myelin proteins have been investigated for decades, their structural properties upon membrane surface binding are still largely unknown. In this study, we have used simplified model systems consisting of synthetic peptides and membrane mimics, such as detergent micelles and/or lipid vesicles, to probe the conformation of peptides using synchrotron radiation circular dichroism spectroscopy (SRCD). Additionally, oriented circular dichroism spectroscopy (OCD) was employed to examine the orientation of myelin peptides in macroscopically aligned lipid bilayers. Various representative peptides from the myelin basic protein (MBP), P0, myelin/oligodencrocyte glycoprotein, and connexin32 (cx32) were studied. A helical peptide from the central immunodominant epitope of MBP showed a highly tilted orientation with respect to the membrane surface, whereas the N-terminal cytoplasmic segment of cx32 folded into a helical structure that was only slightly tilted. The folding of full-length myelin basic protein was, furthermore, studied in a bicelle environment. Our results provide information on the conformation and membrane alignment of important membrane-binding peptides in a membrane-mimicking environment, giving novel insights into the mechanisms of membrane binding and stacking by myelin proteins.

  18. Influence of an electric field on oriented films of DMPC/gramicidin bilayers: a circular dichroism study.

    PubMed

    Fiche, J B; Laredo, T; Tanchak, O; Lipkowski, J; Dutcher, J R; Yada, R Y

    2010-01-19

    A film of oriented bilayers containing a mixture of gramicidin and dimyristoylphosphatidylcholine (DMPC) has been deposited on a fused-silica window coated with a 10 nm thick gold layer. The thin layer of gold allows the application of an electric potential across the film and the study of its influence on the structure and integrity of the bilayers. Electrochemical measurements, ellipsometry, and far-UV circular dichroism (CD) were employed to characterize the properties of the film of bilayers as a function of the potential applied to the gold electrode. For potentials across the film that are within the range approximately +300 to -150 mV the oriented film of bilayers is stable, and no change in the CD spectra of gramicidin molecule is observed. At more negative potentials, an increase in the film thickness and water content measured by ellipsometry indicated that the film swells and incorporates water, which causes a change in the circular dichroism spectrum of gramicidin molecules in the film. This transformation was interpreted as a change in the average orientation of gramicidin molecules within the film due to a decrease in the ordering of the molecules upon swelling.

  19. Inferring surface solar absorption from broadband satellite measurements

    NASA Technical Reports Server (NTRS)

    Cess, Robert D.; Vulis, Inna L.

    1989-01-01

    An atmospheric solar radiation model and surface albedo models that include wavelength dependence and surface anisotropy are combined to study the possibility of inferring the surface solar absorption from satellite measurements. The model includes ocean, desert, pasture land, savannah, and bog surface categories. Problems associated with converting narrowband measurements to broadband quantities are discussed, suggesting that it would be easier to infer surface solar absorption from broadband measurements directly. The practice of adopting a linear relationship between planetary and surface albedo to estimate surface albedos from satellite measurements is examined, showing that the linear conversion between broadband planetary and surface albedos is strongly dependent on vegetation type. It is suggested that there is a linear slope-offset relationship between surface and surface-atmosphere solar absorption.

  20. Electrothermal linear actuator

    NASA Technical Reports Server (NTRS)

    Derr, L. J.; Tobias, R. A.

    1969-01-01

    Converting electric power into powerful linear thrust without generation of magnetic fields is accomplished with an electrothermal linear actuator. When treated by an energized filament, a stack of bimetallic washers expands and drives the end of the shaft upward.

  1. A linear programming manual

    NASA Technical Reports Server (NTRS)

    Tuey, R. C.

    1972-01-01

    Computer solutions of linear programming problems are outlined. Information covers vector spaces, convex sets, and matrix algebra elements for solving simultaneous linear equations. Dual problems, reduced cost analysis, ranges, and error analysis are illustrated.

  2. Lipids: Absorption and transport

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Due to the hydrophobic nature of lipids, dietary fat is handled differently than protein or carbohydrate with respect with digestion and absorption. Dietary fats are broken down throughout the gastrointestinal system. A unique group of enzymes and cofactors allows this process to proceed in an eff...

  3. Absorption driven focus shift

    NASA Astrophysics Data System (ADS)

    Harrop, N.; Wolf, S.; Maerten, O.; Dudek, K.; Ballach, S.; Kramer, R.

    2016-03-01

    Modern high brilliance near infrared lasers have seen a tremendous growth in applications throughout the world. Increased productivity has been achieved by higher laser power and increased brilliance of lasers. Positive impacts on the performance and costs of parts are opposed to threats on process stability and quality, namely shift of focus position over time. A high initial process quality will be reduced by contamination of optics, eventually leading to a focus shift or even destruction of the optics. Focus analysis at full power of multi-kilowatt high brilliance lasers is a very demanding task because of high power densities in the spot and the high power load on optical elements. With the newly developed high power projection optics, the High-Power Micro-Spot Monitor High Brilliance (HP-MSM-HB) is able to measure focus diameter as low as 20 μm at power levels up to 10 kW at very low internal focus shift. A main driving factor behind thermally induced focus shift is the absorption level of the optical element. A newly developed measuring system is designed to determine the relative absorption level in reference to a gold standard. Test results presented show a direct correlation between absorption levels and focus shift. The ability to determine the absorption level of optical elements as well as their performance at full processing power before they are put to use, enables a high level of quality assurance for optics manufacturers and processing head manufacturers alike.

  4. Two-Phonon Absorption

    ERIC Educational Resources Information Center

    Hamilton, M. W.

    2007-01-01

    A nonlinear aspect of the acousto-optic interaction that is analogous to multi-photon absorption is discussed. An experiment is described in which the second-order acousto-optically scattered intensity is measured and found to scale with the square of the acoustic intensity. This experiment using a commercially available acousto-optic modulator is…

  5. Cholesterol Absorption and Metabolism.

    PubMed

    Howles, Philip N

    2016-01-01

    Inhibitors of cholesterol absorption have been sought for decades as a means to treat and prevent cardiovascular diseases (CVDs) associated with hypercholesterolemia. Ezetimibe is the one clear success story in this regard, and other compounds with similar efficacy continue to be sought. In the last decade, the laboratory mouse, with all its genetic power, has become the premier experimental model for discovering the mechanisms underlying cholesterol absorption and has become a critical tool for preclinical testing of potential pharmaceutical entities. This chapter briefly reviews the history of cholesterol absorption research and the various gene candidates that have come under consideration as drug targets. The most common and versatile method of measuring cholesterol absorption is described in detail along with important considerations when interpreting results, and an alternative method is also presented. In recent years, reverse cholesterol transport (RCT) has become an area of intense new interest for drug discovery since this process is now considered another key to reducing CVD risk. The ultimate measure of RCT is sterol excretion and a detailed description is given for measuring neutral and acidic fecal sterols and interpreting the results. PMID:27150091

  6. Linear-Algebra Programs

    NASA Technical Reports Server (NTRS)

    Lawson, C. L.; Krogh, F. T.; Gold, S. S.; Kincaid, D. R.; Sullivan, J.; Williams, E.; Hanson, R. J.; Haskell, K.; Dongarra, J.; Moler, C. B.

    1982-01-01

    The Basic Linear Algebra Subprograms (BLAS) library is a collection of 38 FORTRAN-callable routines for performing basic operations of numerical linear algebra. BLAS library is portable and efficient source of basic operations for designers of programs involving linear algebriac computations. BLAS library is supplied in portable FORTRAN and Assembler code versions for IBM 370, UNIVAC 1100 and CDC 6000 series computers.

  7. Aerosol Angstrom Absorption Coefficient Comparisons during MILAGRO.

    NASA Astrophysics Data System (ADS)

    Marley, N. A.; Marchany-Rivera, A.; Kelley, K. L.; Mangu, A.; Gaffney, J. S.

    2007-12-01

    Measurements of aerosol absorption were obtained as part of the MAX-Mex component of the MILAGRO field campaign at site T0 (Instituto Mexicano de Petroleo in Mexico City) by using a 7-channel aethalometer (Thermo- Anderson) during the month of March, 2006. The absorption measurements obtained in the field at 370, 470, 520, 590, 660, 880, and 950 nm were used to determine the aerosol Angstrom absorption exponents by linear regression. Since, unlike other absorbing aerosol species (e.g. humic like substances, nitrated PAHs), black carbon absorption is relatively constant from the ultraviolet to the infrared with an Angstrom absorption exponent of -1 (1), a comparison of the Angstrom exponents can indicate the presence of aerosol components with an enhanced UV absorption over that expected from BC content alone. The Angstrom exponents determined from the aerosol absorption measurements obtained in the field varied from - 0.7 to - 1.3 during the study and was generally lower in the afternoon than the morning hours, indicating an increase in secondary aerosol formation and photochemically generated UV absorbing species in the afternoon. Twelve-hour integrated samples of fine atmospheric aerosols (<0.1micron) were also collected at site T0 and T1 (Universidad Technologica de Tecamac, State of Mexico) from 5 am to 5 pm (day) and from 5 pm to 5 am (night) during the month of March 2006. Samples were collected on quartz fiber filters with high volume impactor samplers. Continuous absorption spectra of these aerosol samples have been obtained in the laboratory from 280 to 900nm with the use of an integrating sphere coupled to a UV spectrometer (Beckman DU with a Labsphere accessory). The integrating sphere allows the detector to collect and spatially integrate the total radiant flux reflected from the sample and therefore allows for the measurement of absorption on highly reflective or diffusely scattering samples. These continuous spectra have also been used to obtain the

  8. [Absorption of extractive Polygonum orientale in rat everted gut sacs].

    PubMed

    Liu, Yue; Tang, Li; Cao, Xu; Zheng, Lin; Wang, Ai-Min; Huang, Yong

    2014-06-01

    Using in vitro everted gut to investigate the intestinal absorption of the extracts from Polygonum orientale at different concentration. UPLC-MS/MS was used to detect the content of protocatechuic acid, isoorientin, orientin, vitexin, cynaroside, quercitrin, kaempferol-rhamnoside in different intestinal segments, then compared the results with the absorption of chemical components of extractive P. orientale in each intestinal segments, and calculated the absorption parameter. We took the statistic analysis with SPSS statistic software. The influence significance of each factors were analyzed to describe the character of absorption. The absorption of each component is linearity in different intestinal segments and different dose, and the square of coeficient correlation exceed 0.95, which consistent with zero order rate process. The K(a) increase along with the raised dosage of the extractive P. orientale (R2 > 0.95), indicated it is the passive absorption; different intestinal segments have different absorption. And the absorption trend in intestinal is duodenum, jejunum, ileum are greater than the colon. As ingredients are selectively absorbed in intestinal sac, the everted intestinal sac method is selected to assess the intestinal absorption charcteristics of ingredients of extractive P. orientale. PMID:25272855

  9. Intestinal absorption of biotin in the rat

    SciTech Connect

    Bowman, B.B.; Selhub, J.; Rosenberg, I.H.

    1986-07-01

    We examined the absorption of biotin using the in vivo intestinal loop technique. Jejunal segments from male rats were filled with solutions containing (/sup 3/H)biotin and (/sup 14/C)inulin in Krebs-Ringer phosphate buffer, pH 6.5. Absorption was determined on the basis of luminal tritium disappearance after correction for inulin recovery. At biotin concentrations of 0.1 and 5.0 microM, luminal biotin disappearance was linear for at least 10 min. At biotin concentrations ranging from 2.3 nM to 75 microM, 10-28% of the administered dose was absorbed in 10 min. The concentration dependence of luminal biotin disappearance is consistent with the presence of both saturable and nonsaturable (linear) components of biotin uptake, with estimated Km = 9.6 microM and Jmax = 75.2 pmol/(2.5 cm loop X min). The rate constant for nonsaturable uptake is 3.1 pmol/(2.5 cm loop X min X microM). We conclude that at biotin concentrations less than 5 microM, biotin absorption proceeds largely by the saturable process, whereas at concentrations above 25 microM, nonsaturable uptake predominates. Additional studies demonstrated significantly less biotin uptake in the ileum than in the jejunum, a finding in agreement with previous in vitro studies.

  10. Absorption Features in Soil Spectra Assessment.

    PubMed

    Vašát, Radim; Kodešová, Radka; Borůvka, Luboš; Jakšík, Ondřej; Klement, Aleš; Drábek, Ondřej

    2015-12-01

    From a wide range of techniques appropriate to relate spectra measurements with soil properties, partial least squares (PLS) regression and support vector machines (SVM) are most commonly used. This is due to their predictive power and the availability of software tools. Both represent exclusively statistically based approaches and, as such, benefit from multiple responses of soil material in the spectrum. However, physical-based approaches that focus only on a single spectral feature, such as simple linear regression using selected continuum-removed spectra values as a predictor variable, often provide accurate estimates. Furthermore, if this approach extends to multiple cases by taking into account three basic absorption feature parameters (area, width, and depth) of all occurring features as predictors and subjecting them to best subset selection, one can achieve even higher prediction accuracy compared with PLS regression. Here, we attempt to further extend this approach by adding two additional absorption feature parameters (left and right side area), as they can be important diagnostic markers, too. As a result, we achieved higher prediction accuracy compared with PLS regression and SVM for exchangeable soil pH, slightly higher or comparable for dithionite-citrate and ammonium oxalate extractable Fe and Mn forms, but slightly worse for oxidizable carbon content. Therefore, we suggest incorporating the multiple linear regression approach based on absorption feature parameters into existing working practices. PMID:26555184

  11. Absorption Features in Soil Spectra Assessment.

    PubMed

    Vašát, Radim; Kodešová, Radka; Borůvka, Luboš; Jakšík, Ondřej; Klement, Aleš; Drábek, Ondřej

    2015-12-01

    From a wide range of techniques appropriate to relate spectra measurements with soil properties, partial least squares (PLS) regression and support vector machines (SVM) are most commonly used. This is due to their predictive power and the availability of software tools. Both represent exclusively statistically based approaches and, as such, benefit from multiple responses of soil material in the spectrum. However, physical-based approaches that focus only on a single spectral feature, such as simple linear regression using selected continuum-removed spectra values as a predictor variable, often provide accurate estimates. Furthermore, if this approach extends to multiple cases by taking into account three basic absorption feature parameters (area, width, and depth) of all occurring features as predictors and subjecting them to best subset selection, one can achieve even higher prediction accuracy compared with PLS regression. Here, we attempt to further extend this approach by adding two additional absorption feature parameters (left and right side area), as they can be important diagnostic markers, too. As a result, we achieved higher prediction accuracy compared with PLS regression and SVM for exchangeable soil pH, slightly higher or comparable for dithionite-citrate and ammonium oxalate extractable Fe and Mn forms, but slightly worse for oxidizable carbon content. Therefore, we suggest incorporating the multiple linear regression approach based on absorption feature parameters into existing working practices.

  12. Theoretical investigation on bridged triarylamine helicenes: UV/visible and circular dichroism spectra

    NASA Astrophysics Data System (ADS)

    Spassova, Milena; Asselberghs, Inge; Verbiest, Thierry; Clays, Koen; Botek, Edith; Champagne, Benoît

    2007-05-01

    The UV/visible and CD spectra of bridged triarylamine helicenes have been simulated using the TDDFT/B3LYP/6-31+G(d) method. They reproduce well the experimental spectra. For M-helicenes, the Cotton effect associated with the lowest-energy transition is negative for the smallest helicenes and becomes positive for the largest one, as a result of the variations of the angle between the electric and magnetic transition dipole moments. Since these species are stable upon oxidation, the UV/visible and CD spectra of their radical cations have been simulated. They show low-energy absorption and CD bands, figuring out enhancement of the first hyperpolarizability.

  13. 69. INTERIOR VIEW OF THE ABSORPTION TOWER BUILDING, ABSORPTION TOWER ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    69. INTERIOR VIEW OF THE ABSORPTION TOWER BUILDING, ABSORPTION TOWER UNDER CONSTRUCTION. (DATE UNKNOWN). - United States Nitrate Plant No. 2, Reservation Road, Muscle Shoals, Muscle Shoals, Colbert County, AL

  14. Effect of nonlinear absorption on electric field applied lead chloride by Z-scan technique

    SciTech Connect

    Rejeena, I.; Lillibai,; Nampoori, V. P. N.; Radhakrishnan, P.; Rahimkutty, M. H.

    2014-10-15

    The preparation, spectral response and optical nonlinearity of gel grown lead chloride single crystals subjected to electric field of 20V using parallel plate arrangements have been investigated. Optical band gap of the samples were determined using linear absorption spectra. Open aperture z-scan was employed for the determination of nonlinear absorption coefficient of PbCl{sub 2} solution. The normalized transmittance curve exhibits a valley shows reverse saturable absorption. The non linear absorption at different input fluences were recorded using a single Gaussian laser beam in tight focus geometry. The RSA nature of the sample makes it suitable for optical limiting applications.

  15. Effect of nonlinear absorption on electric field applied lead chloride by Z-scan technique

    NASA Astrophysics Data System (ADS)

    Rejeena, I.; Lillibai, Rahimkutty, M. H.; Nampoori, V. P. N.; Radhakrishnan, P.

    2014-10-01

    The preparation, spectral response and optical nonlinearity of gel grown lead chloride single crystals subjected to electric field of 20V using parallel plate arrangements have been investigated. Optical band gap of the samples were determined using linear absorption spectra. Open aperture z-scan was employed for the determination of nonlinear absorption coefficient of PbCl2 solution. The normalized transmittance curve exhibits a valley shows reverse saturable absorption. The non linear absorption at different input fluences were recorded using a single Gaussian laser beam in tight focus geometry. The RSA nature of the sample makes it suitable for optical limiting applications.

  16. Vaginal Absorption of Penicillin.

    PubMed

    Rock, J; Barker, R H; Bacon, W B

    1947-01-01

    Except during the last two months of pregnancy, penicillin is easily absorbed from cocoa butter suppositories in the vagina, ordinarily to give therapeutic blood levels for from 4 to 6 hours. Penicillin in the dosage used seems to have a good effect on vaginal infections. In nonpregnant women, during the ovulation phase, considered as including days 14 +/- 2 in the ordinary menstrual cycle of about 28 days, absorption seemed to be somewhat diminished. Higher levels were found in patients who were near the end of their menstrual cycles and in two patients who were menopausal. Patients who were very near term absorbed little or no penicillin, whereas patients 10 days post partum showed excellent absorption.

  17. Photothermal absorption correlation spectroscopy.

    PubMed

    Octeau, Vivien; Cognet, Laurent; Duchesne, Laurence; Lasne, David; Schaeffer, Nicolas; Fernig, David G; Lounis, Brahim

    2009-02-24

    Fluorescence correlation spectroscopy (FCS) is a popular technique, complementary to cell imaging for the investigation of dynamic processes in living cells. Based on fluorescence, this single molecule method suffers from artifacts originating from the poor fluorophore photophysics: photobleaching, blinking, and saturation. To circumvent these limitations we present here a new correlation method called photothermal absorption correlation spectroscopy (PhACS) which relies on the absorption properties of tiny nano-objects. PhACS is based on the photothermal heterodyne detection technique and measures akin FCS, the time correlation function of the detected signals. Application of this technique to the precise determination of the hydrodynamic sizes of different functionalized gold nanoparticles are presented, highlighting the potential of this method. PMID:19236070

  18. THE ABSORPTION OF ADRENALIN

    PubMed Central

    Lyon, D. Murray

    1923-01-01

    1. Adrenalin solution given subcutaneously is usually rapidly absorbed, probably by lymphatic channels. 2. The speed of this process may be influenced by the circulation rate. 3. The relative amounts of adrenalin at any moment unabsorbed at the site of inoculation, carried in the circulating fluids, and taken up by the reacting tissues can be calculated from figures extracted from the curve of the blood pressure changes. The relative rates of transference of adrenalin into the blood and from the circulation into the tissues can also be estimated. 4. When absorption takes place rapidly a large quantity of the drug comes into action at once and the maximum occurs early, the curve of blood pressure reaches a considerable height, and subsides quickly. When absorption is slow the apex appears later and does not reach so high a level. 5. The response to adrenalin bears a logarithmic relationship to the dose employed and a method of allowing for this is indicated. PMID:19868816

  19. Relic Neutrino Absorption Spectroscopy

    SciTech Connect

    Eberle, b

    2004-01-28

    Resonant annihilation of extremely high-energy cosmic neutrinos on big-bang relic anti-neutrinos (and vice versa) into Z-bosons leads to sizable absorption dips in the neutrino flux to be observed at Earth. The high-energy edges of these dips are fixed, via the resonance energies, by the neutrino masses alone. Their depths are determined by the cosmic neutrino background density, by the cosmological parameters determining the expansion rate of the universe, and by the large redshift history of the cosmic neutrino sources. We investigate the possibility of determining the existence of the cosmic neutrino background within the next decade from a measurement of these absorption dips in the neutrino flux. As a by-product, we study the prospects to infer the absolute neutrino mass scale. We find that, with the presently planned neutrino detectors (ANITA, Auger, EUSO, OWL, RICE, and SalSA) operating in the relevant energy regime above 10{sup 21} eV, relic neutrino absorption spectroscopy becomes a realistic possibility. It requires, however, the existence of extremely powerful neutrino sources, which should be opaque to nucleons and high-energy photons to evade present constraints. Furthermore, the neutrino mass spectrum must be quasi-degenerate to optimize the dip, which implies m{sub {nu}} 0.1 eV for the lightest neutrino. With a second generation of neutrino detectors, these demanding requirements can be relaxed considerably.

  20. Absorption lineshapes of molecular aggregates revisited

    SciTech Connect

    Gelzinis, Andrius; Valkunas, Leonas; Abramavicius, Darius

    2015-04-21

    Linear absorption is the most basic optical spectroscopy technique that provides information about the electronic and vibrational degrees of freedom of molecular systems. In simulations of absorption lineshapes, often diagonal fluctuations are included using the cumulant expansion, and the off-diagonal fluctuations are accounted for either perturbatively, or phenomenologically. The accuracy of these methods is limited and their range of validity is still questionable. In this work, a systematic study of several such methods is presented by comparing the lineshapes with exact results. It is demonstrated that a non-Markovian theory for off-diagonal fluctuations, termed complex time dependent Redfield theory, gives good agreement with exact lineshapes over a wide parameter range. This theory is also computationally efficient. On the other hand, accounting for the off-diagonal fluctuations using the modified Redfield lifetimes was found to be inaccurate.

  1. Detection of biological particles by the use of circular dichroism measurements improved by scattering theory

    NASA Astrophysics Data System (ADS)

    Rosen, David L.; Pendleton, J. David

    1995-09-01

    Light scattered from optically active spheres was theoretically analyzed for biodetection. The circularly polarized signal of near-forward scattering from circularly dichroic spheres was calculated. Both remote and point biodetection were considered. The analysis included the effect of a circular aperture and beam block at the detector. If the incident light is linearly polarized, a false signal would limit the sensitivity of the biodetector. If the incident light is randomly polarized, shot noise would limit the sensitivity. Suggested improvements to current techniques include a beam block, precise angular measurements, randomly polarized light, index-matching fluid, and larger apertures for large particles.

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

    SciTech Connect

    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.

  3. Energy-loss magnetic chiral dichroism study of epitaxial MnAs film on GaAs(001)

    SciTech Connect

    Fu, X.; Warot-Fonrose, B.; Arras, R.; Serin, V.; Demaille, D.; Eddrief, M.; Etgens, V.

    2015-08-10

    The room-temperature ferromagnetic behavior of MnAs/GaAs(001) thin film has been locally explored by Transmission Electron Microscope (TEM). We first differentiated hexagonal α-MnAs and quasi-hexagonal β-MnAs which are very similar in atomic structure by electron diffraction. Local magnetic moment information of the identified α-MnAs was extracted from manganese-L{sub 2,3} edges using Energy-loss Magnetic Circular Dichroism technique and the ratio of orbital to spin magnetic moment was measured. In this experiment, atomic structure identification, chemical analysis, and magnetic moment measurement were simultaneously achieved at high spatial resolution in TEM, thus providing a potential method for in-situ study of local properties of multiphase magnetic materials.

  4. Conformational analysis of quinine and its pseudo enantiomer quinidine: a combined jet-cooled spectroscopy and vibrational circular dichroism study.

    PubMed

    Sen, Ananya; Bouchet, Aude; Lepère, Valeria; Le Barbu-Debus, Katia; Scuderi, D; Piuzzi, F; Zehnacker-Rentien, A

    2012-08-16

    Laser-desorbed quinine and quinidine have been studied in the gas phase by combining supersonic expansion with laser spectroscopy, namely, laser-induced fluorescence (LIF), resonance-enhanced multiphoton ionization (REMPI), and IR-UV double resonance experiments. Density funtional theory (DFT) calculations have been done in conjunction with the experimental work. The first electronic transition of quinine and quinidine is of π-π* nature, and the studied molecules weakly fluoresce in the gas phase, in contrast to what was observed in solution (Qin, W. W.; et al. J. Phys. Chem. C2009, 113, 11790). The two pseudo enantiomers quinine and quinidine show limited differences in the gas phase; their main conformation is of open type as it is in solution. However, vibrational circular dichroism (VCD) experiments in solution show that additional conformers exist in condensed phase for quinidine, which are not observed for quinine. This difference in behavior between the two pseudo enantiomers is discussed.

  5. Mechanical design and analysis of an eight-pole superconducting vector magnet for soft x-ray magnetic dichroism measurements

    SciTech Connect

    Arbelaez, D.; Black, A.; Prestemon, S.O.; Wang, S.; Chen, J.; Arenholz, E.

    2010-01-13

    An eight-pole superconducting magnet is being developed for soft x-ray magnetic dichroism (XMD) experiments at the Advanced Light Source, Lawrence Berkley National Laboratory (LBNL). Eight conical Nb{sub 3}Sn coils with Holmium poles are arranged in octahedral symmetry to form four dipole pairs that provide magnetic fields of up to 5 T in any direction relative to the incoming x-ray beam. The dimensions of the magnet yoke as well as pole taper, diameter, and length were optimized for maximum peak field in the magnet center using the software package TOSCA. The structural analysis of the magnet is performed using ANSYS with the coil properties derived using a numerical homogenization scheme. It is found that the use of orthotropic material properties for the coil has an important influence in the design of the magnet.

  6. Soft x-ray circular dichroism and scattering using a modulated elliptically polarizing wiggler and double synchronous detection

    SciTech Connect

    Sutherland, J.C.; Polewski, K.; Monteleone, D.C.

    1998-01-23

    We have constructed an experimental station (beamline) at the National Synchrotron Light Source to measure circular dichroism (CD) using soft x-rays (250 {le} hv {le} 900 eV) from a time modulated elliptically polarizing wiggler. The polarization of the soft x-ray beam switches periodically between two opposite polarizations, hence permitting the use of phase-sensitive (lock-in) detection. While the wiggler can be modulated at frequencies up to 100 Hz, switching transients limit the actual practical frequency to {approx}25 Hz. With analog detection, switching transients are blocked by a chopper synchronized to the frequency and phase of the wiggler. The CD is obtained from the ratio of the signal recovered at the frequency of polarization modulation, f, to the average beam intensity, which is recovered by synchronous detection at frequency 2f.

  7. Circular dichroism and infrared spectroscopic characterization of secondary structure components of protein Z during mashing and boiling processes.

    PubMed

    Han, Yupeng; Wang, Jinjing; Li, Yongxian; Hang, Yu; Yin, Xiangsheng; Li, Qi

    2015-12-01

    In beer brewing, protein Z is hypothesized to stabilize beer foam. However, few investigations have revealed the relationship between conformational alterations to protein Z during the brewing process and beer foam. In this report, protein Z from sweet wort was isolated during mashing and boiling processes. Circular dichroism (CD) and Fourier transform infrared spectroscopy (FTIR) were used to monitor the structural characteristics of protein Z. The results showed that the α-helix and β-sheet content decreased, whereas the content of β-turn and random coil increased. The complex environment rich in polysaccharides may facilitate conformational alterations and modifications to protein Z. Additionally, the formation of extended structural features to protein Z provides access to reactive amino acid side chains that can undergo modifications and the exposure of hydrophobic core regions of the protein. Analyzing structural transformations should provide a deeper understanding of the mechanism of protein Z on maintaining beer foam.

  8. Electronic and spin states of SrRuO3 thin films: An x-ray magnetic circular dichroism study

    NASA Astrophysics Data System (ADS)

    Agrestini, S.; Hu, Z.; Kuo, C.-Y.; Haverkort, M. W.; Ko, K.-T.; Hollmann, N.; Liu, Q.; Pellegrin, E.; Valvidares, M.; Herrero-Martin, J.; Gargiani, P.; Gegenwart, P.; Schneider, M.; Esser, S.; Tanaka, A.; Komarek, A. C.; Tjeng, L. H.

    2015-02-01

    We report a study of the local magnetism in thin films of SrRuO3 grown on (111) and (001) oriented SrTiO3 substrates using x-ray magnetic circular dichroism spectroscopy (XMCD) at the Ru-L2 ,3 edges. The application of the sum rules to the XMCD data gives an almost quenched orbital moment and a spin moment close to the value expected for the low spin state S =1 . Full-multiplet cluster calculations indicate that the low spin state is quite stable and suggest that the occurrence of a transition to the high spin state S =2 in strained thin films of SrRuO3 is unlikely as it would be too expensive in energy.

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

    NASA Astrophysics Data System (ADS)

    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.

  10. Analysis of vibrational circular dichroism spectra of (s)-(+)-2-butanol by rotational strengths expressed in local symmetry coordinates.

    PubMed

    Shin, Saeko; Nakata, Munetaka; Hamada, Yoshiaki

    2006-02-16

    The vibrational circular dichroism (VCD) spectra of (S)-(+)-2-butanol have been observed in dilute CS(2) solutions. Two strong VCD bands are assigned mainly to the OH bending modes with the aid of quantum chemical calculations. The calculated VCD spectra corresponding to these bands are shown to depend on the conformation of the OH group. To understand this feature, we have calculated the contribution of each local vibrational mode to the rotational strengths and concluded that the coupling of the group vibrations between the in-plane and out-of-plane modes about the locally assumed symmetry planes play a significant role in VCD. This finding has provided a new scope of VCD in relation to molecular vibrations.

  11. Toroidal Interaction and Propeller Chirality of Hexaarylbenzenes. Dynamic Domino Inversion Revealed by Combined Experimental and Theoretical Circular Dichroism Studies.

    PubMed

    Kosaka, Tomoyo; Inoue, Yoshihisa; Mori, Tadashi

    2016-03-01

    Hexaarylbenzenes (HABs) have greatly attracted much attention due to their unique propeller-shaped structure and potential application in materials science, such as liquid crystals, molecular capsules/rotors, redox materials, nonlinear optical materials, as well as molecular wires. Less attention has however been paid to their propeller chirality. By introducing small point-chiral group(s) at the periphery of HABs, propeller chirality was effectively induced, provoking strong Cotton effects in the circular dichroism (CD) spectrum. Temperature and solvent polarity manipulate the dynamics of propeller inversion in solution. As such, whizzing toroids become more substantial in polar solvents and at an elevated temperature, where radial aromatic rings (propeller blades) prefer orthogonal alignment against the central benzene ring (C6 core), maximizing toroidal interactions.

  12. Determination of the composition, encapsulation efficiency and loading capacity in protein drug delivery systems using circular dichroism spectroscopy.

    PubMed

    Peng, Zhili; Li, Shanghao; Han, Xu; Al-Youbi, Abdulrahman O; Bashammakh, Abdulaziz S; El-Shahawi, Mohammad S; Leblanc, Roger M

    2016-09-21

    Peptides and proteins have become very promising drug candidates in recent decades due to their unique properties. However, the application of these drugs has been limited by their high enzymatic susceptibility, low membrane permeability and poor bioavailability when administered orally. Considerable efforts have been made to design and develop drug delivery systems that could transport peptides and proteins to targeted area. Although it is of great importance to determine the composition after loading a drug to the carrier, the ability to do so is significantly limited by current analytical methods. In this letter, five important proteins, α1-antitrypsin, hemoglobin human, human serum albumin, human transferrin and r-globulin were chemically conjugated to two model drug carriers, namely carbon dots and polymer O-(2-carboxyethyl) polyethylene glycol. A simple yet convenient method based on circular dichroism spectroscopy was developed to determine the compositions of the various protein-carrier conjugates. PMID:27590552

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

    PubMed

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

    2015-07-01

    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. PMID:26070096

  14. Linear collider: a preview

    SciTech Connect

    Wiedemann, H.

    1981-11-01

    Since no linear colliders have been built yet it is difficult to know at what energy the linear cost scaling of linear colliders drops below the quadratic scaling of storage rings. There is, however, no doubt that a linear collider facility for a center of mass energy above say 500 GeV is significantly cheaper than an equivalent storage ring. In order to make the linear collider principle feasible at very high energies a number of problems have to be solved. There are two kinds of problems: one which is related to the feasibility of the principle and the other kind of problems is associated with minimizing the cost of constructing and operating such a facility. This lecture series describes the problems and possible solutions. Since the real test of a principle requires the construction of a prototype I will in the last chapter describe the SLC project at the Stanford Linear Accelerator Center.

  15. Corrosion Problems in Absorption Chillers

    ERIC Educational Resources Information Center

    Stetson, Bruce

    1978-01-01

    Absorption chillers use a lithium bromide solution as the medium of absorption and water as the refrigerant. Discussed are corrosion and related problems, tests and remedies, and cleaning procedures. (Author/MLF)

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

    PubMed Central

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

    2014-01-01

    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. PMID:25262612

  17. Spectral characteristics of fluorescence and circular dichroism of aflatoxin B1 reaction with its anti-idiotypic antibody

    NASA Astrophysics Data System (ADS)

    Liu, Aiping; Yang, Hongxiu; Wang, Xiaohong; Chen, Fusheng

    2012-11-01

    Aflatoxin B1 (AFB1) is a toxic secondary metabolite and sensitive methods for its analysis have been developed. In our lab, a number of works have been carried out, including exploitation of detection methods and production of anti-idiotypic antibody (Ab2) against Fab fragment of anti-AFB1 antibody (Ab1). In this paper, Ab2 was generated upon the immunization of mice with F(ab')2 fragment, which was specific to AFB1 and obtained by pepsin digestion of Ab1. The characteristics of Ab2 was primarily investigated by indirect competitive enzyme-linked immunosorbent assay (icELISA), which indicated that Ab2, might bear an internal image of antigen AFB1 and was able to combine to F(ab')2 in competition with AFB1, and the concentration of Ab2 to cause 50% inhibition of binding (IC50) was 131.8 μg/mL. In addition, fluorescence and circular dichroism studies were designed to explore the mutual relationship among AFB1, F(ab')2 and Ab2. The fluorescence spectroscopy implied that both AFB1 and Ab2 act as a quencher upon F(ab')2, and the Ab2 could compete with AFB1 when both of Ab2 and AFB1 reacted with F(ab')2. The circular dichroism (CD) spectrum suggested that both the binding of Ab2 and AFB1 on F(ab')2 brought secondary conformation change of F(ab')2, especially in the changes of α helix and β sheet. The research performed would provide unique insight into the comprehension of interaction among AFB1, F(ab')2 and Ab2 as well as offer structural information for substitution researches of toxic antigen like AFB1.

  18. Interaction of water-soluble amino acid Schiff base complexes with bovine serum albumin: Fluorescence and circular dichroism studies

    NASA Astrophysics Data System (ADS)

    Gharagozlou, Mehrnaz; Boghaei, Davar M.

    2008-12-01

    Fluorescence spectroscopy in combination with circular dichroism (CD) spectroscopy were used to investigate the interaction of water-soluble amino acid Schiff base complexes, [Zn(L 1,2)(phen)] where phen is 1,10-phenanthroline and H 2L 1,2 is amino acid Schiff base ligands, with bovine serum albumin (BSA) under the physiological conditions in phosphate buffer solution adjusted to pH 7.0. The quenching mechanism of fluorescence was suggested as static quenching according to the Stern-Volmer equation. Quenching constants were determined using the Stern-Volmer equation to provide a measure of the binding affinity between amino acid Schiff base complexes and BSA. The thermodynamic parameters Δ G, Δ H and Δ S at different temperatures (298, 310 and 318 K) were calculated. The results indicate that the hydrophobic and hydrogen bonding interactions play a major role in [Zn(L 1)(phen)]-BSA association, whereas hydrophobic and electrostatic interactions participate a main role in [Zn(L 2)(phen)]-BSA binding process. Binding studies concerning the number of binding sites and apparent binding constant Kb were performed by fluorescence quenching method. The distance R between the donor (BSA) and acceptor (amino acid Schiff base complexes) has been obtained utilizing fluorescence resonant energy transfer (FRET). Furthermore, CD spectra were used to investigate the structural changes of the BSA molecule with the addition of amino acid Schiff base complexes. The results indicate that the interaction of amino acid Schiff base complexes with BSA leads to changes in the secondary structure of the protein. Fractional contents of the secondary structure of BSA ( fα, fβ, fturn and frandom) were calculated with and without amino acid Schiff base complexes utilizing circular dichroism spectroscopy. Our results clarified that amino acid Schiff base complexes could bind to BSA and be effectively transported and eliminated in the body, which could be a useful guideline for further drug

  19. Linear mass actuator

    NASA Technical Reports Server (NTRS)

    Holloway, Sidney E., III (Inventor); Crossley, Edward A., Jr. (Inventor); Jones, Irby W. (Inventor); Miller, James B. (Inventor); Davis, C. Calvin (Inventor); Behun, Vaughn D. (Inventor); Goodrich, Lewis R., Sr. (Inventor)

    1992-01-01

    A linear mass actuator includes an upper housing and a lower housing connectable to each other and having a central passageway passing axially through a mass that is linearly movable in the central passageway. Rollers mounted in the upper and lower housings in frictional engagement with the mass translate the mass linearly in the central passageway and drive motors operatively coupled to the roller means, for rotating the rollers and driving the mass axially in the central passageway.

  20. {sup 57}Fe Moessbauer and x-ray magnetic circular dichroism study of magnetic compensation of the rare-earth sublattice in Nd{sub 2-x}Ho{sub x}Fe{sub 14}B compounds

    SciTech Connect

    Chaboy, J.; Piquer, C.; Plugaru, N.; Bartolome, F.; Laguna-Marco, M. A.

    2007-10-01

    We present here a study of the magnetic properties of the Nd{sub 2-x}Ho{sub x}Fe{sub 14}B series. The macroscopic properties of these compounds evolve continuously from those of Nd{sub 2}Fe{sub 14}B to those of Ho{sub 2}Fe{sub 14}B as Ho gradually replaces Nd. The system shows a compensation of the rare-earth sublattice magnetization for a critical concentration, x{sub c}=0.55, that is reflected into the anomalous behavior of both macroscopic and microscopic magnetic probes. The combined analysis of magnetization, {sup 57}Fe Moessbauer spectroscopy and Fe K-edge x-ray magnetic circular dichroism (XMCD) measurements suggests that the origin of the anomalous magnetic behavior found at x{sub c}=0.55 is mainly due to the Ho sublattice. Moreover, the analysis of the Fe K-edge XMCD signals reveal the presence of a rare-earth contribution, reflecting the coupling of the rare-earth and Fe magnetic moments, which can lead to the possibility of disentangling the magnetic behavior of both Fe and R atoms using a single absorption edge.