WorldWideScience

Sample records for circular dichroism spectroscopy

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

    DEFF Research Database (Denmark)

    Lassen, Peter Rygaard

    2006-01-01

    chiral molecules. This project is about application of one such technique, circular dichroism (CD) spectroscopy, which measures the difference in absorption of left- and right circularly polarized light - hence the name circular dichroism. This study has focused on the infrared (IR) range because...... compounds of pharmaceutical interest. Others are transition metal complexes relevant for the search for parity-violation effects in vibrational spectroscopy (rhenium complexes), for asymmetric catalysis (Schiff-base complexes), or as model systems for metal centres in biology (Schiff-bases and heme......). Proteins (primarily myoglobin) have been studied experimentally by VCD, but are far too large for DFT calculations, in which case one must resort to model systems. In the case of organic compounds, the absolute configuration has been determined for molecules as large as ginkgolide B with 11 chiral centres...

  2. Toroidal circular dichroism

    Science.gov (United States)

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

    2016-07-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

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

    DEFF Research Database (Denmark)

    Lassen, Peter Rygaard

    2005-01-01

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

  5. Rashba splitting in an image potential state investigated by circular dichroism two-photon photoemission spectroscopy

    Science.gov (United States)

    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.

  6. A Reference Database for Circular Dichroism Spectroscopy Covering Fold and Secondary Structure Space

    International Nuclear Information System (INIS)

    Circular Dichroism (CD) spectroscopy is a long-established technique for studying protein secondary structures in solution. Empirical analyses of CD data rely on the availability of reference datasets comprised of far-UV CD spectra of proteins whose crystal structures have been determined. This article reports on the creation of a new reference dataset which effectively covers both secondary structure and fold space, and uses the higher information content available in synchrotron radiation circular dichroism (SRCD) spectra to more accurately predict secondary structure than has been possible with existing reference datasets. It also examines the effects of wavelength range, structural redundancy and different means of categorizing secondary structures on the accuracy of the analyses. In addition, it describes a novel use of hierarchical cluster analyses to identify protein relatedness based on spectral properties alone. The databases are shown to be applicable in both conventional CD and SRCD spectroscopic analyses of proteins. Hence, by combining new bioinformatics and biophysical methods, a database has been produced that should have wide applicability as a tool for structural molecular biology

  7. Picosecond circular dichroism spectroscopy: experiment, theory, and applications to protein dynamics

    Science.gov (United States)

    Xie, Sunney; Simon, John D.

    1990-05-01

    An experimental technique for measuring time dependent circular dichroism signals with picosecond resolution is described. The details of the experimental apparatus are presented. Theoretical modeling of the detected signal demonstrates that the circular dichroism signal can be isolated from contributions due to pump-induced linear dichroism and linear birefringence effects. The experimental apparatus is used to examine the comformation relaxation in myoglobin following the photoelimination of CO from carbonmonoxymyoglobin. Probing the circular dichroism of the N-band of the herne at 355 nm reveals a relaxation of several hundreds of picosecond, over two orders of magnitude slower than the photo-induced bond cleavage. These results are discussed in terms of the restructuring of the protein following photodissociation.

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

    Science.gov (United States)

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

    2016-03-01

    X-ray magnetic circular dichroism spectroscopy using an X-ray free electron laser is demonstrated with spectra over the Fe L(3,2)-edges. The high brightness of the X-ray free electron laser combined with high accuracy detection of incident and transmitted X-rays enables ultrafast X-ray magnetic circular dichroism studies of unprecedented sensitivity. This new capability is applied to a study of all-optical magnetic switching dynamics of Fe and Gd magnetic sublattices in a GdFeCo thin film above its magnetization compensation temperature. PMID:27036761

  9. The thermal and storage stability of bovine haemoglobin by ultraviolet-visible and circular dichroism spectroscopies$

    Institute of Scientific and Technical Information of China (English)

    Ruchir Bhomia; Vivek Trivedi n; Nichola J. Coleman; John C. Mitchell

    2016-01-01

    The effects of temperature, pH and long-term storage on the secondary structure and conformation changes of bovine haemoglobin (bHb) were studied using circular dichroism (CD) and ultraviolet–visible (UV–vis) spectroscopies. Neural network software was used to deconvolute the CD data to obtain the fractional content of the five secondary structures. The storage stability of bHb solutions in pH 6, 7 and 8 buffers was significantly higher at 4 °C than at 23 °C for the first 3 days. A complete denaturation of bHb was observed after 40 days irrespective of storage temperature or pH. The bHb solutions were also ex-posed to heating and cooling cycles between 25 and 65 °C and structural changes were followed by UV–vis and CD spectroscopies. These experiments demonstrated that α-helix content of bHb decreased steadily with the increasing temperature above 35 °C at all pH values. The loss inα-helicity and gain in random coil conformations was pH-dependent and the greatest under alkaline conditions. Furthermore, there was minimal recovery of the secondary structure content upon cooling to 25 °C. The use of bHb as a model drug is very common and this study elucidates the significance of storage and processing con-ditions on its stability.

  10. The thermal and storage stability of bovine haemoglobin by ultraviolet–visible and circular dichroism spectroscopies

    Directory of Open Access Journals (Sweden)

    Ruchir Bhomia

    2016-08-01

    Full Text Available The effects of temperature, pH and long-term storage on the secondary structure and conformation changes of bovine haemoglobin (bHb were studied using circular dichroism (CD and ultraviolet--visible (UV–vis spectroscopies. Neural network software was used to deconvolute the CD data to obtain the fractional content of the five secondary structures. The storage stability of bHb solutions in pH 6, 7 and 8 buffers was significantly higher at 4 °C than at 23 °C for the first 3 days. A complete denaturation of bHb was observed after 40 days irrespective of storage temperature or pH. The bHb solutions were also exposed to heating and cooling cycles between 25 and 65 °C and structural changes were followed by UV–vis and CD spectroscopies. These experiments demonstrated that α-helix content of bHb decreased steadily with the increasing temperature above 35 °C at all pH values. The loss in α-helicity and gain in random coil conformations was pH-dependent and the greatest under alkaline conditions. Furthermore, there was minimal recovery of the secondary structure content upon cooling to 25 °C. The use of bHb as a model drug is very common and this study elucidates the significance of storage and processing conditions on its stability.

  11. Circular dichroism spectroscopy of complexes of semiconductor quantum dots with chlorin e6

    Science.gov (United States)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-08-15

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

  13. Orbital Rashba effect and its detection by circular dichroism angle-resolved photoemission spectroscopy

    Science.gov (United States)

    Park, Jin-Hong; Kim, Choong H.; Rhim, Jun-Won; Han, Jung Hoon

    2012-05-01

    We show, by way of tight-binding and first-principles calculations, that a one-to-one correspondence between an electron's crystal momentum k and nonzero orbital angular momentum (OAM) is a generic feature of surface bands. The OAM forms a chiral structure in momentum space much as its spin counterpart in Rashba model does, as a consequence of the inherent inversion symmetry breaking at the surface but not of spin-orbit interaction. This is the orbital counterpart of conventional Rashba effect and may be called the “orbital Rashba effect.” The circular dichroism (CD) angle-resolved photoemission (ARPES) method is an efficient way to detect this new order, and we derive formulas explicitly relating the CD-ARPES signal to the existence of OAM in the band structure. The cases of degenerate p- and d-orbital bands are considered.

  14. Lipid membrane association of myelin proteins and peptide segments studied by oriented and synchrotron radiation circular dichroism spectroscopy.

    Science.gov (United States)

    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.

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

    International Nuclear Information System (INIS)

    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 (∼106-107 M-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

  16. The secondary structure of echistatin from 1H-NMR, circular-dichroism and Raman spectroscopy.

    Science.gov (United States)

    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

  17. Conformational analysis of quinine and its pseudo enantiomer quinidine: a combined jet-cooled spectroscopy and vibrational circular dichroism study.

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Geon Joon, E-mail: gjlee@kw.ac.kr; Sim, Geon Bo; Choi, Eun Ha [Plasma Bioscience Research Center/Department of Electrical and Biological Physics, Kwangwoon University, Seoul 139-701 (Korea, Republic of); Kwon, Young-Wan [KU-KIST Graduate School of Converging Science and Technology, Korea University, Seoul 136-701 (Korea, Republic of); Kim, Jun Young; Jang, Siun; Kim, Seong Hwan, E-mail: piceae@naver.com [Department of Microbiology and Institute of Basic Sciences, Dankook University, Cheonan 330-714 (Korea, Republic of)

    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.

  20. Alkali-hydrolysis of D-glucono-delta-lactone studied by chiral Raman and circular dichroism spectroscopies

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    The alkali-hydrolysis of D-glucono-delta-lactone (GDL) was investigated by chiral Raman and circular dichroism (CD) spectroscopies in combination with density functional theory calculation. Based on the characteristic CD bands of GDL and its hydrolysis product, the dynamics of hydrolysis was studied using stopped-flow CD method. Using chiral Raman spectroscopy (CRS), the stereochemical change of GDL owing to the hydrolysis reaction was discussed on the vibrational scale. The CRS results show that the ring-opening due to hydrolysis has a great influence on the chiral structure around the car-bonyl group, which was evidenced by the disappearance of the CRS band at 1735 cm-1 (C== O stretching vibrational mode). In addition, the change of positions and intensity of CRS bands was also observed, which was ascribed to the perturbation around the C2, C3, C4 and C5 carbons due to ring-opening. It is worthy to note that the stereochemistry of C2, C3, C4 and C5 had no fundamental change during the hydrolysis reaction, which was reflected in the maintenance of the signs of the CRS bands. Our results demonstrate that in comparison with CD technique, CRS may provide more detailed structural information of chiral molecules and open up new vistas of research for chiral reactions.

  1. Ultraviolet-circular dichroism spectroscopy and potentiometric study of the interaction between human serum albumin and sodium perfluorooctanoate.

    Science.gov (United States)

    Messina, Paula; Prieto, Gerardo; Dodero, Verónica; Ruso, Juan M; Schulz, Pablo; Sarmiento, Félix

    2005-12-15

    The interaction of a fluorinated surfactant, sodium perfluorooctanoate, with human serum albumin (HSA) has been investigated by a combination of ultraviolet-circular dichroism (UV-CD) spectroscopy and potentiometry (by a home-built ion-selective electrode) techniques to detect and characterize the conformational transitions of HSA. By using difference spectroscopy, the transition was followed as a function of temperature, and the data were analyzed to obtain the parameters characterizing the thermodynamics of unfolding. The results indicate that the presence of surfactant drastically changes the melting unfolding, acting as a structure stabilizer and delaying the unfolding process. Potentiometric measurements were used to determine the binding isotherms and binding capacity for this system. The isotherm shows a high affinity of surfactant molecules for HSA. The average number of surfactant molecules absorbed per protein molecule (at 28 mM of surfactant concentration) was found to be approximately 900, about 6 g of surfactant per gram of protein. The shape of the binding capacity curve and the relation between binding capacity and extend of cooperativity were examined. From these analysis, the values of g (number of ligand-binding sites), KH (Hill binding constant), and nH (Hill coefficient) were determined.

  2. Gauge-Invariant Formulation of Circular Dichroism.

    Science.gov (United States)

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

    2016-07-12

    Standard formulations of magnetic response properties, such as circular dichroism spectra, are plagued by gauge dependencies, which can lead to unphysical results. In this work, we present a general gauge-invariant and numerically efficient approach for the calculation of circular dichroism spectra from the current density. First we show that in this formulation the optical rotation tensor, the response function from which circular dichroism spectra can be obtained, is independent of the origin of the coordinate system. We then demonstrate that its trace is independent of the gauge origin of the vector potential. We also show how gauge invariance can be retained in practical calculations with finite basis sets. As an example, we explain how our method can be applied to time-dependent current-density-functional theory. Finally, we report gauge-invariant circular dichroism spectra obtained using the adiabatic local-density approximation. The circular dichroism spectra we thus obtain are in good agreement with experiment. PMID:27295541

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

    Directory of Open Access Journals (Sweden)

    Genet H. Zemede

    2012-08-01

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

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

    Science.gov (United States)

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

    2016-04-01

    An efficient and rapid process for isoquercitrin production by hesperidinase-catalyzed hydrolysis of rutin was successfully developed under microwave irradiation detecting the affinity by circular dichroism (CD) and surface plasmon resonance (SPR) spectroscopy. A maximum isoquercitrin yield of 91.5±2.7% was obtained in 10min with the conditions of 10g/L hesperidinase, 2g/L rutin, 30°C and microwave power density 88.9W/L. Enzymatic reaction rate and Vm/Km in the microwave reactor were 6.34-fold higher than in a continuous flow microreactor and 1.24-fold higher than in a biphasic system. CD and SPR analysis results also showed that hesperidinase has a better selectivity and affinity (3.3-fold than in a batch reactor) to generate isoquercitrin under microwave irradiation. Microwave irradiation greatly improved the reaction efficiency and productivity, leading to a more positive economical assessment. The binding affinity indicates the presence of strong multivalent interactions between rutin and hesperidinase under microwave irradiation. PMID:26803794

  5. IR and Vibrational Circular Dichroism Spectroscopy of Matrine- and Artemisinin-Type Herbal Products: Stereochemical Characterization and Solvent Effects.

    Science.gov (United States)

    Zhang, Yuefei; Poopari, M Reza; Cai, Xiaoli; Savin, Aliaksandr; Dezhahang, Zahra; Cheramy, Joseph; Xu, Yunjie

    2016-04-22

    Five Chinese herbal medicines--matrine, oxymatrine, sophoridine, artemisinin, and dihydroartemisinin--were investigated using vibrational circular dichroism (VCD) experiments and density functional theory calculations to extract their stereochemical information. The three matrine-type alkaloids are available from the dry roots of Sophora flavescens and have long been used in various traditional Chinese herbal medicines to combat diseases such as cancer and cardiac arrhythmia. Artemisinin and the related dihydroartemisinin, discovered in 1979 by Professor Youyou Tu, a 2015 Nobel laureate in medicine, are effective drugs for the treatment of malaria. The VCD measurements were carried out in CDCl3 and DMSO-d6, two solvents with different dielectric constants and hydrogen-bonding characteristics. A "clusters-in-a-liquid" approach was used to model both explicit and implicit solvent effects. The studies show that effectively accounting for solvent effects is critical to using IR and VCD spectroscopy to provide unique spectroscopic features to differentiate the potential stereoisomers of these Chinese herbal medicines. PMID:27070079

  6. IR and Vibrational Circular Dichroism Spectroscopy of Matrine- and Artemisinin-Type Herbal Products: Stereochemical Characterization and Solvent Effects.

    Science.gov (United States)

    Zhang, Yuefei; Poopari, M Reza; Cai, Xiaoli; Savin, Aliaksandr; Dezhahang, Zahra; Cheramy, Joseph; Xu, Yunjie

    2016-04-22

    Five Chinese herbal medicines--matrine, oxymatrine, sophoridine, artemisinin, and dihydroartemisinin--were investigated using vibrational circular dichroism (VCD) experiments and density functional theory calculations to extract their stereochemical information. The three matrine-type alkaloids are available from the dry roots of Sophora flavescens and have long been used in various traditional Chinese herbal medicines to combat diseases such as cancer and cardiac arrhythmia. Artemisinin and the related dihydroartemisinin, discovered in 1979 by Professor Youyou Tu, a 2015 Nobel laureate in medicine, are effective drugs for the treatment of malaria. The VCD measurements were carried out in CDCl3 and DMSO-d6, two solvents with different dielectric constants and hydrogen-bonding characteristics. A "clusters-in-a-liquid" approach was used to model both explicit and implicit solvent effects. The studies show that effectively accounting for solvent effects is critical to using IR and VCD spectroscopy to provide unique spectroscopic features to differentiate the potential stereoisomers of these Chinese herbal medicines.

  7. Alkali-hydrolysis of D-glucono-delta-lactone studied by chiral Raman and circular dichroism spectroscopies

    Institute of Scientific and Technical Information of China (English)

    JIA GuoQing; QIU Shi; LI GuanNa; ZHOU Jun; FENG ZhaoChi; LI Can

    2009-01-01

    The alkali-hydrolysis of D-glucono-delta-lactone (GDL) was investigated by chiral Raman and circular dichroism (CD) spectroecopies in combination with density functional theory calculation. Based on the characteristic CD bands of GDL and its hydrolysis product, the dynamics of hydrolysis was studied using stopped-flow CD method. Using chiral Raman spectroscopy (CRS), the stereochemical change of GDL owing to the hydrolysis reaction was discussed on the vibrational scale. The CRS results show that the ring-opening due to hydrolysis has a great influence on the chiral structure around the cer-bonyl group, which was evidenced by the disappearance of the CRS band at 1735 cm-1 (C=0 stretching vibrational mode). In addition, the change of positions and intensity of CRS bands was also observed, which was ascribed to the perturbation around the C2, C3, C4 and C5 carbons due to ring-opening. It is worthy to note that the stereochemistry of C2, C3, C4 and C5 had no fundamental change during the hydrolysis reaction, which was reflected in the maintenance of the signs of the CRS bands. Our results demonstrate that in comparison with CD technique, CRS may provide more detailed structural infor-mation of chiral molecules and open up new vistas of research for chirel reactions.

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

    Science.gov (United States)

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

    2016-04-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2010-03-02

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

  10. Detailed structural study of β-artemether: Density functional theory (DFT) calculations of Infrared, Raman spectroscopy, and vibrational circular dichroism

    Science.gov (United States)

    Wang, Zhiqiang; Chen, Jianchao; Li, Linwei; Zhou, Zhixu; Geng, Yiding; Sun, Tiemin

    2015-10-01

    In this study, the experimental and theoretical studies on the structure of β-artemether are presented. The optimized molecular structure, Mulliken atomic charges, vibrational spectra (IR, Raman and vibrational circular dichroism), and molecular electrostatic potential have been calculated by density functional theory (DFT) using B3LYP method with the 6-311++G (2d, p) basis set. Reliable vibrational assignments for Artemether have been made on the basis of potential energy distribution (PED). The vibrational circular dichroism (VCD) has been explored by ab initio calculations, and then was used to compare with the experimental VCD. The consistence between them confirmed the absolute configuration of Artemether. In addition, HOMO-LUMO of the title compound as well as thermo-dynamical parameters has illustrated the stability of β-artemether.

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

    Science.gov (United States)

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

    2006-10-27

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

  12. Linear dichroism and circular dichroism in photosynthesis research

    NARCIS (Netherlands)

    Garab, G.; Amerongen, van H.

    2009-01-01

    The efficiency of photosynthetic light energy conversion depends largely on the molecular architecture of the photosynthetic membranes. Linear- and circular-dichroism (LD and CD) studies have contributed significantly to our knowledge of the molecular organization of pigment systems at different lev

  13. Magnetic Circular Dichroism spectroscopy in epitaxial La0.7Sr0.3MnO3 thin films

    OpenAIRE

    Nath, T. K.; Neal, J. R.; G A Gehring

    2008-01-01

    Magneto optic measurements are a very powerful tool for investigating the polarization of a conduction band as a function of temperature and are used here to study the polarization of the mobile electrons in 50nm LSMO (x=0.3) strained thin films grown epitaxially on single crystalline (001) LaAlO3 (LAO) and (001) lattice matched substrate (LSAT). The magnetic circular dichroism (MCD) has been investigated in magnetic fields up to 0.5 T and over a temperature range (10 to 450 K). The MCD spect...

  14. Chemistry of porphyrin-appended cellulose strands with a helical structure: spectroscopy, electrochemistry, and in situ circular dichroism spectroelectrochemistry.

    Science.gov (United States)

    Redl, F X; Lutz, M; Daub, J

    2001-12-17

    Around 100 porphyrin units have been selectively linked at C(6)-O to a cellulose (Avicel). The properties of the metal-free and zincated porphyrin-celluloses 2 and Zn-2 have been determined by optical and electrochemical methods. Circular dichroism indicates a helical arrangement of the porphyrin units and reveals intra-chain coupling reminiscent, in the broadest sense, of strands of nucleic acids. Cyclic voltammetry and spectroelectrochemistry have been used to characterize the radical ions and dianions. The electrochromism of the oxidation of cellulose 2 to porphyrin radical cations of 2 has been employed for both molecular switching and the transduction of an electrochemical input into chiroptical signal expression. PMID:11822435

  15. UV and VUV spectrum of matrix-isolated In: an investigation by absorption, magnetic circular dichroism and emission yield spectroscopy

    Science.gov (United States)

    Schroeder, W.; Rotermund, H.-H.; Wiggenhauser, H.; Schrittenlacher, W.; Hormes, J.; Krebs, W.; Laaser, W.

    1986-05-01

    The electronic absorption spectra of In atoms isolated in neon, argon, krypton and xenon matrices have been measured in the energy range between 2.5 and 9.0 eV. This region includes the 5s 25p → 5s 26s and 5s 25p → 5s 25d resonance transitions, higher members of the corresponding s- and d-Rydberg series and the inner shell 5s 25p → 5s5p 2 transitions. A correlation of the absorption spectra with results obtained from magnetic circular dichroism and fluorescence measurements has made it possible to provide a detailed assignment of most of the features in the spectra in spite of the complexities associated with their behavior. For example, the transition to 5s 26s could not be detected in any of the matrices and the 5s 25d configuration was found to be strongly quenched in intensity as compared to the other transitions. In contrast, several Rydberg transitions could be observed for In in Ne. These were satisfactorily interpreted within the Frenkel formalism. Some of these observations have been rationalized by assuming that the average radius of the wavefunction for the excited state is the dominant parameter for the matrix interaction.

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

    International Nuclear Information System (INIS)

    The electronic structure and magnetic moments of free Mn2+ and Mn3+ 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 μB are created by 3d5(6S) 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 μB for Mn2+ and 16 μB for Mn3+, with no contribution of orbital angular momentum

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

    Energy Technology Data Exchange (ETDEWEB)

    Zamudio-Bayer, V. [Physikalisches Institut, Universität Freiburg, Stefan-Meier-Straße 21, 79104 Freiburg (Germany); Institut für Methoden und Instrumentierung der Forschung mit Synchrotronstrahlung, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Albert-Einstein-Straße 15, 12489 Berlin (Germany); Hirsch, K.; Langenberg, A.; Kossick, M. [Institut für Methoden und Instrumentierung der Forschung mit Synchrotronstrahlung, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Albert-Einstein-Straße 15, 12489 Berlin (Germany); Institut für Optik und Atomare Physik, Technische Universität Berlin, Hardenbergstraße 36, 10623 Berlin (Germany); Ławicki, A.; Lau, J. T., E-mail: tobias.lau@helmholtz-berlin.de [Institut für Methoden und Instrumentierung der Forschung mit Synchrotronstrahlung, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Albert-Einstein-Straße 15, 12489 Berlin (Germany); Terasaki, A. [Cluster Research Laboratory, Toyota Technological Institute, 717-86 Futamata, Ichikawa, Chiba 272-0001 (Japan); Department of Chemistry, Kyushu University, 6-10-1 Hakozaki, Higashi-ku, Fukuoka 812-8581 (Japan); Issendorff, B. von [Physikalisches Institut, Universität Freiburg, Stefan-Meier-Straße 21, 79104 Freiburg (Germany)

    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.

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

    DEFF Research Database (Denmark)

    Johannessen, Christian; Thulstrup, Peter W.

    2007-01-01

    . The spectroscopic results were compared to measurements performed on the free ligand and to theoretical calculations using density functional theory (B3LYP/TZVP). The results of the VCD analysis of the coordination compound identified an electronic, dipole-forbidden, magnetic dipole-allowed low-lying d-d transition......Vibrational absorption (VA) and vibrational circular dichroism (VCD) spectroscopy was applied in the analysis of vibrational and low lying electronic transitions of a triplet ground state cobalt(III) coordination compound. The spectroscopic measurements were performed on the tetrabutylammonium salt...... located in the mid infrared, as well as several amide stretch transitions located in the fingerprint region (1800-1100 cm(-1)), in both the liquid and solid phase. VCD signals were found to be 5-10 times higher than expected, indicating enhancement of the vibrational CD signals, caused by coupling...

  19. Direct Observation of High-Spin States in Manganese Dimer and Trimer Cations by X-ray Magnetic Circular Dichroism Spectroscopy in an Ion Trap

    CERN Document Server

    Zamudio-Bayer, Vicente; Langenberg, Andreas; Kossick, Martin; Ławicki, Arkadiusz; Terasaki, Akira; von Issendorff, Bernd; Lau, J Tobias

    2015-01-01

    The electronic structure and magnetic moments of free Mn$_2^+$ and Mn$_3^+$ are characterized by $2p$ x-ray absorption and x-ray magnetic circular dichroism spectroscopy in a cryogenic ion trap that is coupled to a synchrotron radiation beamline. Our results show directly that localized magnetic moments of 5 $\\mu_B$ are created by $3d^5 (^6\\mathrm{S})$ states at each ionic core, which are coupled in parallel to form molecular high-spin states via indirect exchange that is mediated in both cases by a delocalized valence electron in a singly-occupied $4s$ derived orbital with an unpaired spin. This leads to total magnetic moments of 11 $\\mu_B$ for Mn$_2^+$ and 16 $\\mu_B$ for Mn$_3^+$, with no contribution of orbital angular momentum.

  20. Simulation of magnetic circular dichroism in the electron microscope

    Science.gov (United States)

    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. Proteolytically-induced changes of secondary structural protein conformation of bovine serum albumin monitored by Fourier transform infrared (FT-IR) and UV-circular dichroism spectroscopy

    Science.gov (United States)

    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.

  2. GROUND-STATE OF FERROMAGNETIC NICKEL AND MAGNETIC CIRCULAR-DICHROISM IN 2P AND 3P CORE X-RAY ABSORPTION SPECTROSCOPIES

    NARCIS (Netherlands)

    JO, T; YOSHIDA, A; SAWATZKY, GA

    1992-01-01

    The electronic state of ferromagnetic Ni and an interpretation of magnetic circular dichroism (MCD) in Ni 2p --> 3d and 3p --> 3d X-ray absorption (XAS) are discussed from a viewpoint of 3d configuration interaction. Inclusion of the 3d8 configuration and an orbital-magnetic-moment contribution of 0

  3. Paracelsin; characterization by NMR spectroscopy and circular dichroism, and hemolytic properties of a peptaibol antibiotic from the cellulolytically active mold Trichoderma reesei. Part B.

    Science.gov (United States)

    Brückner, H; Graf, H; Bokel, M

    1984-11-15

    Paracelsin, a hemolytic and membrane active polypeptide antibiotic of the peptaibol class which is excreted by the mold Trichoderma reesei, was obtained by a simplified and rapid isolation procedure utilizing hydrophobic adsorber resins. Investigation by 13C nuclear magnetic resonance spectroscopy and circular dichroism revealed considerable helical portions in solution, and the very recently accomplished sequence determination of paracelsin allows the discussion of the results with regard to the closely related analogues, alamethicin and suzukacillin. A selective cleavage of the peptide was achieved by careful treatment with various acids, and a buffer of pH 8.25 and of high ionic strength made possible the quantitative determination of the C-terminal phenylalaninol released by means of ion-exchange chromatography. The significance of the production of paracelsin and related mycotoxins of the peptaibol class, exhibiting various kinds of biological activity, is discussed with respect to the extensive effort being made towards biotechnological applications of species, strains and cellulolytically highly active mutants of the fungus Trichoderma. PMID:6500005

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

    Energy Technology Data Exchange (ETDEWEB)

    Ito, Keita, E-mail: keita.ito.729@gmail.com [Institute of Applied Physics, Graduate School of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki 305-8573 (Japan); Department of Electronic Engineering, Graduate School of Engineering, Tohoku University, Sendai 980-8579 (Japan); Japan Society for the Promotion of Science (JSPS), Chiyoda, Tokyo 102-0083 (Japan); Toko, Kaoru; Suemasu, Takashi [Institute of Applied Physics, Graduate School of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki 305-8573 (Japan); Takeda, Yukiharu; Saitoh, Yuji [Condensed Matter Science Division, Japan Atomic Energy Agency (JAEA), Sayo, Hyogo 679-5148 (Japan); Oguchi, Tamio [The Institute of Scientific and Industrial Research (ISIR), Osaka University, Ibaraki, Osaka 567-0047 (Japan); Kimura, Akio [Graduate School of Science, Hiroshima University, Higashi-Hiroshima, Hiroshima 739-8526 (Japan)

    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.

  5. Probing the Interaction of Human Serum Albumin with Norfloxacin in the Presence of High-Frequency Electromagnetic Fields: Fluorescence Spectroscopy and Circular Dichroism Investigations

    Directory of Open Access Journals (Sweden)

    Jamshidkhan Chamani

    2011-11-01

    Full Text Available The present study describes an investigation by fluorescence quenching, circular dichroism and UV-visible spectroscopy of the interaction between norfloxacin (NRF and human serum albumin (HSA in the presence of electromagnetic fields (EMFs. The results obtained from this study indicated that NRF had a strong ability to quench HSA at λex = 280 nm. In addition, a slight blue shift occurred, which suggested that the microenvironment of the protein became more hydrophobic after addition of NRF. The interaction between the NRF and HSA, whether in the absence or presence of an EMF, was considered to be a static quenching mechanism. Moreover, synchronous fluorescence demonstrated that the microenvironment around Trp became modified. Data of HSA-NRF in the presence of EMFs between 1 Hz–1 MHz confirmed the results of quenching and blue shifts. Corresponding Stern-Volmer plots were also drawn and the resultant Ksv and kq values were compared. Moreover, the binding parameters, including the number of binding sites, the binding constant and the distance, r, between donor and acceptor, were calculated based on Förster’s non-radiative energy transfer theory. According to far and near UV-CD, the formation of the complex caused changes of the secondary and tertiary structures of HSA. The obtained results are significant for patients who are subjected to high-frequency radiation as this was found to reduce the affinity of NRF to HSA.

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

    Science.gov (United States)

    Johannessen, Christian; Thulstrup, Peter W

    2007-03-14

    Vibrational absorption (VA) and vibrational circular dichroism (VCD) spectroscopy was applied in the analysis of vibrational and low lying electronic transitions of a triplet ground state cobalt(III) coordination compound. The spectroscopic measurements were performed on the tetrabutylammonium salt of (6S,7S)-1,3,5,8,10,12-hexaaza-2,4,9,11-tetraoxo-6,7-diphenyl-dodecanato(4-)cobaltate(III) in DMSO solution and in potassium bromide pellets. The chiral anion exhibits an unusual geometry for cobalt(III), being four-coordinate, planar, and paramagnetic with an intermediate spin state. The spectroscopic results were compared to measurements performed on the free ligand and to theoretical calculations using density functional theory (B3LYP/TZVP). The results of the VCD analysis of the coordination compound identified an electronic, dipole-forbidden, magnetic dipole-allowed low-lying d-d transition located in the mid infrared, as well as several amide stretch transitions located in the fingerprint region (1800-1100 cm(-1)), in both the liquid and solid phase. VCD signals were found to be 5-10 times higher than expected, indicating enhancement of the vibrational CD signals, caused by coupling of the vibrational transitions with the close-lying electronic transition.

  7. Circular dichroism readout of sugar recognition in the cleft of a fused-pyridine receptor

    OpenAIRE

    Tamaru, Shun-ichi; Shinkai, Seiji; Khasanov, Alisher B.; Bell, Thomas W.

    2002-01-01

    Dicarboxamide host 2 forms 1:1 complexes with n-octyl pyranosides derived from d-glucose, d-mannose, d-galactose, d-fucose, d-lyxose, and d-arabinose. Association constants (Ka) in the range of 77–940 M−1 were measured in chloroform by means of induced circular dichroism and fluorescence spectroscopy. Variations in Ka values correspond qualitatively to expected differences in hydrogen-bonding abilities of guest hydroxyl groups. Induced circular dichroism effects for...

  8. Fingerprinting the macro-organisation of pigment-protein complexes in plant thylakoid membranes in vivo by circular-dichroism spectroscopy.

    Science.gov (United States)

    Tóth, Tünde N; Rai, Neha; Solymosi, Katalin; Zsiros, Ottó; Schröder, Wolfgang P; Garab, Győző; van Amerongen, Herbert; Horton, Peter; Kovács, László

    2016-09-01

    Macro-organisation of the protein complexes in plant thylakoid membranes plays important roles in the regulation and fine-tuning of photosynthetic activity. These delicate structures might, however, undergo substantial changes during isolating the thylakoid membranes or during sample preparations, e.g., for electron microscopy. Circular-dichroism (CD) spectroscopy is a non-invasive technique which can thus be used on intact samples. Via excitonic and psi-type CD bands, respectively, it carries information on short-range excitonic pigment-pigment interactions and the macro-organisation (chiral macrodomains) of pigment-protein complexes (psi, polymer or salt-induced). In order to obtain more specific information on the origin of the major psi-type CD bands, at around (+)506, (-)674 and (+)690nm, we fingerprinted detached leaves and isolated thylakoid membranes of wild-type and mutant plants and also tested the effects of different environmental conditions in vivo. We show that (i) the chiral macrodomains disassemble upon mild detergent treatments, but not after crosslinking the protein complexes; (ii) in different wild-type leaves of dicotyledonous and monocotyledonous angiosperms the CD features are quite robust, displaying very similar excitonic and psi-type bands, suggesting similar protein composition and (macro-) organisation of photosystem II (PSII) supercomplexes in the grana; (iii) the main positive psi-type bands depend on light-harvesting protein II contents of the membranes; (iv) the (+)506nm band appears only in the presence of PSII-LHCII supercomplexes and does not depend on the xanthophyll composition of the membranes. Hence, CD spectroscopy can be used to detect different macro-domains in the thylakoid membranes with different outer antenna compositions in vivo.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-04-21

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

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

    Science.gov (United States)

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

    2015-04-01

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

  11. Characterization of the binding of metoprolol tartrate and guaifenesin drugs to human serum albumin and human hemoglobin proteins by fluorescence and circular dichroism spectroscopy.

    Science.gov (United States)

    Duman, Osman; Tunç, Sibel; Kancı Bozoğlan, Bahar

    2013-07-01

    The interactions of metoprolol tartrate (MPT) and guaifenesin (GF) drugs with human serum albumin (HSA) and human hemoglobin (HMG) proteins at pH 7.4 were studied by fluorescence and circular dichroism (CD) spectroscopy. Drugs quenched the fluorescence spectra of HSA and HMG proteins through a static quenching mechanism. For each protein-drug system, the values of Stern-Volmer quenching constant, bimolecular quenching constant, binding constant and number of binding site on the protein molecules were determined at 288.15, 298.15, 310.15 and 318.15 K. It was found that the binding constants of HSA-MPT and HSA-GF systems were smaller than those of HMG-MPT and HMG-GF systems. For both drugs, the affinity of HMG was much higher than that of HSA. An increase in temperature caused a negative effect on the binding reactions. The number of binding site on blood proteins for MPT and GF drugs was approximately one. Thermodynamic parameters showed that MPT interacted with HSA through electrostatic attraction forces. However, hydrogen bonds and van der Waals forces were the main interaction forces in the formation of HSA-GF, HMG-MPT and HMG-GF complexes. The binding processes between protein and drug molecules were exothermic and spontaneous owing to negative ∆H and ∆G values, respectively. The values of binding distance between protein and drug molecules were calculated from Förster resonance energy transfer theory. It was found from CD analysis that the bindings of MPT and GF drugs to HSA and HMG proteins altered the secondary structure of HSA and HMG proteins. PMID:23471625

  12. Study on the interaction of phthalate esters to human serum albumin by steady-state and time-resolved fluorescence and circular dichroism spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Xie, Xiaoyun [National Key Laboratory of Organic Chemistry, Lanzhou University, Lanzhou 730000 (China); College of Earth and Environmental Sciences, Lanzhou University, Lanzhou 730000 (China); Wang, Zhaowei [College of Earth and Environmental Sciences, Lanzhou University, Lanzhou 730000 (China); Zhou, Ximin; Wang, Xiaoru [National Key Laboratory of Organic Chemistry, Lanzhou University, Lanzhou 730000 (China); Chen, Xingguo, E-mail: chenxg@lzu.edu.cn [National Key Laboratory of Organic Chemistry, Lanzhou University, Lanzhou 730000 (China); Department of Chemistry, Lanzhou University, Lanzhou 730000 (China)

    2011-09-15

    Highlights: {center_dot} Molecular docking revealed PAEs to be located in the hydrophobic pocket of HSA. {center_dot} HSA-DMP had one class of binding sites while HSA-BBP and HSA-DEHP had two types. {center_dot} Hydrophobic and hydrogen interactions dominated in the association of HSA-PAEs. {center_dot} The lifetime of Trp residue of HSA decreased after the addition of PAEs. {center_dot} The presences of PAEs could alter the second structure of HSA. - Abstract: Phthalate esters (PAEs) are globally pervasive contaminants that are considered to be endocrine disruptor chemicals and toxic environmental priority pollutants. In this paper, the interactions between PAEs and human serum albumin (HSA) were examined by molecular modelling, steady state and time-resolved fluorescence, ultraviolet-visible spectroscopy (UV-vis) and circular dichroism spectroscopy (CD). The association constants between PAEs and HSA were determined using the Stern-Volmer and Scatchard equations. The binding of dimethyl phthalate (DMP) to HSA has a single class of binding site and its binding constants (K) are 4.08 x 10{sup 3}, 3.97 x 10{sup 3}, 3.45 x 10{sup 3}, and 3.20 x 10{sup 3} L mol{sup -1} at 289, 296, 303, and 310 K, respectively. The Stern-Volmer and Scatchard plots both had two regression curves for HSA-butylbenzyl phthalate (BBP) and HSA-di-2-ethylhexyl phthalate (DEHP), which indicated that these bindings were via two types of binding sites: the numbers of binding site for the first type were lower than for the second type. The binding constants of the first type binding site were higher than those of the second type binding site at corresponding temperatures, the results suggesting that the first type of binding site had high affinity and the second binding site involved other sites with lower binding affinity and selectivity. The thermodynamic parameters of the binding reactions ({Delta}G{sup o}, {Delta}H{sup o} and {Delta}S{sup o}) were measured, and they indicated the presences

  13. Uncertainty in measurement of protein circular dichroism spectra

    Science.gov (United States)

    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.

  14. The circular dichroism of ribosomal ribonucleic acids.

    Science.gov (United States)

    Cox, R A; Hirst, W; Godwin, E; Kaiser, I

    1976-05-01

    1. The c.d. (circular dichroism) of Drosophila melanogaster rRNA (42% G+C) and of G+C-rich fragments (78% G+C) obtained by partial hydrolysis of rabbit L-rRNA (the largest RNA species isolated from the large subribosomal particle) were measured and found to differ substantially. 2. To interpret these spectra a relation between c.d. of bihelical RNA and % G+C was derived, namely delta epsilonfG = AFG2+bfG+c, where deltaepsilonfG is the c.d. of RNA characterized by a mole fraction, fG, of guanine nucleotides and a, b and c are constants. 3. A frame of reference was established by studying the c.d. of a range of rRNA species, including S-rRNA (the RNA species isolated from the smaller subribosomal particle) and L-rRNA of Escherichia coli. 4. It was found for the rRNA species studied that 0.60+/-0.05 of residues appear to form bihelical secondary structure. 5. A higher helical content, 0.66+/-0.05, was found for the G+C-rich fragment of L-rRNA. The difference in the c.d. of rabbit L-rRNA and of D. melanogaster rRNA is attributable to the dependence of c.d. of the bihelical parts on %G+C. 6. The minimum in c.d. at 295 nm increases with increasing %G+C. The c.d. of rRNA was compared with that of the parent subparticle in this region of the spectrum, where high precision may be attained.

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

    Science.gov (United States)

    Abbate, Sergio; Longhi, Giovanna; Lebon, France; Tommasini, Matteo

    2012-09-01

    Apomorphine is a chiral drug molecule; notwithstanding its extraordinary importance, little attention has been paid to the characterization of its chiroptical properties. Here we report on its electronic circular dichroism (ECD) spectra, recorded in methanol and water, and vibrational circular dichroism (VCD) in methanol and dimethyl sulfoxide (DMSO) solutions. Density functional theory (DFT) calculations have allowed us to interpret the spectra and to evaluate the role of possible conformations, charge-states and interactions with counter ions.

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

    CERN Document Server

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

    2016-01-01

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

  17. Circular dichroism from Fano resonances in planar chiral oligomers

    Science.gov (United States)

    Hopkins, Ben; Poddubny, Alexander N.; Miroshnichenko, Andrey E.; Kivshar, Yuri S.

    2015-05-01

    Here we present a general approach for describing the physics of Fano resonances in nanoparticle oligomers. It is shown that the interference of nonorthogonal collective eigenmodes is a sufficient condition to produce Fano resonances. We then show that such nonorthogonality between eigenmodes also permits the existence of a new form circular dichroism in the absorption and scattering cross-sections, even when circular dichroism is forbidden in the extinction cross-section.

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

    Science.gov (United States)

    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.

  19. High orbital angular momentum quantum numbers in the electronic ground states of Fe$_2^+$ and Co$_2^+$ as determined by x-ray absorption and x-ray magnetic circular dichroism spectroscopy

    CERN Document Server

    Zamudio-Bayer, V; Langenberg, A; Lawicki, A; Terasaki, A; Issendorff, B v; Lau, J T

    2015-01-01

    The $^6\\Delta$ electronic ground state of the Co$_2^+$ diatomic molecular cation has been assigned experimentally by x-ray absorption and x-ray magnetic circular dichroism spectroscopy in a cryogenic ion trap. Three candidates, $^6\\Phi$, $^6\\Gamma$, and $^8\\Gamma$, for the electronic ground state of Fe$_2^+$ have been identified. These states carry sizable ground-state orbital angular momenta that disagree with theoretical predictions from multireference configuration interaction and density functional theory. Our results show that the ground states of neutral and cationic diatomic molecules of $3d$ elements cannot be assumed to be connected by a one-electron process.

  20. Large Enhancement of Circular Dichroism Using an Embossed Chiral Metamaterial

    CERN Document Server

    Mousavi, S Hamed Shams; El-Sayed, Mostafa A; Eftekhar, Ali A; Adibi, Ali

    2016-01-01

    In the close vicinity of a chiral nanostructure, the circular dichroism of a biomolecule could be greatly enhanced, due to the interaction with the local superchiral fields. Modest enhancement of optical activity using a planar metamaterial, with some chiral properties, and achiral nanoparticles has been previously reported. A more substantial chirality enhancement can be achieved in the local filed of a chiral nanostructure with a three-dimensional arrangement. Using an embossed chiral nanostructure designed for chiroptical sensing, we measure the circular dichroism spectra of two biomolecules, Chlorophylls A and B, at the molecular level, using a simple polarization resolved reflection measurement. This experiment is the first realization of the on-resonance surface-enhanced circular dichroism, achieved by matching the chiral resonances of a strongly chiral metamaterial with that of a chiral molecule, resulting in an unprecedentedly large differential CD spectrum from a monolayer of a chiral material.

  1. Circular dichroism as a means to follow DNA gymnastics: on the shoulders of giants

    Directory of Open Access Journals (Sweden)

    H.H. Klump

    2010-01-01

    Full Text Available This is the first report of DNA stem-loops self-assembled by ‘foot-loop’ interactions into either two-dimensional strings or three-dimensional spirals, distinguished by circular dichroism spectroscopy. All subunits are linked by cooperative Watson-Crick hydrogen bonds.

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

    Science.gov (United States)

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

    2016-10-01

    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.

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

    DEFF Research Database (Denmark)

    Pedersen, Jesper Goor; Mortensen, Asger

    2007-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  5. Circular dichroism of graphene oxide: the chiral structure model

    Institute of Scientific and Technical Information of China (English)

    Jing CAO; Hua-Jie YIN; Rui SONG

    2013-01-01

    We have observed the circular dichroism signal of dilute graphene oxide (GO), then systematically investigated the chirality of GO and established a probable chiral unit model, This study may open up a new field for understanding the structure of GO and lay the foundation for fabrication of GO-based materials.

  6. Optical activity and circular dichroism of plasmonic nanorod assemblies

    Science.gov (United States)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Bürck, Jochen, E-mail: jochen.buerck@kit.edu; Roth, Siegmar; Windisch, Dirk; Wadhwani, Parvesh; Moss, David [Karlsruhe Institute of Technology (KIT), POB 3640, D-76021 Karlsruhe (Germany); Ulrich, Anne S., E-mail: jochen.buerck@kit.edu [Karlsruhe Institute of Technology (KIT), POB 3640, D-76021 Karlsruhe (Germany); Karlsruhe Institute of Technology (KIT), Fritz-Haber-Weg 6, D-76131 Karlsruhe (Germany)

    2015-04-11

    UV-CD12 at ANKA and its current end-station are described, with a standard module for vacuum-UV synchrotron radiation circular dichroism of bio-macromolecules in the liquid state, and a unique module for macroscopically oriented lipid membranes (oriented circular dichroism). 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.

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

    Science.gov (United States)

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2012-09-11

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

  10. On the analysis of membrane protein circular dichroism spectra

    OpenAIRE

    Sreerama, Narasimha; Woody, Robert W.

    2004-01-01

    Analysis of circular dichroism spectra of proteins provides information about protein secondary structure. Analytical methods developed for such an analysis use structures and spectra of a set of reference proteins. The reference protein sets currently in use include soluble proteins with a wide range of secondary structures, and perform quite well in analyzing CD spectra of soluble proteins. The utility of soluble protein reference sets in analyzing membrane protein CD spectra, however, has ...

  11. Photoemission and magnetic circular dichroism studies of magnetic semiconductors

    Science.gov (United States)

    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.

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

    International Nuclear Information System (INIS)

    Full text: We investigated the effects of a strong circularly polarized 1064 nm laser field on electron capture and emission in slow (keV) proton-hydrogen collisions within a reduced-dimensionality model of the scattering system in which both the motion of the active electron and the laser electric field vector are confined to the scattering plane. During the collision, the proton is assumed to move on a straight-line trajectory with impact parameter b. The rotating laser electric field breaks the azimuthal symmetry, and the projectile either follows the rotating laser field ('co-rotating' collisions) or moves against the rotating electric field ('counter-rotating' collisions). By solving the time-dependent Schroedinger equation, we examined the probabilities for electron capture and ionization as a function of laser intensity, impact parameter, and the laser phase 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 the helicity of the circularly polarized laser light. For intensities above 2x1012 W/cm2, our model predicts a noticeable circular dichroism in the capture probability. Interestingly, this dichroism persists after averaging over . 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. For a fixed impact parameter, the capture probability as a function of φ shows large amplitude oscillations and differs from the field-free results most strikingly at φ = 0o and 180o. It displays a strong dichroism effect, i.e., a substantial difference in the electron capture probability for co-rotating as compared to counter-rotating collisions. Ionization

  13. Plasmonic nanohelix metamaterials with tailorable giant circular dichroism

    Science.gov (United States)

    Gibbs, J. G.; Mark, A. G.; Eslami, S.; Fischer, P.

    2013-11-01

    Plasmonic nanohelix arrays are shown to interact with electromagnetic fields in ways not typically seen with ordinary matter. Chiral metamaterials (CMMs) with feature sizes small with respect to the wavelength of visible light are a promising route to experimentally achieve such phenomena as negative refraction without the need for simultaneously negative ɛ and μ. Here we not only show that giant circular dichroism in the visible is achievable with hexagonally arranged plasmonic nanohelix arrays, but that we can precisely tune the optical activity via morphology and lattice spacing. The discrete dipole approximation is implemented to support experimental data.

  14. Circular dichroism in XUV + IR multiphoton ionization of atoms

    International Nuclear Information System (INIS)

    Circular dichroism (CD) is theoretically considered for two-colour multiphoton ionization of arbitrary atomic subshells. In particular, p-subshell ionization is analysed and compared with s-subshell ionization. Simple analytical expressions for the CD are obtained for both s- and p-subshell ionization. The calculations performed for Ne(2p) ionization by an extreme ultraviolet pulse in the presence of an infrared laser pulse show that the CD in this case is appreciably larger than in previously discussed s-shell ionization. It makes this case favourable for applications as a sensitive tool for measuring the helicity of short-wavelength free-electron laser beams. (paper)

  15. Calculation of magnetic circular dichroism of rare-earth elements

    International Nuclear Information System (INIS)

    We present atomic calculations for the magnetic circular dichroism (MCD) in the 4d→4f excitation region of Eu, Gd, Tb, Dy, and Ho metal. The spectral shapes at T=0 K for non-polarized, right and left circularly polarized light, and their difference spectra are given. The interference effect between the 4d→4f excitation followed by 4d-4f4f super-Coster-Kronig decay process and the 4f→εg direct excitation process, which is known as the Fano effect, is considered in the calculations. The result reproduces the overall features of recently measured experiments. It is essential to consider the Fano effect for the understanding of the heavy rare-earth 4d→4f absorption and their MCD. (author)

  16. 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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  18. Vibrational Circular Dichroism Absolute Configuration of 9,12-Cyclomulin-13-ol, a Diterpene from Azorella and Laretia Species.

    Science.gov (United States)

    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.

  19. A new multichannel detector for proteomics studies and circular dichroism

    International Nuclear Information System (INIS)

    The conventional instrument for the measurement of Circular Dichroism (CD) comprises of a single anode photomultiplier tube (PMT) detector connected to a 'lock-in' amplifier. This requires the sequential scanning across the wavelength spectrum, making it a useful method for structure determination but not for time-resolved measurements and the observation of structural changes. In this paper, we report on our progress to develop a novel system based on a semiconductor linear array detector that will overcome the limitations of the conventional systems and will allow for the observation of dynamic phenomena to the time limits imposed by the technique itself, i.e. 20 μs with conventional light modulation methods. Our final aim is to develop an instrument that will enable the simultaneous measurement of both spectroscopic and time resolved CD by the realisation of energy-dispersive experiments (EDE-CD)

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

    Science.gov (United States)

    Mendicuti, Francisco; Gonzalez-Alvarez, Maria Jose

    2010-01-01

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

  1. Circular dichroism and fluorescence spectroscopy of cysteinyl-tRNA synthetase from Halobacterium salinarum ssp. NRC-1 demonstrates that group I cations are particularly effective in providing structure and stability to this halophilic protein.

    Directory of Open Access Journals (Sweden)

    Christopher J Reed

    Full Text Available Proteins from extremophiles have the ability to fold and remain stable in their extreme environment. Here, we investigate the presence of this effect in the cysteinyl-tRNA synthetase from Halobacterium salinarum ssp. NRC-1 (NRC-1, which was used as a model halophilic protein. The effects of salt on the structure and stability of NRC-1 and of E. coli CysRS were investigated through far-UV circular dichroism (CD spectroscopy, fluorescence spectroscopy, and thermal denaturation melts. The CD of NRC-1 CysRS was examined in different group I and group II chloride salts to examine the effects of the metal ions. Potassium was observed to have the strongest effect on NRC-1 CysRS structure, with the other group I salts having reduced strength. The group II salts had little effect on the protein. This suggests that the halophilic adaptations in this protein are mediated by potassium. CD and fluorescence spectra showed structural changes taking place in NRC-1 CysRS over the concentration range of 0-3 M KCl, while the structure of E. coli CysRS was relatively unaffected. Salt was also shown to increase the thermal stability of NRC-1 CysRS since the melt temperature of the CysRS from NRC-1 was increased in the presence of high salt, whereas the E. coli enzyme showed a decrease. By characterizing these interactions, this study not only explains the stability of halophilic proteins in extremes of salt, but also helps us to understand why and how group I salts stabilize proteins in general.

  2. Soft x-ray magnetic circular dichroism study of Cr tellurides

    OpenAIRE

    Yaji, Koichiro; Kimura, Akio; Koyama, Michie; Hirai, Chiyuki; Sato, Hitoshi; Shimada, Kenya; Tanaka, Arata; Taniguchi, Masaki

    2005-01-01

    Ferromagnetic chromium tellurides Cr5 Te6 (δ=0.17) and Cr2 Te3 (δ=0.33) have been investigated by Cr 2p x-ray absorption spectroscopy and x-ray magnetic circular dichroism (XMCD). The observed XMCD spectra have been analyzed by means of a configuration-interaction cluster model calculation. From calculated results, we suggest that the doped holes created by the Cr deficiency exist mainly in the Te 5p orbital of Cr1-δ Te.

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

    Science.gov (United States)

    Niederhausen, Thomas; Feuerstein, Bernold; Thumm, Uwe

    2004-08-01

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

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

    Science.gov (United States)

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

    2016-08-01

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

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

    Science.gov (United States)

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

    2016-01-01

    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

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

    Science.gov (United States)

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

    2016-06-01

    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.

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

    Science.gov (United States)

    Rafiee Fanood, Mohammad M; Janssen, Maurice H M; Powis, Ivan

    2015-04-14

    Limonene is ionized by circularly polarized 420 nm femtosecond laser pulses. Ion mass and photoelectron energy spectra identify the dominant (2 + 1) multiphoton ionization mechanism, aided by TDDFT calculations of the Rydberg excitations. Photoelectron circular dichroism measurements on pure enantiomers reveal a chiral asymmetry of ±4 %. PMID:25744283

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

    Directory of Open Access Journals (Sweden)

    Tatyana G Karabencheva-Christova

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

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

    Energy Technology Data Exchange (ETDEWEB)

    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

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

    Energy Technology Data Exchange (ETDEWEB)

    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

  11. Ligand induced circular dichroism and circularly polarized luminescence in CdSe quantum dots.

    Science.gov (United States)

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

    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.

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

    DEFF Research Database (Denmark)

    Kaminski, Maciej; Cukras, Janusz; Pecul, Magdalena;

    2015-01-01

    on the response function formalism and is implemented at the level of time-dependent density functional theory. It has been employed to calculate the spin-forbidden circular dichroism and circularly polarized phosphorescence signals of valence n - p* and n ’ p* transitions, respectively, in several chiral enones......We present a computational methodology to calculate the intensity of circular dichroism (CD) in spinforbidden absorption and of circularly polarized phosphorescence (CPP) signals, a manifestation of the optical activity of the triplet–singlet transitions in chiral compounds. The protocol is based...... structure. In many cases the sign of the spin-forbidden CD and CPP signals are opposite. For the b,g-enones under investigation, where there are two minima on the lowest triplet excited state potential energy surface, each minimum exhibits a CPP signal of a different sign....

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

    Science.gov (United States)

    Abriata, Luciano A.

    2011-01-01

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

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

    DEFF Research Database (Denmark)

    Jalkanen, Karl J.

    2003-01-01

    , similar to the characteristic features in electronic circular dichroism spectra with respect to those in the UV-vis electronic absorption spectra. Finally, we have also attempted to stabilize the zwitterionic species by treating the aqueous environment by using a continuum solvent approach, the Onsager...

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

    DEFF Research Database (Denmark)

    Nesgaard, Lise W.; Hoffmann, Søren Vrønning; Andersen, Christian Beyschau;

    2008-01-01

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

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

    DEFF Research Database (Denmark)

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

    2015-01-01

    A successful elucidation of the near-ultraviolet electronic circular dichroism spectrum of a short double-stranded DNA is reported. Time-dependent density functional theory methods are shown to accurately predict spectra and assign bands on the microscopic base-pair scale, a finding that opens the...

  17. Circular dichroism study on the diastereoselective self-assembly of bacteriochlorophyll cs

    Science.gov (United States)

    Balaban, Teodor S.; Holzwarth, Alfred R.; Schaffner, Kurt

    1995-04-01

    Circular dichroism (CD) spectra of self-assembled bacteriochlorophyll cs (BChl cs) aggregates show a pronounced dependency on the solvent, the concentration and on the stereochemistry of the 3 1-hydroxy groups. In n-hexane a psi-type CD is obtained due to the formation of nanostructural aggregates.

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

    DEFF Research Database (Denmark)

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

    2012-01-01

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

  19. Detection Limits for Natural Circular Dichroism of Chiral Complexes in the X-ray Range

    NARCIS (Netherlands)

    Goulon, José; Sette, Francesco; Moise, Claude; Fontaine, Alain; Perey, Danièle; Rudolf, Petra; Baudelet, François

    1993-01-01

    Whereas both Magnetic Circular Dichroism and Faraday Rotation studies have been successfully carried out at the K-, L- and M- absorption edges of metal atoms in ferromagnetic systems, Natural optical activity of chiral complexes has not yet been detected quite unambiguously in the X-ray range. We re

  20. Magnetic Circular Dichroism in Resonant Raman Scattering in the Perpendicular Geometry at the L edge of 3d Transition Metal Systems

    International Nuclear Information System (INIS)

    We measured circular dichroism in resonant x-ray scattering 3dn→2p53dn+1→3s13dn+1 with incidence perpendicular to the magnetization where the absorption dichroism vanishes. The advantages of photon scattering over other techniques make it possible to study a wide range of materials. The Ni L3 dichroism in NiFe2O 4 is (28±5)% in agreement with a localized model. In the metal Co the dichroism is reduced to (10.4±1)% (L3) and (6.8±1.5)% (7.5 eV above L3 ), indicating a large sensitivity to the nature of the valence states despite the fact that this spectroscopy is based on inner shell transitions. copyright 1999 The American Physical Society

  1. Solvent-induced conformational changes in cyclic peptides: a vibrational circular dichroism study.

    Science.gov (United States)

    Merten, Christian; Li, Fee; Bravo-Rodriguez, Kenny; Sanchez-Garcia, Elsa; Xu, Yunjie; Sander, Wolfram

    2014-03-28

    The three-dimensional structure of a peptide is strongly influenced by its solvent environment. In the present study, we study three cyclic tetrapeptides which serve as model peptides for β-turns. They are of the general structure cyclo(Boc-Cys-Pro-X-Cys-OMe) with the amino acid X being either glycine (1), or L- or D-leucine (L- or D-2). Using vibrational circular dichroism (VCD) spectroscopy, we confirm previous NMR results which showed that D-2 adopts predominantly a βII turn structure in apolar and polar solvents. Our results for L-2 indicate a preference for a βI structure over βII. With increasing solvent polarity, the preference for 1 is shifted from βII towards βI. This conformational change goes along with the breaking of an intramolecular hydrogen bond which stabilizes the βII conformation. Instead, a hydrogen bond with a solvent molecule can stabilize the βI turn conformation. PMID:24513908

  2. Circular dichroism spectra of langasite family crystals in the range of electronic transitions of structure defects

    International Nuclear Information System (INIS)

    The absorption and circular dichroism spectra of langasite family crystals are studied. Wide bands in the range of 285-500 nm that are related to the structure lattice defects are found. For all the crystals, these bands are in approximately the same spectral region, have identical structures, and can be attributed to one type of defects formed by cation vacancies and excess oxygen atoms in the optically active positions.

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

    CERN Document Server

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

    2016-01-01

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

  4. Fano resonance assisting plasmonic circular dichroism from nanorice heterodimers for extrinsic chirality

    OpenAIRE

    Li Hu; Yingzhou Huang; Liang Fang; Guo Chen; Hua Wei; Yurui Fang

    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 la...

  5. Circular magnetic dichroism of the Fa center adsorption in KCl doped with Li and Na

    International Nuclear Information System (INIS)

    The spin-orbit structure of FA in KCl:Li and KCl:Na have been studied by means of the magnetic circular dichroism. Due to their C4V, symmetry the FA centers have two different spin-orbit parameters, Δ* and Δ*, which only in the KCl:Li case follow the relation: Δ* F A centers have been determined using the method of moment

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

    NARCIS (Netherlands)

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

    1992-01-01

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

  7. High-Flux Beamline for Ultraviolet and Vacuum-Ultraviolet Circular Dichroism at NSRL

    International Nuclear Information System (INIS)

    This paper describes the commissioning and characterization of an NSRL bending magnet beamline constructed for the measurement of vacuum-ultraviolet circular dichroism on biological and other materials. The beamline provides high fluxes of ultraviolet and vacuum-ultraviolet radiation, which is converted into plane polarized light using a polarizer and subsequently converted into circularly polarized light using a photoelastic modulator with a switching frequency of 50 kHz. The beamline has the best wavelength resolution of 0.3 nm and stray light levels better than 0.03%. Example spectra of (1s)-(+)-10-camphorsulphonic acid (CSA) and myoglobin are given

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

    CERN Document Server

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

    2013-01-01

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

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

    DEFF Research Database (Denmark)

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

    2008-01-01

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

  10. Surface characterization of human serum albumin and sodium perfluorooctanoate mixed solutions by pendant drop tensiometry and circular dichroism.

    Science.gov (United States)

    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. X-ray magnetic circular dichroism strongly influenced by non-magnetic cover layers

    Energy Technology Data Exchange (ETDEWEB)

    Zafar, K.; Audehm, P.; Schütz, G. [Max-Planck-Institute for Intelligent Systems (Former Metals Research), Stuttgart 70569 (Germany); Goering, E., E-mail: goering@is.mpg.de [Max-Planck-Institute for Intelligent Systems (Former Metals Research), Stuttgart 70569 (Germany); Pathak, M.; Chetry, K.B.; LeClair, P.R.; Gupta, A. [MINT Center, University of Alabama, Tuscaloosa, AL 35487 (United States)

    2013-12-15

    Highlights: •Energy filtering gives much larger sampling depth and escape length as expected. •XMCD sum rules could be dramatically altered by this effect. •Strong enhanced effective escape length for buried layers. •A “universal curve” model gives semi quantitative understanding. •Buried layers are more sensitive to self-absorption phenomena. -- Abstract: Total electron yield (TEY) is the dominating measurement mode in soft X-ray absorption spectroscopy (XAS), where the sampling depth is generally assumed to be quite small and constant, and the related self-absorption or saturation phenomena are about to be negligible at normal incidence conditions. From the OK edge to CrL{sub 2,3} edge XAS ratio we determined a strong change in the effective electron escape length between an uncovered and a RuO{sub 2} covered CrO{sub 2} sample. This effect has been explained by a simple electron energy filtering model, providing a semi quantitative description. In addition, this simple model can quantitatively describe the unexpected reduced and positive CrL{sub 2,3} X-ray magnetic circular dichroism (XMCD) signal of a RuO{sub 2}/CrO{sub 2} bilayer, while previous results have identified a clear negative Cr magnetization at the RuO{sub 2}/CrO{sub 2} interface. In our case this escape length enhancement has strong impact on the XMCD sum rule results and in general it provides much deeper sampling depth, but also larger self-absorption or saturation effects.

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

    Energy Technology Data Exchange (ETDEWEB)

    Lehmann, C. Stefan; Ram, N. Bhargava; Janssen, Maurice H. M., E-mail: m.h.m.janssen@vu.nl [LaserLaB Amsterdam, VU University Amsterdam, De Boelelaan 1081, 1081 HV Amsterdam (Netherlands); Powis, Ivan [School of Chemistry, University of Nottingham, Nottingham NG7 2RD (United Kingdom)

    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

  13. X-ray magnetic circular dichroism in (Ge,Mn) compounds: Experiments and modeling

    Energy Technology Data Exchange (ETDEWEB)

    Tardif, Samuel, E-mail: samuel.tardif@spring8.or.jp [Univ. Grenoble Alpes, Inst NEEL, F-38042 Grenoble (France); CNRS, Inst NEEL, F-38042 Grenoble (France); SP2M, INAC, CEA-UJF, F-38054 Grenoble (France); Titov, Andrey [Univ. Grenoble Alpes, Inst NEEL, F-38042 Grenoble (France); CNRS, Inst NEEL, F-38042 Grenoble (France); SP2M, INAC, CEA-UJF, F-38054 Grenoble (France); A. M. Prokhorov General Physics Institute, Russian Academy of Sciences, 38 Vavilov Street, Moscow 119991 (Russian Federation); Arras, Emmanuel; Slipukhina, Ivetta [SP2M, INAC, CEA-UJF, F-38054 Grenoble (France); Hlil, El-Kébir [Univ. Grenoble Alpes, Inst NEEL, F-38042 Grenoble (France); CNRS, Inst NEEL, F-38042 Grenoble (France); Cherifi, Salia [IPCMS, CNRS-UdS, 23 rue du Loess, F-67034 Strasbourg (France); Joly, Yves [Univ. Grenoble Alpes, Inst NEEL, F-38042 Grenoble (France); CNRS, Inst NEEL, F-38042 Grenoble (France); Jamet, Matthieu; Barski, André [SP2M, INAC, CEA-UJF, F-38054 Grenoble (France); Cibert, Joël [Univ. Grenoble Alpes, Inst NEEL, F-38042 Grenoble (France); CNRS, Inst NEEL, F-38042 Grenoble (France); Kulatov, Erkin [A. M. Prokhorov General Physics Institute, Russian Academy of Sciences, 38 Vavilov Street, Moscow 119991 (Russian Federation); Uspenskii, Yurii A. [P. N. Lebedev Physical Institute, Russian Academy of Sciences, 53 Avenue Leninskii, Moscow 119991 (Russian Federation); Pochet, Pascal, E-mail: pascal.pochet@cea.fr [SP2M, INAC, CEA-UJF, F-38054 Grenoble (France)

    2014-03-15

    X-ray absorption (XAS) and x-ray magnetic circular dichroism (XMCD) spectra at the L{sub 2,3} edges of Mn in (Ge,Mn) compounds have been measured and are compared to the results of first principles calculation. Early ab initio studies show that the Density Functional Theory (DFT) can very well describe the valence band electronic properties but fails to reproduce a characteristic change of sign in the L{sub 3} XMCD spectrum of Mn in Ge{sub 3}Mn{sub 5}, which is observed in experiments. In this work we demonstrate that this disagreement is partially related to an underestimation of the exchange splitting of Mn 2p core states within the local density approximation. It is shown that the change in sign experimentally observed is reproduced if the exchange splitting is accurately calculated within the Hartree–Fock approximation, while the final states can be still described by the DFT. This approach is further used to calculate the XMCD in different (Ge,Mn) compounds. It demonstrates that the agreement between experimental and theoretical spectra can be improved by combining state of the art calculations for the core and valence states respectively. - Highlights: • X-ray absorption and magnetic circular dichroism spectra are measured and compared to first principles calculations in (Ge,Mn) compounds. • Standard density functional theory fails in properly describing peculiar features observed in the experiment. • A new approach to calculate theoretical X-ray absorption and magnetic circular dichroism spectra is proposed. • Improved modeling of the core levels splitting using the Hartree–Fock approximation allows for a better matching with the experiment. • This new method could be generalized to any 3d metallic-like system.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2010-01-11

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

  15. Circular dichroism and infrared spectroscopic characterization of secondary structure components of protein Z during mashing and boiling processes.

    Science.gov (United States)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-01-28

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

  17. Circular dichroism spectroscopic studies on structures formed by telomeric DNA sequences in vitro

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    Telomere plays an important role in cellular processes, such as cell aging, death and carcinogenisis. Having special sequences, it can form quadruplex structure in vitro. Circular dichroism (CD) spectroscopic studies show that TTAGGG, (TTAGGG)2 and (TTAGGG)4 can all form quadruplex in vitro and exist mainly as parallel quadruplex without metal ions. Both K+ and Na+ can stabilize the tetrameric structure and facilitate the forming of anti-parallel conformation. Furthermore, the conformations of quadruplex can also be affected by sequence length, the nature and concentration of metal ions.

  18. The design and commissioning of the vacuum-ultraviolet circular dichroism facility at NSRL

    International Nuclear Information System (INIS)

    This paper describes the design and commissioning of the vacuum-ultraviolet circular dichroism facility at NSRL. At 0.5nm resolution, the normal incident beamline can provide ultraviolet and vacuum-ultraviolet radiation at fluxes higher than 1012ph/s, which is converted into the plane polarized light using a polarizer and subsequently converted into the circularly polarized light using a photoelastic modulator with a switching frequency of 50 kHz. Example spectra of (1s)-(+)-10-camphorsulphonic acid (CSA) and myoglobin are given. Normally, the measurable wavelength range is 178--300 nm. But the short wavelength limit can be shifted to 140nm by using special solvent and short light-pass sample cell. (authors)

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

    Directory of Open Access Journals (Sweden)

    Loret Erwann P

    2008-09-01

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

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

    Science.gov (United States)

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

    2013-08-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2004-09-15

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

  2. Energy-dispersive phase plate for magnetic circular dichroism experiments in the X-ray range

    International Nuclear Information System (INIS)

    A 220 diamond phase plate was combined with an energy-dispersive absorption spectrometer to convert linearly polarized X-rays into circularly polarized photons and to detect circular magnetic X-ray dichroism (CMXD) from ferromagnetic samples. In these experiments, carried out at LURE, the energy-dispersive spectrometer was equipped with a bent Si (311) polychromator and vertically collimating slits accepting essentially a linearly polarized incident beam. The quarter-wave plate was operated in the Bragg geometry but well outside the range of quasi total reflection, with the consequence that the forward-diffracted beam was circularly polarized with a polarization rate approaching 80% over the whole energy bandpass of the polychromator. CMXD spectra of GdFe2 and GdCo2 intermetallic compounds were recorded at ca 7.2 keV near the Gd LIII absorption edge: they are essentially identical to the spectra commonly recorded with elliptically polarized X-ray photons collected out of the orbit plane of the storage ring. It is suggested that the energy-dispersive phase plate will be very useful to detect CMXD spectra with energy-dispersive spectrometers exploiting the well collimated linearly polarized emission of standard undulators installed on the storage rings of the third generation. (orig.)

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

    Science.gov (United States)

    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. Stability of some Cactaceae proteins based on fluorescence, circular dichroism, and differential scanning calorimetry measurements.

    Science.gov (United States)

    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

  5. Photoemission and core-level magnetic circular dichroism studies of diluted magnetic semiconductors

    Energy Technology Data Exchange (ETDEWEB)

    Fujimori, A. [Department of Complexity Science and Engineering, Universtiy of Tokyo, 1-5-1 Kashiwanoha, Kashiwa, Chiba 277-8561 (Japan) and Synchrotron Radiation Research Center, Japan Atomic Energy Research Institute, SPring-8, Mikazuki, Hyogo 679-5148 (Japan)]. E-mail: fujimori@phys.s.u-tokyo.ac.jp; Okabayashi, J. [Department of Applied Chemistry, University of Tokyo, 7-3-1 Hongo, Bunkyou-ku, Tokyo 113-8656 (Japan); Takeda, Y. [Synchrotron Radiation Research Center, Japan Atomic Energy Research Institute, SPring-8, Mikazuki, Hyogo 679-5148 (Japan); Mizokawa, T. [Department of Complexity Science and Engineering, Universtiy of Tokyo, 1-5-1 Kashiwanoha, Kashiwa, Chiba 277-8561 (Japan); Okamoto, J. [Synchrotron Radiation Research Center, Japan Atomic Energy Research Institute, SPring-8, Mikazuki, Hyogo 679-5148 (Japan); Mamiya, K. [Photon Factory, IMSS, High Energy Accelerator Research Organization, Tsukuba, Ibaraki 305 (Japan); Saitoh, Y. [Synchrotron Radiation Research Center, Japan Atomic Energy Research Institute, SPring-8, Mikazuki, Hyogo 679-5148 (Japan); Muramatsu, Y. [Synchrotron Radiation Research Center, Japan Atomic Energy Research Institute, SPring-8, Mikazuki, Hyogo 679-5148 (Japan); Oshima, M. [Department of Applied Chemistry, University of Tokyo, 7-3-1 Hongo, Bunkyou-ku, Tokyo 113-8656 (Japan); Ohya, S. [Department of Electronic Engineering, University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan); Tanaka, M. [Department of Electronic Engineering, University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan)

    2005-06-15

    An overview is given on the photoemission studies of the electronic structure of diluted magnetic semiconductors (DMS's), in particular of the prototypical ferromagnetic DMS Ga{sub 1-x}Mn{sub x}As. Configuration-interaction cluster-model analyses of the photoemission data allow us to estimate the p-d exchange coupling constant and hence to predict how to increase the Curie temperature in new materials. Spectra near the Fermi level combined with the transport and optical properties suggest a highly incoherent metallic state for the ferromagnetic metallic phase. It is shown that new insight into the chemically and magnetically inhomogeneous states of DMS's can be gained by the temperature and magnetic field dependence of core-level magnetic circular dichroism signals.

  6. X-Ray Magnetic Circular Dichroism Measurement of Fe-Co Alloy Films Prepared by Electrodeposition

    Institute of Scientific and Technical Information of China (English)

    LI Zong-Mu; XU Fa-Qiang; WANG Li-Wu; WANG Jie; ZHU Jun-Fa; ZHANG Wen-Hua

    2007-01-01

    The macro- and micro-magnetic properties of Fe-Co alloy films eletrodeposited on GaAs(100) are studied by synchrotron radiation x-ray magnetic circular dichroism (XMCD) in combination with the magneto-optical Kerr effect (MOKE) measurements and magnetic force microscopy (MFM). The orbital and spin magnetic moments of each element in the Fe-Co alloy are determined by the sum rules of XMCD. Element-specific hysteresis loops (ESHL) are obtained by recording the La MCD signals as a function of applied magnetic field. MOKE results reveal that the amorphous films are magnetically isotropic in the surface plane. The MFM image shows that the dimension of the magnetic domains is about 1-2 μm, which is much larger than that of the grains, indicating that there are intergranular correlations among these grains. Both ESHL and MOKE hysteresis loops indicate the strong ferromagnetic coupling of Fe and Co in the alloy films.

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

    CERN Document Server

    Ganesan, Aravindhan; Wang, Feng

    2013-01-01

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

  8. Light flux density threshold at which protein denaturation is induced by synchrotron radiation circular dichroism beamlines.

    Science.gov (United States)

    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.

  9. Detection of magnetic circular dichroism on the two-nanometer scale

    Science.gov (United States)

    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).

  10. Stability of some Cactaceae proteins based on fluorescence, circular dichroism, and differential scanning calorimetry measurements.

    Science.gov (United States)

    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.

  11. Vibrational circular dichroism of tetraphenylporphyrin in peptide complexes? A computational study.

    Science.gov (United States)

    Bour, P; Záruba, K; Urbanová, M; Setnicka, V; Matejka, P; Fiedler, Z; Král, V; Volka, K

    2000-05-01

    The Raman and absorption spectra of tetraphenylporphyrin (TPP) were calculated and compared to experiment. The computation was based on the harmonic molecular force field and electric tensors obtained ab initio at the BPW91/6-31G* level. Good agreement was found between experimental and calculated frequencies and intensities. In order to estimate whether induced optical activity in chiral complexes interferes with the signal of peptide vibrations, the vibrational circular dichroism (VCD) spectra of TPP were simulated. The magnetic field perturbation theory (MFP) and the gauge-invariant atomic orbitals (GIAO) were used for the simulation. Such spectra were compared to theoretical VCD intensities of a model tripeptide as well to experimental spectra of a complex of the peptide and tetrakis(p-sulfonatophenyl)porphyrin (TSPP). No significant contribution to VCD signal from the TPP residue was found in experimental spectra. Thus, possible peptide conformational changes occurring during the complexation can be monitored directly in the amide I frequency region. PMID:10790189

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

    Directory of Open Access Journals (Sweden)

    H. S. Hsu

    2012-09-01

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

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

    CERN Document Server

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

    2016-01-01

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

  14. Circular dichroism and Raman spectroscopic study of the spider venom toxin V50F17

    Science.gov (United States)

    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.

  15. Infrared, Raman and ultraviolet with circular dichroism analysis and theoretical calculations of tedizolid

    Science.gov (United States)

    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.

  16. Photoelectron circular dichroism of bicyclic ketones from multiphoton ionization with femtosecond laser pulses.

    Science.gov (United States)

    Lux, Christian; Wollenhaupt, Matthias; Sarpe, Cristian; Baumert, Thomas

    2015-01-12

    Photoelectron circular dichroism (PECD) is a CD effect up to the ten-percent regime and shows contributions from higher-order Legendre polynomials when multiphoton ionization is compared to single-photon ionization. We give a full account of our experimental methodology for measuring the multiphoton PECD and derive quantitative measures that we apply on camphor, fenchone and norcamphor. Different modulations and amplitudes of the contributing Legendre polynomials are observed despite the similarity in chemical structure. In addition, we study PECD for elliptically polarized light employing tomographic reconstruction methods. Intensity studies reveal dissociative ionization as the origin of the observed PECD effect, whereas ionization of the intermediate resonance is dominating the signal. As a perspective, we suggest to make use of our tomographic data as an experimental basis for a complete photoionization experiment and give a prospect of PECD as an analytic tool. PMID:25492564

  17. Optically detected electron paramagnetic resonance by microwave modulated magnetic circular dichroism

    Science.gov (United States)

    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.

  18. Fano resonance assisting plasmonic circular dichroism from nanorice heterodimers for extrinsic chirality

    CERN Document Server

    Hu, Li; 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.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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

  1. 4-Arylflavan-3-ols as Proanthocyanidin Models: Absolute Configuration via Density Functional Calculation of Electronic Circular Dichroism

    Science.gov (United States)

    Density functional theory/B3LYP has been employed to optimize the conformations of selected 4-arylflavan-3-ols and their phenolic methyl ether 3-O-acetates. The electronic circular dichroism spectra of the major conformers have been calculated using time-dependent density functional theory to valida...

  2. Understanding the changes in the circular dichroism of light harvesting complex IIupon varying its pigment composition and organization

    NARCIS (Netherlands)

    Georgakopoulou, S.; Zwan, van der G.; Bassi, R.; Grondelle, van R.; Amerongen, van H.; Croce, R.

    2007-01-01

    In this work we modeled the circular dichroism (CD) spectrum of LHCII, the main light harvesting antenna of photosystem II of higher plants. Excitonic calculations are performed for a monomeric subunit, taken from the crystal structure of trimeric LHCII from spinach. All of the major features of the

  3. Synthesis and vibrational circular dichroism of enantiopure chiral oxorhenium(V) complexes containing the hydrotris(1-pyrazolyl)borate ligand

    DEFF Research Database (Denmark)

    Lassen, Peter Rygaard

    2006-01-01

    The infrared and vibrational circular dichroism (VCD) spectra of six chiral oxorhenium(V) complexes, bearing a hydrotris(1-pyrazolyl)borate (Tp) ligand, have been investigated. These complexes are promising candidates for observation of parity violation (symmetry breaking due to the weak nuclear ...

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

    NARCIS (Netherlands)

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

    1996-01-01

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

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

    KAUST Repository

    Furumaki, Shu

    2012-12-06

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

  6. Circular and elliptical dichroism effects in two-photon disintegration of atoms and molecules

    International Nuclear Information System (INIS)

    Full text: Compact convenient for the analysis expressions for the cross sections considerably simplify studying the interaction of electromagnetic radiation with atomic systems and allow us to discover some fine effects. In the present paper on the basis of the general symmetry considerations taking only into account the dipole approximation and without any other approximations used in atomic calculations we derive the compact invariant expressions for the angular distribution of photoelectrons escaping from atoms or molecules in the process of two-photon ionization and for the angular distribution of fragments forming under two-photon two-particle dissociation of molecules. The dependence on all geometric parameters - the unit vector p determining the direction of photoelectron (photofragments in the case of dissociation) motion, k specifying the direction of propagation for the electromagnetic radiation and the unit complex vector e specifying polarization of the radiation - is completely separated in the angular distributions in the form of scalar and triple scalar products of the vectors. The information of the intrinsic structure of the atomic system is included in few constant dynamic parameters of the system that can independently be calculated using the well-known approximations. In case of atoms and optically inactive molecules the angular distributions contain the term linear in the pseudoscalar degree of circular polarization of the electromagnetic radiation ξik · (e x e*): ξaRe[k · (p x e)(p · e*)], where a is a scalar dynamic parameter of the atomic system. The term leads to the interesting effect of elliptical dichroism in the angular distribution of photoelectrons (photo-fragments of the molecule): under elliptical polarization of the radiation, 0 1ξk · p + b2ξk · p(|p · e|2 - 1/5), where b1 and b2 are the pseudoscalar dynamic parameters of the chiral molecule. The terms (2) do not vanish in case of circular polarization and, therefore

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

    Science.gov (United States)

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

    2016-05-01

    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.

  8. Site-specific conformational determination in thermal unfolding studies of helical peptides using vibrational circular dichroism with isotopic substitution

    Science.gov (United States)

    Silva, R. A. G. D.; Kubelka, Jan; Bour, Petr; Decatur, Sean M.; Keiderling, Timothy A.

    2000-01-01

    Understanding the detailed mechanism of protein folding requires dynamic, site-specific stereochemical information. The short time response of vibrational spectroscopies allows evaluation of the distribution of populations in rapid equilibrium as the peptide unfolds. Spectral shifts associated with isotopic labels along with local stereochemical sensitivity of vibrational circular dichroism (VCD) allow determination of the segment sequence of unfolding. For a series of alanine-rich peptides that form α-helices in aqueous solution, we used isotopic labeling and VCD to demonstrate that the α-helix noncooperatively unwinds from the ends with increasing temperature. For these blocked peptides, the C-terminal is frayed at 5°C. Ab initio level theoretical simulations of the IR and VCD band shapes are used to analyze the spectra and to confirm the conformation of the labeled components. The VCD signals associated with the labeled residues are amplified by coupling to the nonlabeled parts of the molecule. Thus small labeled segments are detectable and stereochemically defined in moderately large peptides in this report of site-specific peptide VCD conformational analysis. PMID:10880566

  9. International comparability in spectroscopic measurements of protein structure by circular dichroism: CCQM-P59.1

    Science.gov (United States)

    Ravi, Jascindra; Rakowska, Paulina D.; Garfagnini, Tommaso; Baron, Bruno; Charlet, Philippe; Jones, Christopher; Milev, Stoyan; DeSa Lorenz, Julie; Plusquellic, David; Wien, Frank; Wu, Liqing; Meuse, Curtis W.; Knight, Alex E.

    2010-12-01

    Circular dichroism (CD) 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. A previous inter-laboratory study, CCQM-P59, showed that there was a poor level of comparability between laboratories in CD spectroscopy. In a follow-up study reported here, we achieved our goal of demonstrating improved comparability and data quality, primarily by addressing the problems identified in the previous study, which included cell path-length measurement, instrument calibration and good practice in general. Multivariate analysis techniques (principal component analysis and soft independent modelling of class analogies) were shown to be useful in comparing large spectral data sets and in classifying spectra. However, our results also show that there is more work to be done to improve confidence in the technique as the discrepancies observed were partially due to systematic effects, which the statistical approaches do not consider. We therefore conclude that there is a need for an improved understanding of the uncertainties in CD measurement.

  10. Dimethyl Sulfoxide Induced Destabilization and Disassembly of Various Structural Variants of Insulin Fibrils Monitored by Vibrational Circular Dichroism.

    Science.gov (United States)

    Zhang, Ge; Babenko, Viktoria; Dzwolak, Wojciech; Keiderling, Timothy A

    2015-12-15

    Dimethyl sulfoxide (DMSO) induced destabilization of insulin fibrils has been previously studied by Fourier transform infrared spectroscopy and interpreted in terms of secondary structural changes. The variation of this process for fibrils with different types of higher-order morphological structures remained unclear. Here, we utilize vibrational circular dichroism (VCD), which has been reported to provide a useful biophysical probe of the supramolecular chirality of amyloid fibrils, to characterize changes in the macroscopic chirality following DMSO-induced disassembly for two types of insulin fibrils formed under different conditions, at different reduced pH values with and without added salt and agitation. We confirm that very high concentrations of DMSO can disaggregate both types of insulin fibrils, which initially maintained a β-sheet conformation and eventually changed their secondary structure to a disordered form. The two types responded to varying concentrations of DMSO, and disaggregation followed different mechanisms. Interconversion of specific insulin fibril morphological types also occurred during the destabilization process as monitored by VCD. With transmission electron microscopy, we were able to correlate the changes in VCD sign patterns to alteration of morphology of the insulin fibrils.

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

    CERN Document Server

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

    1999-01-01

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

  12. Applied Circular Dichroism: A Facile Spectroscopic Tool for Configurational Assignment and Determination of Enantiopurity

    Directory of Open Access Journals (Sweden)

    Macduff O. Okuom

    2015-01-01

    Full Text Available In order to determine if electronic circular dichroism (ECD is a good tool for the qualitative evaluation of absolute configuration and enantiopurity in the absence of chiral high performance liquid chromatography (HPLC, ECD studies were performed on several prescriptions and over-the-counter drugs. Cotton effects (CE were observed for both S and R isomers between 200 and 300 nm. For the drugs examined in this study, the S isomers showed a negative CE, while the R isomers displayed a positive CE. The ECD spectra of both enantiomers were nearly mirror images, with the amplitude proportional to the enantiopurity. Plotting the differential extinction coefficient (Δε versus enantiopurity at the wavelength of maximum amplitude yielded linear standard curves with coefficients of determination (R2 greater than 97% for both isomers in all cases. As expected, Equate, Advil, and Motrin, each containing a racemic mixture of ibuprofen, yielded no chiroptical signal. ECD spectra of Suphedrine and Sudafed revealed that each of them is rich in 1S,2S-pseudoephedrine, while the analysis of Equate vapor inhaler is rich in R-methamphetamine.

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

    Science.gov (United States)

    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.

  14. Can circular dichroism in core-level photoemission provide a spectral fingerprint of adsorbed chiral molecules?

    Energy Technology Data Exchange (ETDEWEB)

    Allegretti, F [Physics Department, University of Warwick, Coventry CV4 7AL (United Kingdom); Polcik, M [Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, D 14195 Berlin (Germany); Sayago, D I [Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, D 14195 Berlin (Germany); Demirors, F [Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, D 14195 Berlin (Germany); O' Brien, S [Physics Department, University of Warwick, Coventry CV4 7AL (United Kingdom); Nisbet, G [Centre for Applied Catalysis, Department of Chemical and Biological Sciences, University of Huddersfield, Queensgate, Huddersfield HD1 3DH (United Kingdom); Lamont, C L A [Centre for Applied Catalysis, Department of Chemical and Biological Sciences, University of Huddersfield, Queensgate, Huddersfield HD1 3DH (United Kingdom); Woodruff, D P [Physics Department, University of Warwick, Coventry CV4 7AL (United Kingdom)

    2005-04-01

    The results of experimental measurements and theoretical simulations of circular dichroism in the angular distribution (CDAD) of photoemission from atomic core levels of each of the enantiomers of a chiral molecule, alanine, adsorbed on Cu(1 1 0) are presented. Measurements in, and out of, substrate mirror planes allow one to distinguish the CDAD due to the chirality of the sample from that due to a chiral experimental geometry. For these studies of oriented chiral molecules, the CDAD is seen not only in photoemission from the molecular chiral centre, but also from other atoms which have chiral geometries as a result of the adsorption. The magnitude of the CDAD due to the sample chirality differs for different adsorption phases of alanine, and for different emission angles and energies, but is generally small compared with CDAD out of the substrate mirror planes which is largely unrelated to the molecular chirality. While similar measurements of other molecules may reveal larger CDAD due to molecular chirality, the fact that the results for one chiral molecule show weak effects means that such CDAD is unlikely to provide a simple and routine general spectral fingerprint of adsorbed molecular chirality.

  15. Applications of Circular Dichroism for Structural Analysis of Gelatin and Antimicrobial Peptides

    Directory of Open Access Journals (Sweden)

    Yoonkyung Park

    2012-03-01

    Full Text Available Circular dichroism (CD is a useful technique for monitoring changes in the conformation of antimicrobial peptides or gelatin. In this study, interactions between cationic peptides and gelatin were observed without affecting the triple helical content of the gelatin, which was more strongly affected by anionic surfactant. The peptides did not adopt a secondary structure in the presence of aqueous solution or Tween 80, but a peptide secondary structure formed upon the addition of sodium dodecyl sulfate (SDS. The peptides bound to the phosphate group of lipopolysaccharide (LPS and displayed an alpha-helical conformation while (KW4 adopted a folded conformation. Further, the peptides did not specifically interact with the fungal cell wall components of mannan or laminarin. Tryptophan blue shift assay indicated that these peptides interacted with SDS, LPS, and gelatin but not with Tween 80, mannan, or laminarin. The peptides also displayed antibacterial activity against P. aeruginosa without cytotoxicity against HaCaT cells at MIC, except for HPA3NT3-analog peptide. In this study, we used a CD spectroscopic method to demonstrate the feasibility of peptide characterization in numerous environments. The CD method can thus be used as a screening method of gelatin-peptide interactions for use in wound healing applications.

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

    Directory of Open Access Journals (Sweden)

    Igor V. Uporov

    2015-09-01

    Full Text Available 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.

  17. Simulations of circular dichroism spectra of a pair of diterpene enantiomers by time-dependent density functional theory

    Science.gov (United States)

    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.

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

    CERN Document Server

    Guo, Zhi-Ying; Xing, Hai-Ying; Tang, Kun; Xui, Wei; Chen, Dong-liang; Cui, Ming-Qi; Zhao, YI-Dong

    2014-01-01

    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: 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 0.5T 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 t...

  19. Computational Study of the Structure, the Flexibility, and the Electronic Circular Dichroism of Staurosporine - a Powerful Protein Kinase Inhibitor

    Science.gov (United States)

    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.

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

    CERN Document Server

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

    2012-01-01

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

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

    Science.gov (United States)

    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.

  2. Circular dichroism and polarized fluorescence characteristics of blue-green algal allophycocyanins

    Energy Technology Data Exchange (ETDEWEB)

    Canaani, O.D.; Gantt, E.

    1980-06-24

    Allophycocyanin, the terminal pigment in the phycobiliprotein transfer sequence, isolated from dissociated phycobilisomes of Nostoc sp., was fractionated on calcium phosphate columns into four spectral forms: APC I, II, III, and B. These forms had distinctive isoelectric points of 5.15, 4.68, 4.82, and 4.98, respectively. The APC forms differed in their secondary structure as suggested by the varying percentages of their ..cap alpha.. helix and ..beta..-pleated sheets. APC II and III are short-emitting forms with a fluorescence maximum at 660 nm, while APC I and B are long-emitting forms with a maximum at 681 nm. The maximum of APC I and B at -196/sup 0/C in 0.1 M phosphate and 20% glycerol shifted to 688 nm. Fluorescence polarization spectra suggest that there are at least two groups of chromophores responsible for the absorption of APC I and similarly of APC B. In APC II and III, the fluorescence was mostly depolarized. Circular dichroism revealed extensive positive and negative ellipticity band multiplicities in the chromophore absorption region of APC I and B, but not in APC II and III. Two main CD extrema in APC B, a negative band and a positive band, are probably the result of exciton coupling of phycocyanobilin chromophores absorbing at longer wavelength. In APC I three different peaks are revealed in the absorption spectrum and four ellipticity bands in the CD spectrum at -196/sup 0/C. These can best be explained as being due to the combined interactions of the chromophore with the protein and exciton coupling between chromophores.

  3. Conformation and stability properties of B17: I. Analytical investigations using circular dichroism.

    Science.gov (United States)

    Khachfe, Hassan M; Atkinson, David

    2012-08-01

    Structural characterization of B17, the 17% N-terminal domain of apo B, was carried out using circular dichroic (CD) spectroscopy, where secondary and tertiary structures were studied as a function of temperature and pH. Mild acidic conditions that correlate with histidine protonation invoked a change in the α-helix and random coil contents of the protein, with no apparent change in the β-sheet structural content. Specific changes in the structure of the protein that occur in response to temperature were also investigated to understand the stability and conformational changes of B17. Far- and near-UV CDs were used to probe the thermal changes in the protein. The protonation of some histidine residues was attributed to underlie the increase in the helical content of the protein.

  4. Circular dichroism study of stacking properties of oligodeoxyadenylates and polydeoxyadenylate. A three-state conformational model.

    Science.gov (United States)

    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

  5. Electronic states of model hydrocarbon chromophores investigated by Synchrotron Radiation Linear Dichroism (SRLD) spectroscopy on aligned samples

    DEFF Research Database (Denmark)

    Nguyen, Duy Duc; Hoffmann, Søren Vrønning; Jones, Nykola;

    2010-01-01

    Conventional UV-VIS absorption spectroscopy provides information on transition energies and intensities. Linear dichroism (LD) spectroscopy on aligned molecular samples yields additional information on transition moment directions, thereby frequently leading to resolution of otherwise overlapping...

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

    DEFF Research Database (Denmark)

    Fahleson, Tobias; Kauczor, Joanna; Norman, Patrick;

    2015-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Sander, Anke; Christl, Maik [Institute of Physics, Martin-Luther-Universität Halle-Wittenberg, Von-Danckelmann-Platz 3, 06120 Halle(Saale) (Germany); Chiang, Cheng-Tien [Max Planck Institute of Microstructure Physics, Weinberg 2, 06120 Halle(Saale) (Germany); Institute of Physics, Martin-Luther-Universität Halle-Wittenberg, Von-Danckelmann-Platz 3, 06120 Halle(Saale) (Germany); Alexe, Marin [Department of Physics, University of Warwick, Coventry CV4 7AL (United Kingdom); Widdra, Wolf, E-mail: wolf.widdra@physik.uni-halle.de [Institute of Physics, Martin-Luther-Universität Halle-Wittenberg, Von-Danckelmann-Platz 3, 06120 Halle(Saale) (Germany); Max Planck Institute of Microstructure Physics, Weinberg 2, 06120 Halle(Saale) (Germany)

    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.

  8. Theoretical description of circular dichroism in photoelectron angular distributions of randomly oriented chiral molecules after multi-photon photoionization

    CERN Document Server

    Goetz, R E; Nikoobakht, B; Berger, R; Koch, C P

    2016-01-01

    Photoelectron circular dichroism refers to the forward/backward asymmetry in the photoelectron angular distribution with respect to the propagation axis of circularly polarized light. It has recently been demonstrated in femtosecond multi-photon photoionization experiments with randomly oriented camphor and fenchone molecules [C. Lux et al., Angew. Chem. Int. Ed. 51, 5001 (2012);C. S. Lehmann et al., J. Chem. Phys. 139, 234307 (2013)]. A theoretical framework describing this process as (2+1) resonantly enhanced multi-photon ionization is constructed, which consists of two-photon photoselection from randomly oriented molecules and successive one-photon ionisation of the photoselected molecules. It combines perturbation theory for the light-matter interaction with ab initio calculations for the two-photon absorption and a single-center expansion of the photoelectron wavefunction in terms of hydrogenic continuum functions. It is verified that the model correctly reproduces the basic symmetry behavior expected un...

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

    Directory of Open Access Journals (Sweden)

    Lees Jonathan G

    2008-01-01

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

  10. Structural alterations of human serum albumin caused by glycative and oxidative stressors revealed by circular dichroism analysis.

    Science.gov (United States)

    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.

  11. PILOT STUDY International comparability in spectroscopic measurements of protein structure by circular dichroism: CCQM-P59

    Science.gov (United States)

    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).

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

    Science.gov (United States)

    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. Laser-driven electron dynamics for circular dichroism in mass spectrometry: from one-photon excitations to multiphoton ionization.

    Science.gov (United States)

    Kröner, Dominik

    2015-07-15

    The distinction of enantiomers is a key aspect of chemical analysis. In mass spectrometry the distinction of enantiomers has been achieved by ionizing the sample with circularly polarized laser pulses and comparing the ion yields for light of opposite handedness. While resonant excitation conditions are expected to be most efficient, they are not required for the detection of a circular dichroism (CD) in the ion yield. However, the prediction of the size and sign of the circular dichroism becomes challenging if non-resonant multiphoton excitations are used to ionize the sample. Employing femtosecond laser pulses to drive electron wavepacket dynamics based on ab initio calculations, we attempt to reveal underlying mechanisms that determine the CD under non-resonant excitation conditions. Simulations were done for (R)-1,2-propylene oxide, using time-dependent configuration interaction singles with perturbative doubles (TD-CIS(D)) and the aug-cc-pVTZ basis set. Interactions between the electric field and the electric dipole and quadrupole as well as between the magnetic field and the magnetic dipole were explicitly accounted for. The ion yield was determined by treating states above the ionization potential as either stationary or non-stationary with energy-dependent lifetimes based on an approved heuristic approach. The observed population dynamics do not allow for a simple interpretation, because of highly non-linear interactions. Still, the various transition pathways are governed by resonant enantiospecific n-photon excitation, with preferably high transition dipole moments, which eventually dominate the CD in the ionized population. PMID:26151731

  14. Magnetism of unconventional nanoscaled materials. An X-ray circular dichroism and muon spin rotation study

    International Nuclear Information System (INIS)

    The physical properties of nanoparticles deviate strongly from its bulk counterparts. In particular, the magnetic properties change strongly due to an elevated number of surface compared to bulk atoms. As a consequence the orbital magnetic moment in nanoparticles as well as the magnetic anisotropy is enhanced. Therefore, such nanoparticles have great potential in e.g. next generation high density data storage devices. A promising way to realize such devices is to deposit nanoparticles on graphene. Depending on the preparation conditions the templated growth of nanocluster arrays with different particle size and shape is possible. Since graphene possesses outstanding properties as well it is congruous to combine the advantages of both systems and to investigate its principle properties in more detail. Thus, one part of this work is dedicated to the size and shape dependence of electronic and magnetic properties of Ni nanoclusters on graphene. The magnetic properties were investigated using X-ray Magnetic Circular Dichroism (XMCD). From the corresponding absorption spectra, the electronic structure and the nanoparticle substrate interaction could be determined. Two sets of nanoparticles were investigated, with triangular and spherical shape. For each set the size was varied. Nonmagnetic absorption spectra indicate a strong interaction between the Ni nanoclusters and the graphene substrate. The integrated absorption signal which is a measure of the number of unoccupied states in the Ni d shell decreases strongly with decreasing cluster size. This means an enhanced occupancy of the Ni d states, most likely caused by charge transfer at the Ni nanocluster/graphene interface. As a consequence the magnetic moment was much smaller than expected for nanoclusters for all samples investigated. The smallest value obtained was only 50% of the respective bulk magnetic moment. The magnetic moment increases disproportionally and converges towards bulk properties above 2 ML. No

  15. Magnetism of unconventional nanoscaled materials. An X-ray circular dichroism and muon spin rotation study

    Energy Technology Data Exchange (ETDEWEB)

    Tietze, Thomas Hermann

    2014-12-15

    The physical properties of nanoparticles deviate strongly from its bulk counterparts. In particular, the magnetic properties change strongly due to an elevated number of surface compared to bulk atoms. As a consequence the orbital magnetic moment in nanoparticles as well as the magnetic anisotropy is enhanced. Therefore, such nanoparticles have great potential in e.g. next generation high density data storage devices. A promising way to realize such devices is to deposit nanoparticles on graphene. Depending on the preparation conditions the templated growth of nanocluster arrays with different particle size and shape is possible. Since graphene possesses outstanding properties as well it is congruous to combine the advantages of both systems and to investigate its principle properties in more detail. Thus, one part of this work is dedicated to the size and shape dependence of electronic and magnetic properties of Ni nanoclusters on graphene. The magnetic properties were investigated using X-ray Magnetic Circular Dichroism (XMCD). From the corresponding absorption spectra, the electronic structure and the nanoparticle substrate interaction could be determined. Two sets of nanoparticles were investigated, with triangular and spherical shape. For each set the size was varied. Nonmagnetic absorption spectra indicate a strong interaction between the Ni nanoclusters and the graphene substrate. The integrated absorption signal which is a measure of the number of unoccupied states in the Ni d shell decreases strongly with decreasing cluster size. This means an enhanced occupancy of the Ni d states, most likely caused by charge transfer at the Ni nanocluster/graphene interface. As a consequence the magnetic moment was much smaller than expected for nanoclusters for all samples investigated. The smallest value obtained was only 50% of the respective bulk magnetic moment. The magnetic moment increases disproportionally and converges towards bulk properties above 2 ML. No

  16. Applications of circular dichroism (CD) for structural analysis of proteins: qualification of near- and far-UV CD for protein higher order structural analysis.

    Science.gov (United States)

    Li, Cynthia H; Nguyen, Xichdao; Narhi, Linda; Chemmalil, Letha; Towers, Edward; Muzammil, Salman; Gabrielson, John; Jiang, Yijia

    2011-11-01

    Circular dichroism (CD) spectroscopy is routinely used in the biopharmaceutical industry to study the effects of manufacturing, formulation, and storage conditions on protein conformation and stability, and these results are often included in regulatory filings. In this context, the purpose of CD spectroscopy is often to verify that a change in the formulation or manufacturing process of a product has not produced a change in the conformation of a protein. A comparison of two or more spectra is often required to confirm that the protein's structure has been maintained. Traditionally, such comparisons have been qualitative in nature, based on visually inspecting the overlaid spectra. However, visual assessment is inherently subjective and therefore prone to error. Furthermore, recent requests from regulatory agencies to demonstrate the suitability of the CD spectroscopic method for the purpose of comparing spectra have highlighted the need to appropriately qualify CD spectroscopy for characterization of biopharmaceutical protein products. In this study, we use a numerical spectral comparison approach to establish the precision of the CD spectroscopic method and to demonstrate that it is suitable for protein structural characterization in numerous biopharmaceutical applications. PMID:21732370

  17. Present status of vacuum ultraviolet natural circular dichroism measurement system using polarizing undulator at TERAS BL5 beamline

    Energy Technology Data Exchange (ETDEWEB)

    Tanaka, Masahito, E-mail: masahito-tanaka@aist.go.j [Research Institute of Instrumentation Frontier, National Institute of Advanced Industrial Science and Technology (AIST), Central 2, Umezono 1-1-1, Tsukuba, Ibaraki 305-8568 (Japan); Yagi-Watanabe, Kazutoshi; Kaneko, Fusae [Research Institute of Instrumentation Frontier, National Institute of Advanced Industrial Science and Technology (AIST), Central 2, Umezono 1-1-1, Tsukuba, Ibaraki 305-8568 (Japan); Nakagawa, Kazumichi [Graduate School of Human Development and Environment, Kobe University, Tsurukabuto 3-11, Nada-ku, Kobe 657-8501 (Japan)

    2010-08-15

    The study of natural circular dichroism (CD) in the vacuum and extreme ultraviolet (VUV and EUV) regions has been providing us with chirality and structural information on biomolecules. We have developed the beamline BL5 at TERAS, Tsukuba, which is equipped with a compact Onuki-type polarizing undulator. This beamline is dedicated to measuring the CD spectra in the VUV and EUV regions for the photon energy region of 5-40 eV. The use of a polarization modulation technique with a polarizing undulator is essential for detecting a weak CD signal. Using this CD system, the natural CD spectrum has been measured in the EUV region up to 40 eV for the first time. In addition, the differences and the similarities between the CD spectra of four amino acid films (alanine, valine, leucine, and phenylalanine) in the VUV region up to 9.5 eV are determined.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2012-06-05

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

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

    Science.gov (United States)

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

    2012-06-01

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

  20. Gigantic transverse x-ray magnetic circular dichroism in ultrathin Co in Au/Co/Au(001)

    International Nuclear Information System (INIS)

    Transverse-geometry x-ray magnetic circular dichroism (TXMCD) measurements on Au/Co-staircase/Au(001) reveal the orbital origin of intrinsic in-plane magnetic anisotropy A gigantic TXMCD was successfully observed at the Co L3,2 edges for Co thickness (tC0) in the 2-monolayer regime. A TXMCD-sum-rule analysis shows a remarkable enhancement of an orbital-moment anisotropy (Δmorb) and of an in-plane magnetic dipole moment (m||T). Both Δmorb and m||T exhibit close similarity in tCo dependence, reflecting the in-plane magnetic anisotropy These observations evidence that extremely strong, intrinsic, in-plane magnetic anisotropy originates from the anisotropic orbital part of the wave function, dominating the dipole-dipole-interaction-derived, extrinsic, in-plane magnetic anisotropy.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2009-11-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2009-01-01

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

  3. First principles structures and circular dichroism spectra for the close-packed and the 7/2 motif of collagen

    CERN Document Server

    Jalkanen, Karl J; Knapp-Mohammady, Michaela; Bohr, Jakob

    2012-01-01

    The recently proposed close-packed motif for collagen is investigated using first principles semi-empirical wave function theory and Kohn-Sham density functional theory. Under these refinements the close-packed motif is shown to be stable. For the case of the 7/2 motif a similar stability exists. The electronic circular dichroism of the close-packed model has a significant negative bias and a large signal. An interesting feature of the close-packed structure is the existence of a central channel. Simulations show that, if hydrogen atoms are placed in the cavity, a chain of molecular hydrogens is formed suggesting a possible biological function for molecular hydrogen.

  4. Toroidal Interaction and Propeller Chirality of Hexaarylbenzenes. Dynamic Domino Inversion Revealed by Combined Experimental and Theoretical Circular Dichroism Studies.

    Science.gov (United States)

    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.

  5. Soft x-ray circular dichroism and scattering using a modulated elliptically polarizing wiggler and double synchronous detection

    Energy Technology Data Exchange (ETDEWEB)

    Sutherland, J.C.; Polewski, K.; Monteleone, D.C. [and others

    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.

  6. Toroidal Interaction and Propeller Chirality of Hexaarylbenzenes. Dynamic Domino Inversion Revealed by Combined Experimental and Theoretical Circular Dichroism Studies.

    Science.gov (United States)

    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. PMID:26882341

  7. A circular dichroism sensor for Ni2+ and Co2+ based on L-cysteine capped cadmium sulfide quantum dots

    International Nuclear Information System (INIS)

    Highlights: • Demonstrated a new efficient sensor platform based quantum dots. • Used chiral quantum dots as CD sensor for the detection of heavy metal ions for the first time. • The proposed CD sensor showed highest selectivity towards Ni2+ and Co2+. • Low detection limits of 7.33 μM and 1.13 μM for Ni2+ and Co2+, respectively. • Can be used in real water samples comparing with ICP-OES. - Abstract: A new circular dichroism sensor for detecting Ni2+ and Co2+ 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 Ni2+ or Co2+. 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 Ni2+ and Co2+. On the other hand, other studied cations did not alter the original CD spectrum. Moreover, when increasing the concentration of Ni2+ or Co2+, 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 μM and 1.13 μM for the detection of Ni2+ and Co2+, 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 Ni2+ and Co2+ in real water samples, and the results agreed well with the analysis using the standard ICP-OES

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    Kwaambwa, H M; Maikokera, R

    2008-06-15

    The secondary structure of a water treatment coagulant protein extracted from Moringa oleifera (MO) seeds has been investigated by Fourier transform infrared spectroscopy (FTIR) in the dried state, and by circular dichroism (CD) spectroscopy. The FTIR and CD spectra indicate that the secondary structure of the protein is dominated by alpha-helix. The FTIR spectrum recorded two distinct and strong absorption bands at 1656 cm(-1) and 1542 cm(-1), in the usual range of absorption of helices of proteins. The CD spectrum showed the shape of mainly alpha-helical secondary structure (estimated to be 58+/-4%) characteristic of negative ellipticity bands near 222 nm and 208 nm and a positive band at 192 nm. The beta-sheet structure composition was estimated to be 10+/-3% whereas unordered structures were around 33%. Changes in solution pH affected the protein secondary structure significantly only at pH values above 10, as indicated by CD spectra, whereas ionic strength had minimal effect. CD data also showed that sodium dodecyl sulphate (SDS) interacts with the coagulant protein and modifies the protein conformation. The surfactant-induced conformational change of the coagulant protein was confirmed by quenching of tryptophan fluorescence of the protein. PMID:18296034

  10. Circular dichroism and UV melting studies on formation of an intramolecular triplex containing parallel T*A:T and G*G:C triplets: netropsin complexation with the triplex.

    OpenAIRE

    Gondeau, C.; Maurizot, J C; Durand, M

    1998-01-01

    We have used circular dichroism and UV absorption spectroscopy to characterize the formation and melting behaviour of an intramolecular DNA triple helix containing parallel T*A:T and G*G:C triplets. Our approach to induce and to stabilize a parallel triplex involves the oligonucleotide 5'-d(G4A4G4[T4]C4T4C4-[T4]G4T4G4) ([T4] represents a stretch of four thymine residues). In a 10 mM sodium cacodylate, 0.2 mM disodium EDTA (pH 7) buffer, we have shown the following significant results. (i) Whi...

  11. Circular Dichroism in Mass Spectrometry: Quantum Chemical Investigations for the Differences between (R)-3-Methylcyclopentanone and Its Cation.

    Science.gov (United States)

    Kröner, Dominik; Gaebel, Tina

    2015-08-27

    In mass spectrometry enantiomers can be distinguished by multiphoton ionization employing circular polarized laser pulses. The circular dichroism (CD) is detected from the normalized difference in the ion yield after excitation with light of opposite handedness. While there are cases in which fragment and parent ions exhibit the same sign of the CD in the ion yield, several experiments show that they might also differ in sign and magnitude. Supported by experimental observations it has been proposed that the parent ion, once it has been formed, is further excited by the laser, which may result in a change of the CD in the ion yield of the formed fragments compared to the parent ion. To gain a deeper insight in possible excitation pathways we calculated and compared the electronic CD absorption spectra of neutral and cationic (R)-3-methylcyclopentanone, applying density functional theory. In addition, electron wavepacket dynamics were used to compare the CD of one- and two-photon transitions. Our results support the proposed subsequent excitation of the parent ion as a possible origin of the difference of the CD in the ion yield between parent ion and fragments. PMID:26214257

  12. Direct evidence of Ni magnetic moment in TbNi{sub 2}Mn—X-ray magnetic circular dichroism

    Energy Technology Data Exchange (ETDEWEB)

    Yu, D.H., E-mail: dyu@ansto.gov.au [Bragg Institute, Australian Nuclear Science and Technology Organisation, Lucas Heights, Sydney, NSW 2234 (Australia); Huang, Meng-Jie [National Synchrotron Radiation Research Center, 101 Hsin-Ann Road, Hsinchu Science Park, Hsinchu 30076, Taiwan (China); Wang, J.L. [Bragg Institute, Australian Nuclear Science and Technology Organisation, Lucas Heights, Sydney, NSW 2234 (Australia); School of Physical, Environmental and Mathematical Sciences, University of New South Wales, Canberra at the Australian Defense Force Academy, Sydney, ACT 2600 (Australia); Institute for Superconductivity and Electronic Materials, University of Wollongong, Wollongong, NSW 2522 (Australia); Su, Hui-Chia; Lin, Hong-Ji; Chen, Chien-Te [National Synchrotron Radiation Research Center, 101 Hsin-Ann Road, Hsinchu Science Park, Hsinchu 30076, Taiwan (China); Campbell, S.J. [School of Physical, Environmental and Mathematical Sciences, University of New South Wales, Canberra at the Australian Defense Force Academy, Sydney, ACT 2600 (Australia)

    2014-12-15

    We have investigated the individual magnetic moments of Ni, Mn and Tb atoms in the intermetallic compound TbNi{sub 2}Mn in the Laves phase (magnetic phase transition temperature T{sub C} ∼131 K) by X-ray magnetic circular dichroism (XMCD) studies at 300 K, 80 K and 20 K. Analyses of the experimental results reveal that Ni atoms at 20 K in an applied magnetic field of 1 T carry an intrinsic magnetic moment of spin and orbital magnetic moment contributions 0.53±0.01 μ{sub B} and 0.05±0.01 μ{sub B}, respectively. These moment values are similar to those of the maximum saturated moment of Ni element. A very small magnetic moment of order <0.1 μ{sub B} has been measured for Mn. This suggests that Mn is antiferromagnetically ordered across the two nearly equally occupied sites of 16d and 8a. A magnetic moment of up to ∼0.3 μ{sub B} has been observed for the Tb atoms. Identification of a magnetic moment on the Ni atoms has provided further evidence for the mechanism of enhancement of the magnetic phase transition temperature in TbNi{sub 2}Mn compared with TbNi{sub 2} (T{sub C}∼37.5 K) and TbMn{sub 2} (T{sub C}∼54 K) due to rare earth–transition metal (R–T) and transition metal–transition metal (T–T) interactions. The behaviour of the X-ray magnetic circular dichroism spectra of TbNi{sub 2}Mn at 300 K, 80 K and 20 K – above and below the magnetic ordering temperature T{sub C} ∼131 K – is discussed. - Highlights: • We study the magnetic moment of TbNi{sub 2}Mn with XMCD. • We observe directly the Ni intrinsic magnetic moment in TbNi{sub 2}Mn. • We find that Mn ordered antiferromagnetically across the 16d and 8a sites. • We confirm the mechanism for increasing the magnetic phase transition temperature.

  13. All-optical switching in granular ferromagnets caused by magnetic circular dichroism.

    Science.gov (United States)

    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

  14. All-optical switching in granular ferromagnets caused by magnetic circular dichroism

    Science.gov (United States)

    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.

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

    Science.gov (United States)

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

    2016-05-01

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

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

    Science.gov (United States)

    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 (RSDmethod 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.

  17. Exciton circular dichroism couplet arising from nitrile-derivatized aromatic residues as a structural probe of proteins.

    Science.gov (United States)

    Mukherjee, Debopreeti; Gai, Feng

    2016-08-15

    Exciton coupling between two chromophores can produce a circular dichroism (CD) couplet that depends on their separation distance, among other factors. Therefore, exciton CD signals arising from aromatic sidechains, especially those of tryptophan (Trp), have been used in various protein conformational studies. However, the long-wavelength component of the commonly used CD couplet produced by a pair of Trp residues is typically located around 230 nm, thereby overlapping significantly with the protein backbone CD signal. This overlap often prevents a direct and quantitative assessment of the Trp CD couplet in question without further spectral analysis. Here, we show that this inconvenience can be alleviated by using a derivative of Trp, 5-cyanotryptophan (TrpCN), as the chromophore. Specifically, through studying a series of peptides that fold into either α-helical or ß-hairpin conformations, we demonstrate that in comparison with the Trp CD couplet, that arising from two TrpCN residues not only is significantly red-shifted but also becomes more intense due to the larger extinction coefficient of the underlying electronic transition. In addition, we show that a pair of p-cyanophenylalanines (PheCN) or a PheCN-TrpCN pair can also produce a distinct exciton CD couplet that can be useful in monitoring conformational changes in proteins. PMID:27251434

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-05-07

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

  19. Unraveling the thermodynamics and kinetics of RNA assembly: surface plasmon resonance, isothermal titration calorimetry, and circular dichroism.

    Science.gov (United States)

    Hoogstraten, Charles G; Sumita, Minako; White, Neil A

    2014-01-01

    The mechanisms and driving forces of the assembly of RNA tertiary structure are a topic of much current interest. In several systems, including our own work in the docking transition of the hairpin ribozyme, intramolecular RNA tertiary folding has been converted into an intermolecular binding event, allowing the full power of contemporary biophysical techniques to be brought to bear on the analysis. We review the use of three such methods: circular dichroism to isolate the binding of multivalent cations coupled to tertiary assembly, surface plasmon resonance to determine the rates of association and dissociation, and isothermal titration calorimetry to dissect the thermodynamic contributions to RNA assembly events. We pay particular attention to practical aspects of these studies, such as careful preparation of samples with fixed free concentrations of cations in order to avoid errors due to ion depletion effects that are common in RNA systems. Examples of applications from our own work with the hairpin ribozyme are shown. Distinctions among the data handling procedures for the various techniques used and solution conditions encountered are also discussed.

  20. Dependence of magnetic circular dichroism on doping and temperature in In1-xMnxAs epitaxial films

    Science.gov (United States)

    Chiu, P. T.; Wessels, B. W.

    2007-10-01

    To elucidate the nature of the exchange interactions in ferromagnetic In1-xMnxAs , the composition and temperature dependencies of the magnetic circular dichroism (MCD) spectrum were investigated. The spectrum is comprised of both a broad transition from 1.6to3.0eV and a negative peak between 2.68 and 2.8eV associated with L -point sp-d transitions. The spectral response of the MCD is strongly temperature dependent. The magnitude of the negative peak and magnetization increases significantly with decreasing temperature for Tconstant over the same temperature range. The difference in the temperature dependence of the two negative background and peak corroborates previous assertions that the two features are due to two distinct transitions. For a series of films ranging from x=0.020to0.063 , the magnitude of the MCD peak and background exhibits a superlinear dependence on Mn concentration at room temperature. The superlinear dependence is attributed to the formation of atomic scale, tetrahedrally coordinated MnAs clusters.

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

    Science.gov (United States)

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

    2011-01-01

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

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    Goings, Joshua J.; Li, Xiaosong

    2016-06-01

    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.

  4. X-ray magnetic circular dichroism: Orbital and spin moments of iron single-crystal thin film deposited on MgO substrate

    Institute of Scientific and Technical Information of China (English)

    LI Honghong; WANG Jie; LI Ruipeng; GUO Yuxian; WANG Feng; HU Zhiwei

    2005-01-01

    X-ray magnetic circular dichroism in absorption of the single-crystal iron layer deposited epitaxially on MgO substrate is studied. Spin and orbital moment, 0.069 and 2.33 -B, respectively, are calculated in terms of the XMCD sum rules. Our results are accordant to those published. Experiments show that the orbital moment would be decreased to that in bulk materials as iron film is thinned down, but spin moment changes little.

  5. The influence of carbon nanotubes on enzyme activity and structure: investigation of different immobilization procedures through enzyme kinetics and circular dichroism studies

    Energy Technology Data Exchange (ETDEWEB)

    Cang-Rong, Jason Teng; Pastorin, Giorgia [Department of Pharmacy, National University of Singapore, 117543 (Singapore)], E-mail: jasonteng@nus.edu.sg, E-mail: phapg@nus.edu.sg

    2009-06-24

    In the last decade, many environmental organizations have devoted their efforts to identifying renewable biosystems, which could provide sustainable fuels and thus enhance energy security. Amidst the myriad of possibilities, some biofuels make use of different types of waste biomasses, and enzymes are often employed to hydrolyze these biomasses and produce sugars that will be subsequently converted into ethanol. In this project, we aimed to bridge nanotechnology and biofuel production: here we report on the activity and structure of the enzyme amyloglucosidase (AMG), physically adsorbed or covalently immobilized onto single-walled carbon nanotubes (SWNTs) and multi-walled carbon nanotubes (MWNTs). In fact, carbon nanotubes (CNTs) present several properties that render them ideal support systems, without the diffusion limitations displayed by porous material and with the advantage of being further functionalizable at their surface. Chemical ligation was achieved both on oxidized nanotubes (via carbodiimide chemistry), as well as on amino-functionalized nanotubes (via periodate-oxidized AMG). Results showed that AMG retained a certain percentage of its specific activity for all enzyme-carbon nanotubes complexes prepared, with the physically adsorbed samples displaying better catalytic efficiency than the covalently immobilized samples. Analysis of the enzyme's structure through circular dichroism (CD) spectroscopy revealed significant structural changes in all samples, the degree of change being consistent with the activity profiles. This study proves that AMG interacts differently with carbon nanotubes depending on the method employed. Due to the higher activity reported by the enzyme physically adsorbed onto CNTs, these samples demonstrated a vast potential for further development. At the same time, the possibility of inducing magnetic properties into CNTs offers the opportunity to easily separate them from the original solution. Hence, substances to which

  6. Controlled cobalt doping in the spinel structure of magnetosome magnetite: new evidences from element- and site-specific X-ray magnetic circular dichroism analyses.

    Science.gov (United States)

    Li, Jinhua; Menguy, Nicolas; Arrio, Marie-Anne; Sainctavit, Philippe; Juhin, Amélie; Wang, Yinzhao; Chen, Haitao; Bunau, Oana; Otero, Edwige; Ohresser, Philippe; Pan, Yongxin

    2016-08-01

    The biomineralization of magnetite nanocrystals (called magnetosomes) by magnetotactic bacteria (MTB) has attracted intense interest in biology, geology and materials science due to the precise morphology of the particles, the chain-like assembly and their unique magnetic properties. Great efforts have been recently made in producing transition metal-doped magnetosomes with modified magnetic properties for a range of applications. Despite some successful outcomes, the coordination chemistry and magnetism of such metal-doped magnetosomes still remain largely unknown. Here, we present new evidences from X-ray magnetic circular dichroism (XMCD) for element- and site-specific magnetic analyses that cobalt is incorporated in the spinel structure of the magnetosomes within Magnetospirillum magneticum AMB-1 through the replacement of Fe(2+) ions by Co(2+) ions in octahedral (Oh) sites of magnetite. Both XMCD at Fe and Co L2,3 edges, and energy-dispersive X-ray spectroscopy on transmission electron microscopy analyses reveal a heterogeneous distribution of cobalt occurring either in different particles or inside individual particles. Compared with non-doped one, cobalt-doped magnetosome sample has lower Verwey transition temperature and larger magnetic coercivity, related to the amount of doped cobalt. This study also demonstrates that the addition of trace cobalt in the growth medium can significantly improve both the cell growth and the magnetosome formation within M. magneticum AMB-1. Together with the cobalt occupancy within the spinel structure of magnetosomes, this study indicates that MTB may provide a promising biomimetic system for producing chains of metal-doped single-domain magnetite with an appropriate tuning of the magnetic properties for technological and biomedical applications. PMID:27512138

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

    International Nuclear Information System (INIS)

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

  8. High pressure study of gadolinium (silicon-germanium) giant magnetocaloric materials using x-ray magnetic circular dichroism

    Science.gov (United States)

    Tseng, Yuan-Chieh

    The role of Si-doping in enhancing the magnetic ordering temperature (Tc) of Gd5(SixGe1--x )4 giant magnetocaloric compounds was investigated using x-ray magnetic circular dichroism (XMCD) and diamond anvil cell (DAC) techniques. The purpose of the study is to understand the mechanism of doping-induced ferromagnetic order in these compounds that may advance the magnetic refrigeration technology. The results demonstrate that hydrostatic pressure leads to similar effects as Si-doping for x ≥ 0.125 because the P-T phase diagram reproduces the most notable features of the x-T phase diagram, indicating that the magnetic properties of these compounds are volume-driven. The low-x (0 < x ≤ 0.75) region exhibits an inhomogeneous magneto-structural ground state featured by a mixed antiferromagnetic (orthorhombic (II))--ferromagnetic (orthorhombic (I)) phase at low temperature. Pressure was found to remove this magneto-structural inhomogeneity by fully restoring the magnetization that is obtained for x ≥ 0.125. However, unlike the nearly constant dTc/dP obtained for 0.125 ≤ x < 0.5, dTc/dP of the low-x samples is strongly x-dependent. This suggests that the emergence of the ferromagnetic order from within the antiferromagnetic phase of Gd 5Ge4 parent compound cannot be simply described as a volume-effect due to the existence of the magneto-structural inhomogeneity. Finally, the quantitative correspondence between Si-doping and hydrostatic pressure was examined in order to know if the properties of these materials are monotonically volume-dependent. It was found that Si-doping increases Tc much more effectively than pressure, by a factor of ˜ 11 for a given volume reduction. A local lattice contraction was found around Si atoms as a result of the substitution of Ge by the smaller Si atoms resulting in a remarkably high local chemical pressure. This local contraction results in a stronger Si 3p-Gd 5d orbital hybridization benefiting the indirect ferromagnetic exchange

  9. Perpendicular magnetic anisotropy at the interface between ultrathin Fe film and MgO studied by angular-dependent x-ray magnetic circular dichroism

    Energy Technology Data Exchange (ETDEWEB)

    Okabayashi, J. [Research Center for Spectrochemistry, The University of Tokyo, Bunkyo-ku, Tokyo 113-0033 (Japan); Koo, J. W.; Mitani, S. [National Institute for Materials Science (NIMS), Tsukuba 305-0047 (Japan); Graduate School of Pure and Applied Sciences, University of Tsukuba, Tsukuba 305-8577 (Japan); Sukegawa, H. [National Institute for Materials Science (NIMS), Tsukuba 305-0047 (Japan); Takagi, Y.; Yokoyama, T. [Institute of Molecular Science, Okazaki, Aichi 444-8585 (Japan)

    2014-09-22

    Interface perpendicular magnetic anisotropy (PMA) in ultrathin Fe/MgO (001) has been investigated using angular-dependent x-ray magnetic circular dichroism (XMCD). We found that anisotropic orbital magnetic moments deduced from the analysis of XMCD contribute to the large PMA energies, whose values depend on the annealing temperature. The large PMA energies determined from magnetization measurements are related to those estimated from the XMCD and the anisotropic orbital magnetic moments through the spin-orbit interaction. The enhancement of anisotropic orbital magnetic moments can be explained mainly by the hybridization between the Fe 3d{sub z}{sup 2} and O 2p{sub z} states.

  10. Photoelectron circular dichroism in the multiphoton ionization by short laser pulses. I. Propagation of single-active-electron wave packets in chiral pseudo-potentials

    International Nuclear Information System (INIS)

    A theoretical method to study the angle-resolved multiphoton ionization of polyatomic molecules is developed. It is based on the time-dependent formulation of the Single Center (TDSC) method and consists in the propagation of single-active-electron wave packets in the effective molecular potentials in the presence of intense laser pulses. For this purpose, the time-dependent Schrödinger equation for one electron, moving in a molecular field and interacting with an arbitrary laser pulse, is solved in spherical coordinates by an efficient numerical approach. As a test, the method is applied to the one- and two-photon ionizations of a model methane-like chiral system by circularly polarized short intense high-frequency laser pulses. Thereby, we analyze the photoelectron circular dichroism (PECD) in the momentum distribution. The considered model application illustrates the capability of the TDSC method to study multiphoton PECD in fixed-in-space and randomly oriented chiral molecules

  11. Electronic and magnetic properties of off-stoichiometric Co2MnβSi/MgO interfaces studied by x-ray magnetic circular dichroism

    International Nuclear Information System (INIS)

    We have studied the electronic and magnetic states of Co and Mn atoms at the interface of the Co2MnβSi (CMS)/MgO (β = 0.69, 0.99, 1.15, and 1.29) magnetic tunnel junction (MTJ) by means of x-ray magnetic circular dichroism. In particular, the Mn composition (β) dependences of the Mn and Co magnetic moments were investigated. The experimental spin magnetic moments of Mn, mspin(Mn), derived from x-ray magnetic circular dichroism weakly decreased with increasing Mn composition β in going from Mn-deficient to Mn-rich CMS films. This behavior was explained by first-principles calculations based on the antisite-based site-specific formula unit (SSFU) composition model, which assumes the formation of only antisite defect, not vacancies, to accommodate off-stoichiometry. Furthermore, the experimental spin magnetic moments of Co, mspin(Co), also weakly decreased with increasing Mn composition. This behavior was consistently explained by the antisite-based SSFU model, in particular, by the decrease in the concentration of CoMn antisites detrimental to the half-metallicity of CMS with increasing β. This finding is consistent with the higher tunnel magnetoresistance ratios which have been observed for CMS/MgO/CMS MTJs with Mn-rich CMS electrodes

  12. Angle-resolved soft X-ray magnetic circular dichroism in a monatomic Fe layer facing an MgO(0 0 1) tunnel barrier

    Energy Technology Data Exchange (ETDEWEB)

    Mamiya, K. [Photon Factory, Institute of Materials Structure Science (IMSS), High Energy Accelerator Research Organization, 1-1 Oho, Tsukuba, Ibaraki 305-0801 (Japan); Koide, T. [Photon Factory, Institute of Materials Structure Science (IMSS), High Energy Accelerator Research Organization, 1-1 Oho, Tsukuba, Ibaraki 305-0801 (Japan)]. E-mail: tsuneharu.koide@kek.jp; Ishida, Y. [Department of Complexity Science and Engineering, University of Tokyo, 5-1-5 Kashiwanoha, Kashiwa, Chiba 277-8561 (Japan); Osafune, Y. [Department of Complexity Science and Engineering, University of Tokyo, 5-1-5 Kashiwanoha, Kashiwa, Chiba 277-8561 (Japan); Fujimori, A. [Department of Complexity Science and Engineering, University of Tokyo, 5-1-5 Kashiwanoha, Kashiwa, Chiba 277-8561 (Japan); Suzuki, Y. [Graduate School of Engineering Science, Osaka University, 1-3 Toyonaka, Osaka 560-8531 (Japan); NanoElectronics Research Institute, National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba, Ibaraki 305-8568 (Japan); Katayama, T. [NanoElectronics Research Institute, National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba, Ibaraki 305-8568 (Japan); Yuasa, S. [NanoElectronics Research Institute, National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba, Ibaraki 305-8568 (Japan)

    2006-11-15

    The electronic and magnetic states of a monatomic Fe(0 0 1) layer directly facing an MgO(0 0 1) tunnel barrier were studied by angle-resolved X-ray magnetic circular dichroism (XMCD) at the Fe L {sub 2,3} edges in the longitudinal (L) and transverse (T) arrangements. A strong XMCD reveals no oxidation of the 1-ML Fe, showing its crucial role in giant tunnel magnetoresistance effects in Fe/MgO/Fe magnetic tunnel junctions. Sum-rule analyses of the angle-resolved XMCD give values of a spin moment, in-plane and out-of-plane orbital and magnetic dipole moments. Argument is given on their physical implication.

  13. A high-performance liquid chromatography with circular dichroism detector for determination of stereochemistry of 6, 9-oxygen bridge dibenzocyclooctadiene lignans from kadsura coccinea.

    Science.gov (United States)

    Zhu, Hui; Xu, Liang; Yang, Shi-Lin; Li, He-Ran

    2015-10-01

    The stereochemistry of two 6, 9-oxygen bridge dibenzocyclooctadiene lignans from Kadsura coccinea, are difficult to separate and very unstable. The present study was designed to develop a high-performance liquid chromatography using circular dichroism detection for the analysis of the stereochemistry. A new 6, 9-oxygen bridge dibenzocyclooctadiene lignans named Kadsulignan Q was firstly found with an S-biphenyl configuration. The other compound was identified as Kadsulignan L with an R- biphenyl configuration. In order to obtain kinetic data on their reversible interconversion, the stability was measured at different deuterated solvents such as deuterated methanol, deuterated chloroform and deuterated dimethylsulfoxide. The lignans were more unstable and converted more easily in deuterated methanol than in deuterated chloroform and deuterated dimethylsulfoxide. PMID:26481381

  14. Large anisotropic Fe orbital moments in perpendicularly magnetized Co2FeAl Heusler alloy thin films revealed by angular-dependent x-ray magnetic circular dichroism

    Science.gov (United States)

    Okabayashi, Jun; Sukegawa, Hiroaki; Wen, Zhenchao; Inomata, Koichiro; Mitani, Seiji

    2013-09-01

    Perpendicular magnetic anisotropy (PMA) in Heusler alloy Co2FeAl thin films sharing an interface with a MgO layer is investigated by angular-dependent x-ray magnetic circular dichroism. Orbital and spin magnetic moments are deduced separately for Fe and Co 3d electrons. In addition, the PMA energies are estimated using the orbital magnetic moments parallel and perpendicular to the film surfaces. We found that PMA in Co2FeAl is determined mainly by the contribution of Fe atoms with large orbital magnetic moments, which are enhanced at the interface between Co2FeAl and MgO. Furthermore, element specific magnetization curves of Fe and Co are found to be similar, suggesting the existence of ferromagnetic coupling between Fe and Co PMA directions.

  15. Structures, vibrational absorption and vibrational circular dichroism spectra of L-alanine in aqueous solution: a density functional theory and RHF study

    DEFF Research Database (Denmark)

    Frimand, Kenneth; Bohr, Henrik; Jalkanen, Karl J.;

    2000-01-01

    A detailed comparative study of structures, vibrational absorption (VA) and vibrational circular dichroism (VCD) spectra has been carried out for the zwitterionic structure of the amino acid L-alanine. Theoretically determined structures necessary for deriving VA and VCD spectra were calculated...... with three different solvation approaches: the zwitterion surrounded by explicit water molecules only, the zwitterion embedded in a self-consistent reaction field (Onsager model) and the zwitterion plus the explicit water molecules embedded in a self-consistent reaction field. The structures were optimized...... at the density functional theory level using the B3LYP functional with the 6-31G* basis set. The Hessians and atomic polar tensors and atomic axial tensors were all calculated at the B3LYP/6-31G* level of theory. An important result is the method of treating solvent effects by both adding explicit water...

  16. Quantitative x-ray magnetic circular dichroism mapping with high spatial resolution full-field magnetic transmission soft x-ray spectro-microscopy

    Energy Technology Data Exchange (ETDEWEB)

    Robertson, MacCallum J. [Center for X-ray Optics, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States); Physics Department, University of California, Berkeley, California 94720 (United States); Agostino, Christopher J. [Physics Department, University of California, Berkeley, California 94720 (United States); National Center for Electron Microscopy, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States); N' Diaye, Alpha T. [Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States); Chen, Gong [National Center for Electron Microscopy, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States); Im, Mi-Young [Center for X-ray Optics, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States); Department of Emerging Materials Science, Daegu Gyeongbuk Institute of Science and Technology, Daegu 711-873 (Korea, Republic of); Fischer, Peter, E-mail: PJFischer@lbl.gov [Center for X-ray Optics, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States); Physics Department, University of California, Santa Cruz, California 94056 (United States)

    2015-05-07

    The spectroscopic analysis of X-ray magnetic circular dichroism (XMCD), which serves as strong and element-specific magnetic contrast in full-field magnetic transmission soft x-ray microscopy, is shown to provide information on the local distribution of spin (S) and orbital (L) magnetic moments down to a spatial resolution of 25 nm limited by the x-ray optics used in the x-ray microscope. The spatially resolved L/S ratio observed in a multilayered (Co 0.3 nm/Pt 0.5 nm) × 30 thin film exhibiting a strong perpendicular magnetic anisotropy decreases significantly in the vicinity of domain walls, indicating a non-uniform spin configuration in the vertical profile of a domain wall across the thin film. Quantitative XMCD mapping with x-ray spectro-microscopy will become an important characterization tool for systems with topological or engineered magnetization inhomogeneities.

  17. Vibrational analysis of various irotopes of L-alanyl-L-alanine in aqueous solution: Vibrational Absorption (VA), Vibrational Circular Dichroism (VCD), Raman and Raman Optical Activity (ROA) Spectra

    DEFF Research Database (Denmark)

    Jalkanen, Karl J.; Nieminen, R.M.; Knapp-Mohammady, M.;

    2003-01-01

    been reported. Subsequently, the vibrational absorption (VA) and vibrational circular dichroism (VCD) and the Raman and Raman Optical Activity (ROA) spectra have been reported. In this work an analysis of the aqueous solution VA, VCD, Raman, and ROA spectra for various isotopomers of LALA are reported....... DFT Becke3LYP/6-31G* theory has been used to determine the geometry, Hessian, atomic polar tensors (APT), and atomic axial tensors (AAT), and the electric dipole-electric dipole polarizability derivatives (EDEDPD), which are required for us to simulate the VA, VCD, and Raman spectra. The electric...... dipole-magnetic dipole polarizability derivatives (EDMDPD) and the electric dipole-electric cluadrapole polarizability derivatives (EDEQPD) have been calculated at the RHF/6-31G* level of theory, The VA, VCD, Raman, and ROA spectral simulations for the various isotoporners are compared...

  18. Overcoming the existent computational challenges in the ab initio calculations of the two-photon circular dichroism spectra of large molecules using a fragment-recombination approach

    Science.gov (United States)

    Diaz, Carlos; Echevarria, Lorenzo; Hernández, Florencio E.

    2013-05-01

    Herein we report on the development of a fragment-recombination approach (FRA) that allows overcoming the computational limitations found in the ab initio calculation of the two-photon circular dichroism (TPCD) spectra of large optically active molecules. Through the comparative analysis of the corresponding theoretical TPCD spectra of the fragments and that of the entire molecule, we prove that TPCD is an additive property. We also demonstrate that the same property apply to two-photon absorption (TPA). TPCD-FRA is expected to find great applications in the structural-analysis of large catalysts and polypeptides due to its reduced computational complexity, cost and time, and to reveal fingerprints in the obscure spectral region between the near and far UV.

  19. Quantitative x-ray magnetic circular dichroism mapping with high spatial resolution full-field magnetic transmission soft x-ray spectro-microscopy

    International Nuclear Information System (INIS)

    The spectroscopic analysis of X-ray magnetic circular dichroism (XMCD), which serves as strong and element-specific magnetic contrast in full-field magnetic transmission soft x-ray microscopy, is shown to provide information on the local distribution of spin (S) and orbital (L) magnetic moments down to a spatial resolution of 25 nm limited by the x-ray optics used in the x-ray microscope. The spatially resolved L/S ratio observed in a multilayered (Co 0.3 nm/Pt 0.5 nm) × 30 thin film exhibiting a strong perpendicular magnetic anisotropy decreases significantly in the vicinity of domain walls, indicating a non-uniform spin configuration in the vertical profile of a domain wall across the thin film. Quantitative XMCD mapping with x-ray spectro-microscopy will become an important characterization tool for systems with topological or engineered magnetization inhomogeneities

  20. X-ray magnetic circular dichroism photoemission electron microscopy of focused ion beam-induced magnetic patterns on iron–rhodium surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Tohki, Atsushi; Aikoh, Kazuma; Shinoda, Ryoichi [Department of Materials Science, Osaka Prefecture University, 1-1 Gakuen-cho, Naka-ku, Sakai, Osaka 599-8531 (Japan); Ohkochi, Takuo [Japan Synchrotron Radiation Research Institute, SPring-8, Sayo, Hyogo 679-5198 (Japan); Kotsugi, Masato [Japan Synchrotron Radiation Research Institute, SPring-8, Sayo, Hyogo 679-5198 (Japan); CREST-JST, Kawaguchi, Saitama 332-0012 (Japan); Nakamura, Tetsuya [Japan Synchrotron Radiation Research Institute, SPring-8, Sayo, Hyogo 679-5198 (Japan); Kinoshita, Toyohiko [Japan Synchrotron Radiation Research Institute, SPring-8, Sayo, Hyogo 679-5198 (Japan); CREST-JST, Kawaguchi, Saitama 332-0012 (Japan); Iwase, Akihiro [Department of Materials Science, Osaka Prefecture University, 1-1 Gakuen-cho, Naka-ku, Sakai, Osaka 599-8531 (Japan); Matsui, Toshiyuki, E-mail: t-matsui@21c.osakafu-u.ac.jp [Research Organization for the 21st Century, Osaka Prefecture University, 1-1 Gakuen-cho, Sakai, Osaka 599-8531 (Japan)

    2013-05-01

    Iron–rhodium (FeRh) thin films were irradiated with a 30 keV Ga ion beam using a focused ion beam system to produce micrometer scale ferromagnetic square dot arrays. Two-dimensional magnetic square dot arrays with dimensions of 30 × 30, 10 × 10, and 5 × 5 μm were successfully produced on the FeRh surface, which was confirmed by magnetic force microscopy. The results of photoemission electron microscopy combined with X-ray magnetic circular dichroism revealed that the magnetization of the magnetic square dots could be controlled by changing the amount of irradiation. The magnetic domain structure of the magnetic square dots with sides of 5–30 μm was found to be a single domain structure, which was possibly influenced by the interaction between ferromagnetic and antiferromagnetic interfaces.

  1. X-ray magnetic circular dichroism photoemission electron microscopy of focused ion beam-induced magnetic patterns on iron-rhodium surfaces

    Science.gov (United States)

    Tohki, Atsushi; Aikoh, Kazuma; Shinoda, Ryoichi; Ohkochi, Takuo; Kotsugi, Masato; Nakamura, Tetsuya; Kinoshita, Toyohiko; Iwase, Akihiro; Matsui, Toshiyuki

    2013-05-01

    Iron-rhodium (FeRh) thin films were irradiated with a 30 keV Ga ion beam using a focused ion beam system to produce micrometer scale ferromagnetic square dot arrays. Two-dimensional magnetic square dot arrays with dimensions of 30 × 30, 10 × 10, and 5 × 5 μm were successfully produced on the FeRh surface, which was confirmed by magnetic force microscopy. The results of photoemission electron microscopy combined with X-ray magnetic circular dichroism revealed that the magnetization of the magnetic square dots could be controlled by changing the amount of irradiation. The magnetic domain structure of the magnetic square dots with sides of 5-30 μm was found to be a single domain structure, which was possibly influenced by the interaction between ferromagnetic and antiferromagnetic interfaces.

  2. Study on ferromagnetic ordering of FeRh thin films induced by energetic heavy ion irradiation by means of X-ray Magnetic Circular Dichroism

    Science.gov (United States)

    Aikoh, Kazuma; Tohki, Atsushi; Okuda, Shuichi; Saitoh, Yuichi; Kamiya, Tomihiro; Nakamura, Tetsuya; Kinoshita, Toyohiko; Iwase, Akihiro; Matsui, Toshiyuki

    2013-11-01

    We investigated the ion irradiation induced ferromagnetic state of FeRh thin films with 10 MeV I ion beam by the measurements of a superconducting quantum interference device (SQUID) magnetometer as well as of soft X-ray Magnetic Circular Dichroism (XMCD). It was clearly shown in the magnetization loops by SQUID measurements that the ion irradiation induced the ferromagnetic state in the FeRh thin films even below room temperature. This was also confirmed by the Fe L2,3-edge XMCD measurements for the irradiated FeRh film samples. However, we found that the irradiation ion fluence dependence on the magnetization was totally different between two measurement techniques. We also revealed by XMCD sum rule analysis that the ferromagnetism in the ion irradiated FeRh thin films was mainly dominated by the spin moment.

  3. Study on ferromagnetic ordering of FeRh thin films induced by energetic heavy ion irradiation by means of X-ray Magnetic Circular Dichroism

    Energy Technology Data Exchange (ETDEWEB)

    Aikoh, Kazuma; Tohki, Atsushi [Department of Materials Science, Osaka Prefecture University, Sakai, Osaka 599-8531 (Japan); Okuda, Shuichi [Radiation Research Center, Osaka Prefecture University, Sakai, Osaka 599-8570 (Japan); Saitoh, Yuichi; Kamiya, Tomihiro [Takasaki Advanced Radiation Research Institute, Japan Atomic Energy Agency, Takasaki, Gumma 370-1292 (Japan); Nakamura, Tetsuya [Japan Synchrotron Radiation Research Institute, SPring-8, Sayo, Hyogo 679-5198 (Japan); Kinoshita, Toyohiko [Japan Synchrotron Radiation Research Institute, SPring-8, Sayo, Hyogo 679-5198 (Japan); CREST-JST, Kawaguchi, Saitama 332-0012 (Japan); Iwase, Akihiro [Department of Materials Science, Osaka Prefecture University, Sakai, Osaka 599-8531 (Japan); Matsui, Toshiyuki, E-mail: t-matsui@21c.osakafu-u.ac.jp [Research Organization of the 21st Century, Osaka Prefecture University, Sakai, Osaka 599-8531 (Japan)

    2013-11-01

    We investigated the ion irradiation induced ferromagnetic state of FeRh thin films with 10 MeV I ion beam by the measurements of a superconducting quantum interference device (SQUID) magnetometer as well as of soft X-ray Magnetic Circular Dichroism (XMCD). It was clearly shown in the magnetization loops by SQUID measurements that the ion irradiation induced the ferromagnetic state in the FeRh thin films even below room temperature. This was also confirmed by the Fe L{sub 2,3}-edge XMCD measurements for the irradiated FeRh film samples. However, we found that the irradiation ion fluence dependence on the magnetization was totally different between two measurement techniques. We also revealed by XMCD sum rule analysis that the ferromagnetism in the ion irradiated FeRh thin films was mainly dominated by the spin moment.

  4. Quantitative x-ray magnetic circular dichroism mapping with high spatial resolution full-field magnetic transmission soft x-ray spectro-microscopy

    Science.gov (United States)

    Robertson, MacCallum J.; Agostino, Christopher J.; N'Diaye, Alpha T.; Chen, Gong; Im, Mi-Young; Fischer, Peter

    2015-05-01

    The spectroscopic analysis of X-ray magnetic circular dichroism (XMCD), which serves as strong and element-specific magnetic contrast in full-field magnetic transmission soft x-ray microscopy, is shown to provide information on the local distribution of spin (S) and orbital (L) magnetic moments down to a spatial resolution of 25 nm limited by the x-ray optics used in the x-ray microscope. The spatially resolved L/S ratio observed in a multilayered (Co 0.3 nm/Pt 0.5 nm) × 30 thin film exhibiting a strong perpendicular magnetic anisotropy decreases significantly in the vicinity of domain walls, indicating a non-uniform spin configuration in the vertical profile of a domain wall across the thin film. Quantitative XMCD mapping with x-ray spectro-microscopy will become an important characterization tool for systems with topological or engineered magnetization inhomogeneities.

  5. Nuclear velocity perturbation theory for vibrational circular dichroism: An approach based on the exact factorization of the electron-nuclear wave function

    Energy Technology Data Exchange (ETDEWEB)

    Scherrer, Arne [Martin-Luther-University Halle-Wittenberg, von-Danckelmann-Platz 4, D-06120 Halle (Germany); UMR 8640 ENS-CNRS-UPMC, Département de Chimie, 24 rue Lhomond, École Normale Supérieure, 75005 Paris (France); UPMC Université Paris 06, 4, Place Jussieu, 75005 Paris (France); Agostini, Federica; Gross, E. K. U. [Max-Planck-Institute of Microstructure Physics, Weinberg 2, D-06120 Halle (Germany); Sebastiani, Daniel [Martin-Luther-University Halle-Wittenberg, von-Danckelmann-Platz 4, D-06120 Halle (Germany); Vuilleumier, Rodolphe [UMR 8640 ENS-CNRS-UPMC, Département de Chimie, 24 rue Lhomond, École Normale Supérieure, 75005 Paris (France); UPMC Université Paris 06, 4, Place Jussieu, 75005 Paris (France)

    2015-08-21

    The nuclear velocity perturbation theory (NVPT) for vibrational circular dichroism (VCD) is derived from the exact factorization of the electron-nuclear wave function. This new formalism offers an exact starting point to include correction terms to the Born-Oppenheimer (BO) form of the molecular wave function, similar to the complete-adiabatic approximation. The corrections depend on a small parameter that, in a classical treatment of the nuclei, is identified as the nuclear velocity. Apart from proposing a rigorous basis for the NVPT, we show that the rotational strengths, related to the intensity of the VCD signal, contain a new contribution beyond-BO that can be evaluated with the NVPT and that only arises when the exact factorization approach is employed. Numerical results are presented for chiral and non-chiral systems to test the validity of the approach.

  6. Determination of the absolute configuration of perylene quinone-derived mycotoxins by measurement and calculation of electronic circular dichroism spectra and specific rotations.

    Science.gov (United States)

    Podlech, Joachim; Fleck, Stefanie C; Metzler, Manfred; Bürck, Jochen; Ulrich, Anne S

    2014-09-01

    Altertoxins I-III, alterlosins I and II, alteichin (alterperylenol), stemphyltoxins I-IV, stemphyperylenol, stemphytriol, 7-epi-8-hydroxyaltertoxin I, and 6-epi-stemphytriol are mycotoxins derived from perylene quinone, for which the absolute configuration was not known. Electronic circular dichroism (ECD) spectra were calculated for these compounds and compared with measured spectra of altertoxins I-III, alteichin, and stemphyltoxin III and with reported Cotton effects. Specific rotations were calculated and compared with reported specific rotations. The absolute configuration of all the toxins, except for stemphyltoxin IV, could thus be determined. The validity of the assignment was high whenever reported ECD data were available for comparison, and the validity was lower when the assignment was based only on the comparison of calculated and reported specific rotations. ECD spectra are intrinsically different for toxins with a biphenyl substructure and for toxins derived from dihydroanthracene.

  7. Vacuum-Ultraviolet Circular Dichroism Spectra of Escherichia coli Dihydrofolate Reductase and Its Mutants: Contributions of Phenylalanine and Tyrosine Side Chains and Exciton Coupling of Two Tryptophan Side Chains.

    Science.gov (United States)

    Ohmae, Eiji; Tanaka, Suguru; Miyashita, Yurina; Katayanagi, Katsuo; Matsuo, Koichi

    2015-10-15

    Vacuum-ultraviolet (VUV) circular dichroism (CD) spectroscopy has recently been used for secondary structure analysis of proteins; however, the contribution of aromatic side chains to protein VUV CD spectra is unresolved. In this report, VUV CD spectra of 10 Escherichia coli dihydrofolate reductase (DHFR) mutants, in which each phenylalanine or tyrosine residue was mutated to leucine, were measured down to 175 nm at 25 °C and pH 8.0 to elucidate the contributions of these aromatic side chains to the high-energy transitions of peptide bonds. The VUV CD spectra of these mutants were different from the spectrum of the wild-type protein, indicating that the contribution of the phenylalanine and tyrosine side chains of DHFR extends to the VUV region. Furthermore, the VUV CD spectrum and the folate- or NADP(+)-induced spectral change of F103L mutant DHFR indicated a modification and regeneration of exciton coupling between the Trp47 and Trp74 side chains, respectively, suggesting that exciton coupling may also contribute to the CD spectrum of DHFR in the VUV region. These results should be useful for theoretically characterizing the contribution of aromatic side chains to protein CD spectra, leading to the improvement of protein secondary-structure analysis by VUV CD spectroscopy.

  8. Stereochemistry and solid-state circular dichroism spectroscopy of eight-coordinate chiral lanthanide complexes

    Institute of Scientific and Technical Information of China (English)

    ZHOU Nan; WAN ShiGang; ZHAO Jian; LIN YiJi; XUAN WeiMin; FANG XueMing; ZHANG Hui

    2009-01-01

    Eight-coordinate chiral lanthanide complexes[Eu(dbm)_3L~(RR)](1),[Eu(dbm)_3L~(SS)](2) and[Tb(dbm)_3L~(RR)](3)(L~(RR)/L~(SS)=(-)-1(+)-4,5-pineno-2,2'-bipyridine,Hdbm=dibenzoylmethane) were synthesized stereoselectively,which were characterized by UV-vis,CD spectra and X-ray single-crystal diffraction.The mirrorimage structure features of complexes 1 and 2 were obtained by combination of the solid-state CD spectra and the crystal structure analysis.After further comparison with the solid-state CD spectra of six-coordinate and seven-coordinate metal complexes containing β-diketone ligands,the CD spectraabsolute configuration correlation rule for the eight-coordinate β-diketonate lanthanide complexes was proposed through the exciton chirality method for the first time.The △ or Λ absolute configurations of complexes 1-3 with the distorted square antiprism geometry were confirmed by the X-ray single-crystal analysis.

  9. Stereochemistry and solid-state circular dichroism spectroscopy of eight-coordinate chiral lanthanide complexes

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    Eight-coordinate chiral lanthanide complexes [Eu(dbm)3LRR](1),[Eu(dbm)3LSS](2) and [Tb(dbm)3LRR](3)(LRR/LSS =(-)-/(+)-4,5-pineno-2,2’-bipyridine,Hdbm = dibenzoylmethane) were synthesized stereoselectively,which were characterized by UV-vis,CD spectra and X-ray single-crystal diffraction.The mirrorimage structure features of complexes 1 and 2 were obtained by combination of the solid-state CD spectra and the crystal structure analysis.After further comparison with the solid-state CD spectra of six-coordinate and seven-coordinate metal complexes containing β-diketone ligands,the CD spectraabsolute configuration correlation rule for the eight-coordinate β-diketonate lanthanide complexes was proposed through the exciton chirality method for the first time.The △ or Λ absolute configurations of complexes 1―3 with the distorted square antiprism geometry were confirmed by the X-ray single-crystal analysis.

  10. Green Oxidation of Menthol Enantiomers and Analysis by Circular Dichroism Spectroscopy: An Advanced Organic Chemistry Laboratory

    Science.gov (United States)

    Geiger, H. Cristina; Donohoe, James S.

    2012-01-01

    Green chemistry addresses environmental concerns associated with chemical processes and increases awareness of possible harmful effects of chemical reagents. Efficient reactions that eliminate or reduce the use of organic solvents or toxic reagents are increasingly available. A two-week experiment is reported that entails the calcium hypochlorite…

  11. Magnetic circular dichroism spectroscopy of weakly exchange coupled transition metal dimers: A model study

    DEFF Research Database (Denmark)

    Piligkos, S.; Slep, L.D.; Weyhermuller, T.;

    2009-01-01

    A- is the monoanion of pyridine-2-aldoxime. The trivalent metal ion M(III) is either diamagnetic Ga(III) or paramagnetic Cr(III) (S-Cr = 3/2). The divalent metal ion M(II) is either diamagnetic Zn(II) or paramagnetic Ni(II) (S-Ni = 1). The three systems 1 (CrZn), 2 (GaNi) and 3 (CrNi) have been structurally...

  12. Photoelectron circular dichroism in the multiphoton ionization by short laser pulses. I. Propagation of single-active-electron wave packets in chiral pseudo-potentials.

    Science.gov (United States)

    Artemyev, Anton N; Müller, Anne D; Hochstuhl, David; Demekhin, Philipp V

    2015-06-28

    A theoretical method to study the angle-resolved multiphoton ionization of polyatomic molecules is developed. It is based on the time-dependent formulation of the Single Center (TDSC) method and consists in the propagation of single-active-electron wave packets in the effective molecular potentials in the presence of intense laser pulses. For this purpose, the time-dependent Schrödinger equation for one electron, moving in a molecular field and interacting with an arbitrary laser pulse, is solved in spherical coordinates by an efficient numerical approach. As a test, the method is applied to the one- and two-photon ionizations of a model methane-like chiral system by circularly polarized short intense high-frequency laser pulses. Thereby, we analyze the photoelectron circular dichroism (PECD) in the momentum distribution. The considered model application illustrates the capability of the TDSC method to study multiphoton PECD in fixed-in-space and randomly oriented chiral molecules. PMID:26133408

  13. A circular dichroism sensor for Ni{sup 2+} and Co{sup 2+} based on L-cysteine capped cadmium sulfide quantum dots

    Energy Technology Data Exchange (ETDEWEB)

    Tedsana, Wimonsiri [Materials Chemistry Research Center, Department of Chemistry and Center of Excellence for Innovation in Chemistry, Faculty of Science, Khon Kaen University, Khon Kaen 40002 (Thailand); Tuntulani, Thawatchai [Department of Chemistry, Faculty of Science, Chulalongkorn University, Bangkok 10330 (Thailand); Ngeontae, Wittaya, E-mail: wittayange@kku.ac.th [Materials Chemistry Research Center, Department of Chemistry and Center of Excellence for Innovation in Chemistry, Faculty of Science, Khon Kaen University, Khon Kaen 40002 (Thailand)

    2015-03-31

    Highlights: • Demonstrated a new efficient sensor platform based quantum dots. • Used chiral quantum dots as CD sensor for the detection of heavy metal ions for the first time. • The proposed CD sensor showed highest selectivity towards Ni{sup 2+} and Co{sup 2+}. • Low detection limits of 7.33 μM and 1.13 μM for Ni{sup 2+} and Co{sup 2+}, respectively. • Can be used in real water samples comparing with ICP-OES. - Abstract: A new circular dichroism sensor for detecting Ni{sup 2+} and Co{sup 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{sup 2+} or Co{sup 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{sup 2+} and Co{sup 2+}. On the other hand, other studied cations did not alter the original CD spectrum. Moreover, when increasing the concentration of Ni{sup 2+} or Co{sup 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 μM and 1.13 μM for the detection of Ni{sup 2+} and Co{sup 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{sup 2+} and Co{sup 2+} in real water samples, and the results agreed well with the analysis using the standard ICP-OES.

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

    Energy Technology Data Exchange (ETDEWEB)

    Tobin, J.G.; Goodman, K.W. [Lawrence Berkeley National Lab., CA (United States); Schumann, F.O. [Pennsylvania State Univ., University Park, PA (United States)] [and others

    1997-04-01

    Element specific surface magnetometry remains a central goal of synchrotron radiation based studies of nanomagnetic structures. One appealing possibility is the combination of x-ray absorption dichroism measurements and the theoretical framework provided by the {open_quotes}sum rules.{close_quotes} Unfortunately, sum rule analysis are hampered by several limitations including delocalization of the final state, multi-electronic phenomena and the presence of surface dipoles. An alternative experiment, Magnetic X-Ray Dichroism in Photoelectron Spectroscopy, holds out promise based upon its elemental specificity, surface sensitivity and high resolution. Computational simulations by Tamura et al. demonstrated the relationship between exchange and spin orbit splittings and experimental data of linear and circular dichroisms. Now the authors have developed an analytical framework which allows for the direct extraction of core level exchange splittings from circular and linear dichroic photoemission data. By extending a model initially proposed by Venus, it is possible to show a linear relation between normalized dichroism peaks in the experimental data and the underlying exchange splitting. Since it is reasonable to expect that exchange splittings and magnetic moments track together, this measurement thus becomes a powerful new tool for direct surface magnetometry, without recourse to time consuming and difficult spectral simulations. The theoretical derivation will be supported by high resolution linear and circular dichroism data collected at the Spectromicroscopy Facility of the Advanced Light Source.

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

    Science.gov (United States)

    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.

  16. Proximity effects and exchange bias in Co/MnF2(111) heterostructures studied by x-ray magnetic circular dichroism

    Science.gov (United States)

    Suturin, S. M.; Fedorov, V. V.; Banshchikov, A. G.; Baranov, D. A.; Koshmak, K. V.; Torelli, P.; Fujii, J.; Panaccione, G.; Amemiya, K.; Sakamaki, M.; Nakamura, T.; Tabuchi, M.; Pasquali, L.; Sokolov, N. S.

    2013-01-01

    Cobalt nano-structured ultrathin films were grown on orthorhombic MnF2 by molecular beam epitaxy on CaF2 epitaxial layers deposited on Si(111) substrates. The Co film was grown at room temperature. It was found to be polycrystalline, forming nano-islands with height≈diameter≤10 nm. X-ray absorption evidences the chemical stability of the Co/MnF2 interface. Remarkably, x-ray magnetic circular dichroism (XMCD) demonstrates that the Co induces a net magnetization on the Mn ions close to the interface. The magnetic moments of these Mn ions couple antiparallel to the Co and rotate upon field reversal following the magnetization of the Co both below and high above the Néel temperature of MnF2 (TN = 67 K). The density of coupled Mn moments is found to be temperature dependent, with an equivalent thickness of ˜1.5 MnF2 monolayers at 20 K, decreasing to about ˜0.5 ML as the temperature is raised to 300 K. Interestingly, the intensity of the Mn XMCD signal appears to be related to the coercivity of the Co layer. This behavior is interpreted in terms of the competition between thermal fluctuations, exchange coupling between Co and Mn at the interface and, at low temperature, the antiferromagnetic order in MnF2.

  17. Interaction of bovine serum albumin (BSA) with novel gemini surfactants studied by synchrotron radiation scattering (SR-SAXS), circular dichroism (CD), and nuclear magnetic resonance (NMR).

    Science.gov (United States)

    Gospodarczyk, W; Szutkowski, K; Kozak, M

    2014-07-24

    The interaction of three dicationic (gemini) surfactants-3,3'-[1,6-(2,5-dioxahexane)]bis(1-dodecylimidazolium) chloride (oxyC2), 3,3'-[1,16-(2,15-dioxahexadecane)]bis(1-dodecylimidazolium) chloride (oxyC12), and 1,4-bis(butane)imidazole-1-yl-3-dodecylimidazolium chloride (C4)--with bovine serum albumin (BSA) has been studied by the use of small-angle X-ray scattering (SAXS), circular dichroism (CD), and (1)H nuclear magnetic resonance diffusometry. The results of CD studies show that the conformation of BSA was changed dramatically in the presence of all studied surfactants. The greater decrease (from 56 to 24%) in the α-helical structure of BSA was observed for oxyC2 surfactant. The radii of gyration estimated from SAXS data varied between 3 and 26 nm for the BSA/oxyC2 and BSA/oxyC12 systems. The hydrodynamic radius of the BSA/surfactant system estimated from NMR diffusometry varies between 5 and 11 nm for BSA/oxyC2 and 5 and 8 nm for BSA/oxyC12.

  18. Magnetic states of Mn and Co atoms at Co2MnGe/MgO interfaces seen via soft x-ray magnetic circular dichroism

    Science.gov (United States)

    Asakura, D.; Koide, T.; Yamamoto, S.; Tsuchiya, K.; Shioya, T.; Amemiya, K.; Singh, V. R.; Kataoka, T.; Yamazaki, Y.; Sakamoto, Y.; Fujimori, A.; Taira, T.; Yamamoto, M.

    2010-11-01

    The magnetic states of Mn and Co atoms in Co-rich Co2MnGe Heusler alloy thin films facing an MgO barrier were studied by means of soft x-ray magnetic circular dichroism (XMCD). In particular, the Co2MnGe film-thickness dependence of the Mn and Co magnetic moments was investigated. With a decrease in the Co2MnGe film thickness to 1-2 monolayers (MLs), the spin magnetic moment of Mn decreased and the MnL2,3 -edge x-ray absorption spectra (XAS) showed a Mn2+ -like multiplet structure in MnO, in contrast to samples thicker than 4 ML, indicating that the Mn atoms of the 1 and 2 ML samples were oxidized. The Co spin magnetic moment increased slightly with decreasing thickness. A Co2+ -like multiplet structure in CoO was not observed in all the CoL2,3 -edge XAS and XMCD, indicating that, even in the ultrathin samples, the Co atoms were not oxidized, and were more strongly spin polarized than those in the thicker samples. Co spin magnetic moments of 1.40-1.77μB larger than the theoretical value for ideal stoichiometric Co2MnGe (˜1μB) and the Co-rich film composition imply the presence of Co antisites that would lower the spin polarization.

  19. Measuring magnetisation reversal in micron-sized Nd2Fe14B single crystals by microbeam x-ray magnetic circular dichroism

    Science.gov (United States)

    Sugawara, Akira; Ueda, Kazuhiro; Nakayama, T.; Lee, N.; Yamamoto, H.

    2016-10-01

    Magnetisation reversal of micron-sized Nd2Fe14B single crystals with magnetisation as weak as 10-9 emu (1 µm size) was studied. Single-crystal specimens (cylinders with diameter and height of 1 to 6 µm) were prepared by focused-ion beam so that both the magnetic easy and hard axes were included in the basal plane. Their magnetic hysteresis loops were measured when they were rotated with respect to the cylindrical axis by using microbeam hard-x-ray magnetic circular dichroism (XMCD) under transmission geometry. It was found that coercivity is inversely proportional to the cosine of the angle between the magnetocrystalline easy axis and magnetic-field direction and that the magnetisation reversal is dominated by domain-wall pinning in two different modes. One is related to penetration of the reversed domain nucleated in a subsurface soft layer into the bulk hard phase, of which the hysteresis loops exhibit a single-stage abrupt jump in magnetization. The other mode is pinning of the walls within the bulk grain, of which the hysteresis loops exhibit a plateau. The multi-domain structure associated with the pinning was confirmed by XMCD mapping. The proposed method fills the gap between conventional bulk magnetic measurement and submicron-scale electrical-transport measurement for nanofabricated thin films and/or fine particles. It is expected to provide new insights into elemental magnetisation processes in micron-scale regions.

  20. Magnetic circular dichroism of porphyrins containing M = Ca, Ni, and Zn. A computational study based on time-dependent density functional theory.

    Science.gov (United States)

    Peralta, G A; Seth, Michael; Ziegler, Tom

    2007-10-29

    A theoretical study is presented on the magnetic circular dichroism (MCD) exhibited by the porphyrin complexes MP (M = Mg,Ni,Zn), MTPP (M = Mg,Ni,Zn), and NiOEP, where P = porphyrin, TPP = tetraphenylporphyrin, and OEP = octaethylporphyrin. The study makes use of a newly implemented method for the calculation of A and B terms from the theory of MCD and is based on time-dependent density functional theory (TD-DFT). It is shown that the MCD spectrum is dominated by a single positive A term in the Q-band region in agreement with experiment where available. The band can be fully explained as the first transition in Gouterman's four-orbital model for the type of porphyrins studied here. For the Soret band, the experimental MCD spectrum appears as a single positive A term. This is also what is found computationally for NiP and NiTPP, where the second transition in Gouterman's four-orbital model give rise to a positive A term. However, for the remaining systems, the simulated MCD spectrum is actually due to two B terms that have the appearance of one positive pseudo A term. The two B terms appear because the second Gouterman state is coupled strongly to a second excited state (b(2u) --> 2e(g)) of nearly the same energy by the external magnetic field. PMID:17914806

  1. 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.

    Science.gov (United States)

    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

  2. Application of supervised Kohonen map and counter propagation neural network for classification of nucleic acid structures based on their circular dichroism spectra

    Science.gov (United States)

    Ghobadi, Mohadeseh Zarei; Kompany-Zareh, Mohsen

    2014-11-01

    One of the most popular instrumental methods to detect the DNA structure is circular dichroism. Specific experimental conditions are required to form different structures of DNA. However, there is the possibility of different structures establishing in the similar circumstance. So, methods development to improve the classification and prediction of structures using their spectra information are needed. To this end, we applied unsupervised (PCA) and supervised (PLS-DA, SKN, and CPNN) approaches to classify CD spectra dataset of different DNA sequences (random coil (ss-DNA), duplex, hairpin, reversed and normal triplex, parallel and antiparallel G-quadruplex, and i-motif). The main part of this work concentrates on the application of artificial neural networks and weight analysis to obtain more classification and prediction accuracy. For this purpose, the trained network was run 10 times, and the average weights were taken. Also, weight analysis was done for the prediction of mixture samples include different structures. The results prove that new method of weights analysis based on SKN and CPNN is useful for classification of complicated data such as different types of DNA structures.

  3. Photo-induced magnetization dynamics of FeRh thin films investigated by time-resolved X-ray magnetic circular dichroism

    Energy Technology Data Exchange (ETDEWEB)

    Radu, Ilie [Institut fuer Experimentelle Physik, Universitaet Regensburg (Germany); BESSY GmbH, Berlin (Germany); Stamm, Christian; Kachel, Torsten; Pontius, Niko; Duerr, Hermann [BESSY GmbH, Berlin (Germany); Ramm, Paul; Back, Christian [Institut fuer Experimentelle Physik, Universitaet Regensburg (Germany); Thiele, Jan [Hitachi GST, San Jose Research Center (United States)

    2008-07-01

    For close to equiatomic composition the FeRh alloy undergoes a first-order phase transition from the antiferromagnetic (AFM) to ferromagnetic (FM) state upon heating above room temperature. We trigger the magnetic phase transition by femtosecond laser excitation and study the subsequent dynamics of the Fe and Rh magnetic moments in an element specific manner using X-ray magnetic circular dichroism (XMCD) as a probing tool. For both elements we observe a gradual growth of ferromagnetic ordering that takes place on a 200 ps time scale after optical excitation. On the other hand, once in the FM state, FeRh can be demagnetized on a few picoseconds time interval, the observed dynamics being limited by the width of the X-ray probing pulse (here 10 ps). By comparison to the demagnetization dynamics measured on Ni under similar conditions, we retrieve the lower limit of the demagnetization process that evolves on a sub-picosecond time scale. Hence, the AFM-FM phase transition in conjunction with time-resolved XMCD allow us to study at a microscopic level the elementary processes involved in the magnetization growth, demagnetization and re-magnetization phenomena.

  4. Laser-induced generation and quenching of magnetization on FeRh investigated with time-resolved X-ray magnetic circular dichroism

    Energy Technology Data Exchange (ETDEWEB)

    Radu, Ilie [Regensburg University, Regensburg (Germany); BESSY GmbH, Berlin (Germany); Stamm, Christian; Pontius, Niko; Kachel, Torsten; Duerr, Hermann [BESSY GmbH, Berlin (Germany); Ramm, Paul; Back, Christian [Regensburg University, Regensburg (Germany); Thiele, Jan-Ulrich [Hitachi Global Storage, San Jose, CA (United States)

    2009-07-01

    Upon heating, the equiatomic FeRh alloy exhibits a first-order magnetic phase transition from the antiferromagnetic (AFM) to the ferromagnetic (FM) state around room temperature. Here, we study the fs laser-induced AFM-FM phase transition as well as the transition from FM towards the paramagnetic state by employing the time-resolved X-ray magnetic circular dichroism. Both Fe and Rh elements show a gradual growth of the magnetic moment within 200 ps after laser excitation. Temperature-dependent data, measured at intermediate temperatures between AFM and FM state, provide evidence for the rapid nucleation and subsequent slow expansion of the FM regions within an AFM matrix. Once in the FM state, FeRh can be optically demagnetized on a few ps time scale (limited by the X-ray probing pulse). Further time-resolved magneto-optics measurements done in the visible spectral range reveal a demagnetization time constant of 200 fs. For the photo-induced demagnetization process we consider a mechanism that follows the transient electronic structure of the system.

  5. Origin-independent sum over states simulations of magnetic and electronic circular dichroism spectra via the localized orbital/local origin method.

    Science.gov (United States)

    Štěpánek, Petr; Bouř, Petr

    2015-04-15

    Although electronic and magnetic circular dichroism (ECD, MCD) spectra reveal valuable details about molecular geometry and electronic structure, quantum-chemical simulations significantly facilitate their interpretation. However, the simulated results may depend on the choice of coordinate origin. Previously (Štěpánek and Bouř, J. Comput. Chem. 2013, 34, 1531), the sum-over-states (SOS) methodology was found useful for efficient MCD computations. Approximate wave functions were "resolved" using time-dependent density functional theory, and the origin-dependence was avoided by placing the origin to the center of mass of the investigated molecule. In this study, a more elegant way is proposed, based on the localized orbital/local origin (LORG) formalism, and a similar approach is also applied to generate ECD intensities. The LORG-like approach yields fully origin-independent ECD and MCD spectra. The results thus indicate that the computationally relatively cheap SOS simulations open a new way of modeling molecular properties, including those involving the origin-dependent magnetic dipole moment operator. PMID:25662937

  6. Oriented circular dichroism analysis of chiral surface-anchored metal-organic frameworks grown by liquid-phase epitaxy and upon loading with chiral guest compounds

    KAUST Repository

    Gu, Zhigang

    2014-06-17

    Oriented circular dichroism (OCD) is explored and successfully applied to investigate chiral surface-anchored metal-organic frameworks (SURMOFs) based on camphoric acid (D- and Lcam) with the composition [Cu2(Dcam) 2x(Lcam)2-2x(dabco)]n (dabco=1,4-diazabicyclo- [2.2.2]-octane). The three-dimensional chiral SURMOFs with high-quality orientation were grown on quartz glass plates by using a layer-by-layer liquid-phase epitaxy method. The growth orientation, as determined by X-ray diffraction (XRD), could be switched between the [001] and [110] direction by using either OH- or COOH-terminated substrates. These SURMOFs were characterized by using OCD, which confirmed the ratio as well as the orientation of the enantiomeric linker molecules. Theoretical computations demonstrate that the OCD band intensities of the enantiopure [Cu2(Dcam)2(dabco)] n grown in different orientations are a direct result of the anisotropic nature of the chiral SURMOFs. Finally, the enantiopure [Cu 2(Dcam)2(dabco)]n and [Cu2(Lcam) 2(dabco)]n SURMOFs were loaded with the two chiral forms of ethyl lactate [(+)-ethyl-D-lactate and (-)-ethyl-L-lactate)]. An enantioselective enrichment of >60 % was observed by OCD when the chiral host scaffold was loaded from the racemic mixture. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Molecular and vibrational structure of diphenylether and its 4,4' -dibromo derivative. Infrared linear dichroism spectroscopy and density functional theory calculations

    DEFF Research Database (Denmark)

    Eriksen, Troels K; Karlsen, Eva; Spanget-Larsen, Jens

    2015-01-01

    The title compounds were investigated by means of Linear Dichroism (LD) IR spectroscopy on samples partially aligned in uniaxially stretched low-density polyethylene and by density functional theory calculations. Satisfactory overall agreement between observed and calculated vibrational wavenumbe...... and IR intensities are obtained, allowing a fairly detailed assignment of the observed transitions in terms of individual nuclear motions....

  8. Linear and Chiral Dichroism in the Electron Microscope

    CERN Document Server

    Schattschneider, Peter

    2012-01-01

    The growing interest in the miniaturization of magnetic storage media and the quest for novel spintronics applications rely on element specific detection of spin and orbital magnetic moments in a solid. The most sophisticated technique to reach this aim has been XMCD (X-ray magnetic circular dichroism), largely used in synchrotron beam lines. The spatial resolution limit of this technique is of the order of 20 - 50 nm. This poses a sensible limit for the study of nanostructured devices. This book describes EMCD (energy loss magnetic chiral dichroism), a phenomenon in energy loss spectroscopy d

  9. Magnetic x-ray dichroism in ultrathin epitaxial films

    Energy Technology Data Exchange (ETDEWEB)

    Tobin, J.G.; Goodman, K.W. [Lawrence Berkeley National Lab., CA (United States); Cummins, T.R. [Univ. of Missouri, Rolla, MO (United States)] [and others

    1997-04-01

    The authors have used Magnetic X-ray Linear Dichroism (MXLD) and Magnetic X-ray Circular Dichroism (MXCD) to study the magnetic properties of epitaxial overlayers in an elementally specific fashion. Both MXLD and MXCD Photoelectron Spectroscopy were performed in a high resolution mode at the Spectromicroscopy Facility of the ALS. Circular Polarization was obtained via the utilization of a novel phase retarder (soft x-ray quarter wave plate) based upon transmission through a multilayer film. The samples were low temperature Fe overlayers, magnetic alloy films of NiFe and CoNi, and Gd grown on Y. The authors results include a direct comparison of high resolution angle resolved Photoelectron Spectroscopy performed in MXLD and MXCD modes as well as structural studies with photoelectron diffraction.

  10. Infrared, vibrational circular dichroism, and Raman spectral simulations for β-sheet structures with various isotopic labels, interstrand, and stacking arrangements using density functional theory.

    Science.gov (United States)

    Welch, William R W; Kubelka, Jan; Keiderling, Timothy A

    2013-09-12

    Infrared (IR), Raman, and vibrational circular dichroism (VCD) spectral variations for different β-sheet structures were studied using simulations based on density functional theory (DFT) force field and intensity computations. The DFT vibrational parameters were obtained for β-sheet fragments containing nine-amides and constrained to a variety of conformations and strand arrangements. These were subsequently transferred onto corresponding larger β-sheet models, normally consisting of five strands with ten amides each, for spectral simulations. Further extension to fibril models composed of multiple stacked β-sheets was achieved by combining the transfer of DFT parameters for each sheet with dipole coupling methods for interactions between sheets. IR spectra of the amide I show different splitting patterns for parallel and antiparallel β-sheets, and their VCD, in the absence of intersheet stacking, have distinct sign variations. Isotopic labeling by (13)C of selected residues yields spectral shifts and intensity changes uniquely sensitive to relative alignment of strands (registry) for antiparallel sheets. Stacking of multiple planar sheets maintains the qualitative spectral character of the single sheet but evidences some reduction in the exciton splitting of the amide I mode. Rotating sheets with respect to each other leads to a significant VCD enhancement, whose sign pattern and intensity is dependent on the handedness and degree of rotation. For twisted β-sheets, a significant VCD enhancement is computed even for sheets stacked with either the same or opposite alignments and the inter-sheet rotation, depending on the sense, can either further increase or weaken the enhanced VCD intensity. In twisted, stacked structures (without rotation), similar VCD amide I patterns (positive couplets) are predicted for both parallel and antiparallel sheets, but different IR intensity distributions still enable their differentiation. Our simulation results prove useful

  11. Raman, SERS, and induced circular dichroism techniques as a probe of pharmaceuticals in their interactions with the human serum albumin and p-glycoprotein

    Science.gov (United States)

    Fleury, Fabrice; Ianoul, Anatoli I.; Baggetto, Loris; Jardillier, Jean-Claude; Alix, Alain J.; Nabiev, Igor R.

    1999-04-01

    Camptothecin (CPT) derivatives are the well known inhibitors of the human DNA topoisomerase (topo) I. Two of them, irinotecan and topotecan, are just in the clinics; 9-amino- CPT is on the stage II of clinical trials, and the active search for new derivatives is now in progress. Stability of the CPT derivatives on their way to the target and resistance of cancer cells to these drugs present the crucial problem of the chemotherapy. Human serum albumin (HSA) is the mediator of transport and metabolism of numerous pharmaceuticals in the blood and P-glycoprotein (P- gp) plays a crucial role of the mediator of the multidrug resistance (MDR) of the cancer cells. This paper present the result of analysis of molecular interactions of some drugs of CPT family with the HSA and P-gp. Induced circular dichroism (CD) and Raman techniques have been applied for monitoring molecular interaction of drugs with HSA as well as to identify the conformational transition of the protein induced by the drug binding. Drug molecular determinants responsible for interaction have been identified and their binding sites within the HSA have been localized. New cancer cells lines exhibiting an extremely high level of MDR resistance have been established and were shown to contain the P-gp overproduced in the quantities of 35 percent from the all membrane proteins. The membrane fractions of these cells with the controls presented by the membranes of the parental membrane proteins. The membrane fractions of these cells with the controls presented by the membranes of the parental sensitive cells may be used as a model system for spectroscopic analysis of the specific pharmaceuticals/P-gp interactions.

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

    Energy Technology Data Exchange (ETDEWEB)

    Dinh, Thanh-Chung; Renger, Thomas, E-mail: thomas.renger@jku.at [Institut für Theoretische Physik, Johannes Kepler University Linz, Altenberger Str. 69, 4040 Linz (Austria)

    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.

  13. Kramers-Kronig transformation of experimental electronic circular dichroism: application to the analysis of optical rotatory dispersion in dimethyl-L-tartrate.

    Science.gov (United States)

    Polavarapu, Prasad L; Petrovic, Ana G; Zhang, Peng

    2006-09-01

    When a limited region of the experimental electronic circular dichroism (ECD) spectrum is subjected to Kramers-Kronig (KK) transformation, the resulting optical rotatory dispersion (ORD) may or may not reproduce the experimentally measured ORD in the long-wavelength nonresonant region. If the KK transform of experimentally measured ECD in a limited wavelength region reproduces the experimentally measured ORD in the long-wavelength nonresonant region, then that observation indicates that the ORD in the long-wavelength nonresonant region should be satisfactorily predicted from the correspondingly limited number of electronic transitions in a reliable quantum mechanical calculation. On the other hand, if the KK transform of experimentally measured ECD in a limited region does not reproduce the experimentally measured ORD in the long-wavelength nonresonant region, then it should be possible to identify the ECD bands in the shorter wavelength region that are responsible for the differences between experimentally observed ORD and KK-transformed ECD. This approach helps to identify the role of ECD associated with higher energy-excited states in the nature of ORD in the long-wavelength nonresonant region. These concepts are demonstrated here by measuring the experimental ECD and ORD for dimethyl-L-tartrate in different solvents. While ECD spectra of dimethyl-L-tartrate in different solvents show little variation, ORD spectra in the long-wavelength nonresonant region show marked solvent dependence. These observations are explained using the difference between experimental ORD and KK-transformed ECD. Quantum mechanical predictions of ECD and ORD are also presented for isolated (R, R)-dimethyl tartrate at the B3LYP/aug-cc-pVDZ level.

  14. The vibrational structure of (E,E’)-1,4-diphenyl-1,3-butadiene. Linear dichroism FTIR spectroscopy and quantum chemical calculations

    DEFF Research Database (Denmark)

    Hansen, Bjarke Knud Vilster; Møller, Søren; Spanget-Larsen, Jens

    2006-01-01

    The title compound (DPB) was investigated by FTIR spectroscopy in liquid solutions and by FTIR linear dichroism (LD) measurements on samples aligned in stretched polyethylene. The LD data provided experimental assignments of molecular transition moment directions and vibrational symmetries for mo...... of a nearly complete assignment of the IR active fundamentals of DPB, involving reassignment of a number of transitions. In addition, previously published Raman spectra of DPB were well predicted by the B3LYP/cc-pVTZ calculations....

  15. Structure of human Rad51 protein filament from molecular modeling and site-specific linear dichroism spectroscopy

    KAUST Repository

    Reymer, A.

    2009-07-08

    To get mechanistic insight into the DNA strand-exchange reaction of homologous recombination, we solved a filament structure of a human Rad51 protein, combining molecular modeling with experimental data. We build our structure on reported structures for central and N-terminal parts of pure (uncomplexed) Rad51 protein by aid of linear dichroism spectroscopy, providing angular orientations of substituted tyrosine residues of Rad51-dsDNA filaments in solution. The structure, validated by comparison with an electron microscopy density map and results from mutation analysis, is proposed to represent an active solution structure of the nucleo-protein complex. An inhomogeneously stretched double-stranded DNA fitted into the filament emphasizes the strategic positioning of 2 putative DNA-binding loops in a way that allows us speculate about their possibly distinct roles in nucleo-protein filament assembly and DNA strand-exchange reaction. The model suggests that the extension of a single-stranded DNA molecule upon binding of Rad51 is ensured by intercalation of Tyr-232 of the L1 loop, which might act as a docking tool, aligning protein monomers along the DNA strand upon filament assembly. Arg-235, also sitting on L1, is in the right position to make electrostatic contact with the phosphate backbone of the other DNA strand. The L2 loop position and its more ordered compact conformation makes us propose that this loop has another role, as a binding site for an incoming double-stranded DNA. Our filament structure and spectroscopic approach open the possibility of analyzing details along the multistep path of the strand-exchange reaction.

  16. Time-dependent density functional theory applied to ligand-field excitations and their circular dichroism in some transition metal complexes

    International Nuclear Information System (INIS)

    Graphical abstract: Ligand-field (LF) transitions in [Co(en)3]3+ and [Rh(en)3]2+ and the low-energy part of the electronic circular dichroism (CD) spectrum of [Fe(phen)3]2+ are investigated with time-dependent density functional theory (TDDFT). There is a strong functional dependence for [Co(en)3]3+ and [Fe(phen)3]2+. ΔSCF methods reproduce the ligand-field singlet excitation energies of [Co(en)3]3+ and [Rh(en)3]2+ well. For the LF transitions of [Co(en)3]3+ TDDFT with a hybrid functional with around 25correction/Coulomb attenuation offers little improvement for the LF transitions in [Co(en)3]3+ because the occupied and unoccupied orbitals involved are in close spatial proximity. Highlights: ► TDDFT Ligand-field (LF) excitations in 3d metal complexes are functional dependent. ► Study of Co(en)3(3+) links sensitivity to correlation/self-interaction balance. ► Correlation effects on the LF spectra are very large. ► Range separated functionals offer limited improvement due to spatial proximity of orbitals. - Abstract: Ligand-field transitions in [Co(en)3]3+ and [Rh(en)3]3+ as well as the low-energy part of the electronic spectrum of [Fe(phen)3]2+ are investigated with time-dependent density functional theory (TDDFT). There is a strong functional dependence for [Co(en)3]3+ and [Fe(phen)3]2+. ΔSCF methods reproduce the ligand-field singlet excitation energies of [Co(en)3]3+ and [Rh(en)3]3+ very well. The case of [Co(en)3]3+ is analyzed in some detail, in particular regarding the possibility of applying a charge-transfer (CT) correction [M.E. Casida, F. Gutierrez, J. Guan, F.-X. Gadea, D.R. Salahub, J.-P. Daudey, J. Chem. Phys. 113 (2000) 7062]. A simple CT correction would not be sufficient, but the magnitude of the charge transfer correction term in comparison with the calculated excitation energy appears to be indicative of self-interaction problems in the ground state electronic structure and in the calculated excitation energies. For the ligand

  17. Electronic and magnetic properties of off-stoichiometric Co{sub 2}Mn{sub β}Si/MgO interfaces studied by x-ray magnetic circular dichroism

    Energy Technology Data Exchange (ETDEWEB)

    Singh, V. R.; Verma, V. K.; Ishigami, K.; Shibata, G.; Fujimori, A., E-mail: fujimori@wyvern.phys.s.u-tokyo.ac.jp [Department of Physics, University of Tokyo, Bunkyo-ku, Tokyo 113-0033 (Japan); Koide, T. [Photon Factory, IMSS, High Energy Accelerator Research Organization, Tsukuba, Ibaraki 305-0801 (Japan); Miura, Y.; Shirai, M. [Research Institute of Electrical Communication, Tohoku University, Katahira 2-1-1, Aoba-ku, Sendai 980-8577 (Japan); Ishikawa, T.; Li, G.-F.; Yamamoto, M. [Division of Electronics for Informatics, Hokkaido University, Sapporo 060-0814 (Japan)

    2015-05-28

    We have studied the electronic and magnetic states of Co and Mn atoms at the interface of the Co{sub 2}Mn{sub β}Si (CMS)/MgO (β = 0.69, 0.99, 1.15, and 1.29) magnetic tunnel junction (MTJ) by means of x-ray magnetic circular dichroism. In particular, the Mn composition (β) dependences of the Mn and Co magnetic moments were investigated. The experimental spin magnetic moments of Mn, m{sub spin}(Mn), derived from x-ray magnetic circular dichroism weakly decreased with increasing Mn composition β in going from Mn-deficient to Mn-rich CMS films. This behavior was explained by first-principles calculations based on the antisite-based site-specific formula unit (SSFU) composition model, which assumes the formation of only antisite defect, not vacancies, to accommodate off-stoichiometry. Furthermore, the experimental spin magnetic moments of Co, m{sub spin}(Co), also weakly decreased with increasing Mn composition. This behavior was consistently explained by the antisite-based SSFU model, in particular, by the decrease in the concentration of Co{sub Mn} antisites detrimental to the half-metallicity of CMS with increasing β. This finding is consistent with the higher tunnel magnetoresistance ratios which have been observed for CMS/MgO/CMS MTJs with Mn-rich CMS electrodes.

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

    Energy Technology Data Exchange (ETDEWEB)

    Ohresser, P., E-mail: philippe.ohresser@synchrotron-soleil.fr; Otero, E.; Choueikani, F.; Chen, K.; Stanescu, S.; Deschamps, F.; Moreno, T.; Polack, F.; Lagarde, B.; Daguerre, J.-P.; Marteau, F. [Synchrotron SOLEIL, L’Orme des Merisiers, Saint-Aubin - BP 48, 91192 Gif-sur-Yvette (France); Scheurer, F.; Joly, L.; Muller, B. [Institut de Physique et Chimie des Matériaux de Strasbourg, UMR 7504 UdS-CNRS, 67034 Strasbourg Cedex 2 (France); Kappler, J.-P. [Synchrotron SOLEIL, L’Orme des Merisiers, Saint-Aubin - BP 48, 91192 Gif-sur-Yvette (France); Institut de Physique et Chimie des Matériaux de Strasbourg, UMR 7504 UdS-CNRS, 67034 Strasbourg Cedex 2 (France); Bunau, O.; Sainctavit, Ph. [Synchrotron SOLEIL, L’Orme des Merisiers, Saint-Aubin - BP 48, 91192 Gif-sur-Yvette (France); Institut de Minéralogie et de Physique des Milieux Condensés, CNRS UMR 7590, Université Pierre et Marie Curie, 75252 Paris Cedex 5 (France)

    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.

  19. Cluster model calculation for X-ray magnetic circular dichroism at rare-earth (R) L sub 2 sub , sub 3 absorption edges in R sub 2 Fe sub 1 sub 4 B

    CERN Document Server

    Asakura, K; Harada, I; Ogasawara, H; Fukui, K; Kotani, A

    2002-01-01

    X-ray magnetic circular dichroism (MCD) at the L sub 2 sub , sub 3 absorption edges for the entire series of rare-earth (RE) elements in R sub 2 Fe sub 1 sub 4 B (R=RE) is studied based on a cluster model including 10 RE and 16 Fe atoms. The cluster model takes into account band effects of RE 5d states, to which the electric dipole transition occurs from the core 2p states, as well as spin polarization of the 5d states due to the interatomic hybridization with the spin polarized Fe 3d states. We also take into account spin and orbital polarization of the 5d states due to the 5d-4f intra-atomic exchange interaction, and the 2p to 4f quadrupole transition. The calculated results are in satisfactory agreement with experimental ones, suggesting that the cluster model calculation provides a new method to calculate quantitatively MCD spectra of RE systems with complicated atomic arrangements. (author)

  20. Determination of the absolute configuration of chiral α-aryloxypropanoic acids using vibrational circular dichroism studies: 2-(2-chlorophenoxy) propanoic acid and 2-(3-chlorophenoxy) propanoic acid

    Science.gov (United States)

    He, Jiangtao; Polavarapu, Prasad L.

    2005-05-01

    The enantiomers of 2-(2-chlorophenoxy) propanoic acid and 2-(3-chlorophenoxy) propanoic acid were resolved on a chiral HPLC column and investigated using mid-infrared vibrational circular dichroism (VCD). Experimental infrared vibrational absorption and VCD spectra were measured in CDCl 3 solution in the 2000-900 cm -1 region and compared with the ab initio predictions of absorption and VCD spectra. The predicted spectra were obtained with density functional theory using B3LYP/6-31G* basis set for the stable and dominant conformers. But the predicted spectra did not provide unambiguous structural information due to intermolecular hydrogen bonding in solution. To eliminate the hydrogen bonding effects, the acids were converted to the corresponding methyl esters and the experimental absorbance and VCD spectra of methyl esters were measured. B3LYP predicted spectra were also obtained for the stable and dominant conformers of the esters. From a comparison of the experimental VCD spectra of methyl esters with corresponding ab initio predictions, the absolute configurations of esters, and therefore of their parent acids, are unambiguously determined to be (+)-( R).

  1. Electronic states of magnetic refrigerator materials Mn0.9Fe1.1P0.55As0.45 using soft x-ray magnetic circular dichroism

    Science.gov (United States)

    Takeda, Y.; Okane, T.; Ohkochi, T.; Fujimori, S.-i.; Saitoh, Y.; Yamagami, H.; Yabuta, H.; Takabatake, T.

    2010-01-01

    The system of MnFeP1-xAsx is a candidate of a magnetic refrigerator material. We have investigated the temperature (T)- and magnetic field (H)-dependence of the magnetic properties of the Mn and Fe ions for Mn0.9Fe1.1P0.55As0.45 using a soft x-ray magnetic circular dichroism (XMCD) in the regions of the Mn and Fe L2,3 absorption edges. In the ferromagnetic states, the magnetic moments of the Mn and Fe ions turn to the same direction. It is considered that the Mn ions are close to divalent (Mn2+) states and that the Fe ions are a mixture of trivalent (Fe3+) and divalent (Fe2+) states. However, we deduce that the ferromagnetic properties of the Fe ions are mainly derived from the Fe2+ states. Using the XMCD sum rules, we have found that the magnitude of the magnetic moment of the Mn ions is larger than that of the Fe ions. The paramagnetic to ferromagnetic transitions are clearly observed by the T- and H- dependent XMCD measurements. Scince the shapes of the spectra don't change in all experiment conditions, the electronic configurations of the Mn and Fe ions are not changed by the PM-FM transition.

  2. X-ray magnetic circular dichroism (XMCD) study of a methoxide-bridged DyIII-CrIII cluster obtained by fluoride abstraction from cis-[CrIIIF2(phen)2]+

    DEFF Research Database (Denmark)

    Dreiser, Jan; Pedersen, Kasper Steen; Birk, Torben;

    2012-01-01

    An isostructural series of dinuclear chromium(III)-lanthanide(III) clusters is formed by fluoride abstraction of cis-[CrF(2)(phen)(2)](+) by Ln(3+) resulting in LnF(3) and methoxide-bridged Cr-Ln clusters (Ln = Nd (1), Tb (2), Dy (3)) of formula [Cr(III)(phen)(2)(µ-MeO)(2)Ln(NO(3))(4)]·xMeOH (x = 2......-2.73). In contrast to fluoride, methoxide bridges in a nonlinear fashion, which facilitates chelation. For 3, X-ray magnetic circular dichroism (XMCD) provides element-specific magnetization curves that are compared to cluster magnetization and susceptibility data acquired by SQUID magnetometry. The combination...... of XMCD and SQUID is able to resolve very small magnetic coupling values and reveals a weak Cr(III)-Dy(III) coupling of j = -0.04(3) cm(-1). The Dy(III) ion has a ground-state Kramers doublet of m(J) = ±13/2, and the first excited doublet is found to be m(J) = ±11/2 at an energy of d = 57(21) cm(-1...

  3. X-ray magnetic circular dichroism at IrL2,3 edges in Fe100-Ir and Co100-Ir alloys: Magnetism of 5d electronic states

    Indian Academy of Sciences (India)

    V V Krishnamurthy; M Suzuki; N Kawamura; T Ishikawa

    2002-05-01

    The formation of induced 5 magnetic moment on Ir in Fe100-Ir (=3, 10 and 17) and Co100-Ir (=5, 17, 25 and 32) alloys has been investigated by X-ray magnetic circular dichroism (XMCD) at Ir L2,3 absorption edges. Sum rule analysis of the XMCD data show that the orbital moment of Ir is in the range of -0.071(2)B to -0.030(1)B in Fe–Ir alloys and -0.067(2)B to 0.024(1)B in Co–Ir alloys. We find that the total moment of Ir in Fe–Ir alloys is approximately 1/5 of the total 3 moment on Fe at all the three compositions. In contrast, the total moment on Ir in Co–Ir alloys varies between 1/6 to 1/16 of the 3 moment on cobalt. The observed trends of Ir moments and the role of interatomic exchange interactions in 5 moment formation are discussed.

  4. Dichroism in Helicoidal Crystals.

    Science.gov (United States)

    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

  5. Secondary structure of the intact H+,K+ -ATPase and of its membrane-embedded region. An attenuated total reflection infrared spectroscopy, circular dichroism and Raman spectroscopy study

    NARCIS (Netherlands)

    Raussens, V.; Jongh, H. de; Pézolet, M.; Ruysschaert, J.-M.; Goormaghtigh, E.

    1998-01-01

    Models of P-type ATPase predict that membrane-embedded fragments represent about 20% of the protein and adopt an all-α-helical structure. While this prediction was confirmed for the Ca2+ -ATPase [Corbalan-Garcia, S., Teruel, J., Villalain, J. and Gomez-Fernandez, J. (1994) Biochemistry 33, 8247-8254

  6. 基于手性金纳米粒子圆二色光谱法识别与检测银离子%Recognition and Detection of Silver Ion by Circular Dichroism Spectrum Based on Chiral Gold Nanoparticles

    Institute of Scientific and Technical Information of China (English)

    韦克毅; 王猛; 杜宇; 蔡波; 江云宝

    2016-01-01

    In this work,chiral gold particles with optical activity can be obtained by a facile liquid phase method.The textural proper-ties of the as-prepared samples were characterized by high resolution transmission electron microscopy,circular dichroism spectrum and absorption spectrum.The results show that the average particle size for the production is 3.6 nm and silver ion can be selectively recognized from 1 3 kinds of metal ions in 1 2 min with universal recurrence.We also established the standard curve for detecting silver ion.This study demonstrates that the linear range for this curve is 0.2-30μmol/L,the linearly dependent coefficient is 0.995(n=15),which supplies a simple new environmentally friendly method for quickly detecting and recognizing silver ion in environmental water samples with high precision.%采用液相制备方法获得具有光学活性的手性金纳米粒子,通过吸收光谱和圆二色光谱及高分辨透射电镜对手性金纳米粒子进行表征.利用圆二色光谱法建立手性金纳米粒子对 Ag+选择性识别方法,结果表明手性金纳米粒子对Ag+响应时间仅需12 min,手性金纳米粒子能够从13种常见金属离子中选择性识别 Ag+,并对多种常见金属离子具有较好的抗干扰能力,检测灵敏度高并且具有良好的重现性.所建立标准曲线线性范围为0.2~30μmol/L,线性相关系数R2=0.995(n=15),Ag+的检测限为0.2μmol/L;为环境水样中 Ag+的识别和检测提供了一种简单、精确、快速、环境友好的新方法.

  7. Analysis of the major chiral compounds of Artemisia herba-alba essential oils (EOs) using reconstructed vibrational circular dichroism (VCD) spectra: En route to a VCD chiral signature of EOs.

    Science.gov (United States)

    Said, Mohammed El-Amin; Vanloot, Pierre; Bombarda, Isabelle; Naubron, Jean-Valère; Dahmane, El Montassir; Aamouche, Ahmed; Jean, Marion; Vanthuyne, Nicolas; Dupuy, Nathalie; Roussel, Christian

    2016-01-15

    An unprecedented methodology was developed to simultaneously assign the relative percentages of the major chiral compounds and their prevailing enantiomeric form in crude essential oils (EOs). In a first step the infrared (IR) and vibrational circular dichroism (VCD) spectra of the crude essential oils were recorded and in a second step they were modelized as a linear weighted combination of the IR and VCD spectra of the individual spectra of pure enantiomer of the major chiral compounds present in the EOs. The VCD spectra of enantiomer of known enantiomeric excess shall be recorded if they are not yet available in a library of VCD spectra. For IR, the spectra of pure enantiomer or racemic mixture can be used. The full spectra modelizations were performed using a well known and powerful mathematical model (least square estimation: LSE) which resulted in a weighting of each contributing compound. For VCD modelization, the absolute value of each weighting represented the percentage of the associate compound while the attached sign addressed the correctness of the enantiomeric form used to build the model. As an example, a model built with the non-prevailing enantiomer will show a negative sign of the weighting value. For IR spectra modelization, the absolute value of each weighting represented the percentage of the compounds without of course accounting for the chirality of the prevailing enantiomers. Comparison of the weighting values issuing from IR and VCD spectra modelizations is a valuable source of information: if they are identical, the EOs are composed of nearly pure enantiomers, if they are different the chiral compounds of the EOs are not in an optically pure form. The method was applied on four samples of essential oil of Artemisia herba-alba in which the three major compounds namely (-)-α-thujone, (+)-β-thujone and (-)-camphor were found in different proportions as determined by GC-MS and chiral HPLC using polarimetric detector. In order to validate the

  8. Polarimetric investigation of materials with both linear and circular anisotropy

    DEFF Research Database (Denmark)

    Naydenova, I.; Nikolova, L.; Todorov, T.;

    1997-01-01

    We investigate light propagation through materials with both linear and circular anisotropy and find the relation of the amplitude and polarization transfer functions to the four anisotropic characteristics: linear circular birefringence, and linear and circular dichroism. We determine these four...

  9. Transfer of chirality from adsorbed chiral molecules to the substrates highlighted by circular dichroism in angle-resolved valence photoelectron spectroscopy

    DEFF Research Database (Denmark)

    Contini, G.; Turchini, S.; Sanna, Simone;

    2012-01-01

    state, that the presence of molecular chiral domains induces asymmetry in the interaction with the substrate and locally transfers the chiral character to the underlying metal atoms participating in the adsorption process; combined information related to the asymmetry of the initial electronic state......Studies of self-assembled chiral molecules on achiral metallic surfaces have mostly focused on the determination of the geometry of adsorbates and their electronic structure. The aim of this paper is to provide direct information on the chirality character of the system and on the chirality......, which is expected to be chiral, and the final electronic state, which locally probes the asymmetry of the potential, has been obtained. Identification of chirality in the adsorption footprint sheds new light on the transfer of chirality from a chiral modifier to a symmetric metal surface and represents...

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

    Science.gov (United States)

    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.

  11. A complex-polarization-propagator protocol for magneto-chiral axial dichroism and birefringence dispersion

    DEFF Research Database (Denmark)

    Cukras, Janusz; Kauczor, Joanna; Norman, Patrick;

    2016-01-01

    theory. Magneto-chiral dichroism and magneto-chiral birefringence spectra in the (resonant) frequency region below the first ionization threshold of R-methyloxirane and L-alanine are presented and compared with the corresponding results obtained for both the electronic circular dichroism and the magnetic...

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

    Science.gov (United States)

    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.

  13. 圆二色谱研究胶原模拟多肽三螺旋结构及其热稳定性%Study of Collagen Mimetic Peptide’s Triple-Helix Structure and Its Thermostability by Circular Dichroism

    Institute of Scientific and Technical Information of China (English)

    张之宝; 王静洁; 陈晖娟; 熊青青; 刘玲蓉; 张其清

    2014-01-01

    In the present study ,the authors explore the triple-helix conformation and thermal stability of collagen mimetic pep-tides (CMPs) as a function of peptide sequence and/or chain length by circular dichroism (CD) .Five CMPs were designed and synthetized varying the number of POG triplets or incorporating an integrin α2β1 binding motif Gly-Phe-Hyp-Gly-Glu-Arg (GFOGER) .CD spectroscopy from 260 to 190 nm was recorded to confirm the existence of triple-helix conformation at room temperature ,while thermal melting and thermal annealing of triple-helix (thermal unfolding and refolding of triple-helix ,respec-tively) was characterized by monitoring ellipticity at 225 nm as a function of temperature .The results demonstrated that all the CMPs adopted triple-helix conformation ,and the thermal stability of the CMPs was enhanced with increasing the number of POG triplets .In contrast to natural collagen ,the thermal denaturation processes of CMPs were reversible ,i .e .the triple-helix unfol-ded upon heating while refolded upon cooling .Meanwhile ,the phenomenon of “hysteresis” was observed by comparing melting and thermal curves .These findings add new insights to the mechanisms of collagen and CMPs assembly ,as well as provide an alternative approach to the fabrication of artificial collagen-likes biomaterials .%胶原是广泛研究和应用的生物材料,具有独特的三螺旋结构,此结构与其生物学性能密切相关。以胶原模拟多肽(collagen mimetic peptide ,CM P)作为胶原的模型分子,通过圆二色谱研究了CM P的三螺旋结构、热稳定性等随序列或长度的改变所发生的规律性变化。根据形成胶原三螺旋结构的重复序列(POG )n及胶原上α2β1整合素识别位点序列GFOGER设计五种不同序列或长度的CM P ,采用圆二色谱表征了CM P的三螺旋结构,并通过检测CM P的程序升温变性和程序降温复性过程中圆二色谱的变化,研究了CM P三螺旋结

  14. X-ray linear dichroism dependence on ferroelectric polarization

    International Nuclear Information System (INIS)

    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. (paper)

  15. Measurements of linear and circular birefringence in metals by femtosecond optical pump-probe spectroscopy

    CERN Document Server

    Wilks, R

    2002-01-01

    Optically induced transient linear and circular birefringence has been studied in three different materials: ferromagnetic Ni, semiconducting GaAs and the non-magnetic metal Al. A pump-probe experiment with sub-ps resolution was set up for this purpose. The time-resolved reflectivity, rotation and ellipticity of the reflected probe beam were recorded after pumping with light of variable helicity. In the Ni sample an ultrafast demagnetisation effect was observed and the variation of the rotation and ellipticity on sub-picosecond time scales was compared. Rotation and ellipticity were found to have a similar time dependence. In GaAs, optical orientation of spin was achieved and the subsequent spin relaxation was measured for different pump powers. Fitting of the optical rotation data has revealed the power dependence of the various decay constants. In the Al sample a small signal was observed that decays on ps time scales. This was attributed to a linear birefringence effect resulting from a cubic optical nonli...

  16. Use of vibrational spectroscopy to study protein and DNA structure, hydration, and binding of biomolecules: A combined theoretical and experimental approach

    DEFF Research Database (Denmark)

    Jalkanen, Karl J.; Jürgensen, Vibeke Würtz; Claussen, Anetta;

    2006-01-01

    We report on our work with vibrational absorption, vibrational circular dichroism, Raman scattering, Raman optical activity, and surface-enhanced Raman spectroscopy to study protein and DNA structure, hydration, and the binding of ligands, drugs, pesticides, or herbicides via a combined theoretic...

  17. Functional studies of soybean (Glycine max L.) seed LEA proteins GmPM6, GmPM11, and GmPM30 by CD and FTIR spectroscopy

    NARCIS (Netherlands)

    Hoekstra, F.A.

    2012-01-01

    The protein and mRNA levels of late embryogenesis abundant (LEA) genes may be linked to osmotic stresses. Here, we characterized three soybean hydrophilic LEA proteins – GmPM11 (LEA I), GmPM6 (LEA II), and GmPM30 (LEA III) – by circular dichroism and Fourier transform infrared spectroscopy. Structur

  18. Photoinduced Circular Anisotropy in Side-Chain Azobenzene Polyesters

    DEFF Research Database (Denmark)

    Nikolova, L.; Todorov, T.; Ivanov, M.;

    1997-01-01

    We report for the first time the inducing of large circular anisotropy in previously unoriented films of side-chain azobenzene polyesters on illumination with circularly polarized light at a wavelength of 488 nm. The circular dichroism and optical activity are measured simultaneously in real time...

  19. X-ray absorption and magnetic circular dichroism of LaCoO3 , La0.7Ce0.3CoO3 , and La0.7Sr0.3CoO3 films: Evidence for cobalt-valence-dependent magnetism

    Science.gov (United States)

    Merz, M.; Nagel, P.; Pinta, C.; Samartsev, A.; v. Löhneysen, H.; Wissinger, M.; Uebe, S.; Assmann, A.; Fuchs, D.; Schuppler, S.

    2010-11-01

    Epitaxial thin films of undoped LaCoO3 , of electron-doped La0.7Ce0.3CoO3 , and of hole-doped La0.7Sr0.3CoO3 exhibit ferromagnetic order with a transition temperature TC≈84K , 23 K, and 194 K, respectively. The spin-state structure for these compounds was studied by soft x-ray magnetic circular dichroism and by near-edge x-ray absorption fine structure at the CoL2,3 and OK edges. It turns out that superexchange between Co3+ high-spin and Co3+ low-spin states is responsible for the ferromagnetism in LaCoO3 . For La0.7Ce0.3CoO3 the Co3+ ions are in a low-spin state and the spin and orbital moments are predominantly determined by a Co2+ high-spin configuration. A spin blockade naturally explains the low transition temperature and the insulating characteristics of La0.7Ce0.3CoO3 . For La0.7Sr0.3CoO3 , on the other hand, the magnetic moments in the epitaxial films originate from high-spin Co3+ and high-spin Co4+ states. Ferromagnetism is induced by t2g double exchange between the two high-spin configurations. For all systems, a strong magnetic anisotropy is observed, with the magnetic moments essentially oriented within the film plane.

  20. Cyanobacterial phycobilisomes: Selective dissociation monitored by fluorescence and circular dichroism

    OpenAIRE

    Rigbi, Meir; Rosinski, Joanne; Siegelman, Harold W.; Sutherland, John Clark

    1980-01-01

    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°C, as indicated by a blue shift in fluorescence emission, and i...

  1. Administrative Circulars

    CERN Multimedia

    Département des Ressources humaines

    2004-01-01

    Administrative Circular N° 2 (Rev. 2) - May 2004 Guidelines and procedures concerning recruitment and probation period of staff members This circular has been revised. It cancels and replaces Administrative Circular N° 2 (Rev. 1) - March 2000. Administrative Circular N° 9 (Rev. 3) - May 2004 Staff members contracts This circular has been revised. It cancels and replaces Administrative Circular N° 9 (Rev. 2) - March 2000. Administrative Circular N° 26 (Rev. 4) - May 2004 Procedure governing the career evolution of staff members This circular has also been revised. It Administrative Circulars Administrative Circular N° 26 (Rev. 3) - December 2001 and brings up to date the French version (Rev. 4) published on the HR Department Web site in January 2004. Operational Circular N° 7 - May 2004 Work from home This circular has been drawn up. Operational Circular N° 8 - May 2004 Dealing with alcohol-related problems...

  2. Energy-dispersive X-ray absorption spectroscopy at LNLS: investigation on strongly correlated metal oxides

    OpenAIRE

    Cezar, Julio C.; Souza-Neto, Narcizo,; Piamonteze, Cınthia; Tamura, Edilson; Garcia, Flavio; Carvalho, Edson J.; Neueschwander, Régis T.; Ramos, Aline Y.; Tolentino, Hélio; Caneiro, Alberto; Massa, Nestor E.; Jesus Martinez-Lope, Maria; Antonio Alonso, Jose; Itié, Jean-Paul

    2010-01-01

    An energy-dispersive X-ray absorption spectroscopy beamline mainly dedicated to X-ray magnetic circular dichroism (XMCD) and material science under extreme conditions has been implemented in a bending-magnet port at the Brazilian Synchrotron Light Laboratory. Here the beamline technical characteristics are described, including the most important aspects of the mechanics, optical elements and detection set-up. The beamline performance is then illustrated through two case studies on strongly co...

  3. X-ray absorption and x-ray magnetic dichroism study on Ca3CoRhO6 and Ca3FeRhO6

    Science.gov (United States)

    Burnus, T.; Hu, Z.; Wu, Hua; Cezar, J. C.; Niitaka, S.; Takagi, H.; Chang, C. F.; Brookes, N. B.; Lin, H.-J.; Jang, L. Y.; Tanaka, A.; Liang, K. S.; Chen, C. T.; Tjeng, L. H.

    2008-05-01

    By using x-ray absorption spectroscopy at the RhL2,3 , CoL2,3 , and FeL2,3 edges, we find a valence state of Co2+/Rh4+ in Ca3CoRhO6 and of Fe3+/Rh3+ in Ca3FeRhO6 . X-ray magnetic circular dichroism spectroscopy at the CoL2,3 edge of Ca3CoRhO6 reveals a giant orbital moment of about 1.7μB , which can be attributed to the occupation of the minority-spin d0d2 orbital state of the high-spin Co2+ (3d7) ions in trigonal prismatic coordination. This active role of the spin-orbit coupling explains the strong magnetocrystalline anisotropy and Ising-type magnetism of Ca3CoRhO6 .

  4. X-ray absorption and x-ray magnetic dichroism study on Ca3CoRhO6 and Ca3FeRhO6

    OpenAIRE

    Burnus, T.; Z. Hu; Wu, Hua; Cezar, J. C.; Niitaka, S.; Takagi, H.; Chang, C. F.; Brookes, N. B.; Lin, H. -J.; Jang, L. Y.; Tanaka, A.; Liang, K. S.; Chen, C. T.; Tjeng, L. H.

    2008-01-01

    Using x-ray absorption spectroscopy at the Rh-L_2,3, Co-L_2,3, and Fe-L_2,3 edges, we find a valence state of Co^2+/Rh^4+ in Ca3CoRhO6 and of Fe^3+/Rh^3+ in Ca3FeRhO6. X-ray magnetic circular dichroism spectroscopy at the Co-L_2,3 edge of Ca3CoRhO6 reveals a giant orbital moment of about 1.7mu_B, which can be attributed to the occupation of the minority-spin d_0d_2 orbital state of the high-spin Co^2+ (3d^7) ions in trigonal prismatic coordination. This active role of the spin-orbit coupling ...

  5. Microwave Magnetochiral Dichroism in the Chiral-Lattice Magnet Cu_{2}OSeO_{3}.

    Science.gov (United States)

    Okamura, Y; Kagawa, F; Seki, S; Kubota, M; Kawasaki, M; Tokura, Y

    2015-05-15

    Through broadband microwave spectroscopy in Faraday geometry, we observe distinct absorption spectra accompanying magnetoelectric (ME) resonance for oppositely propagating microwaves, i.e., directional dichroism, in the multiferroic chiral-lattice magnet Cu_{2}OSeO_{3}. The magnitude of the directional dichroism critically depends on the magnetic-field direction. Such behavior is well accounted for by considering the relative direction of the oscillating electric polarizations induced via the ME effect with respect to microwave electric fields. Directional dichroism in a system with an arbitrary form of ME coupling can be also discussed in the same manner. PMID:26024193

  6. Perfect Circular Dichroic Metamirrors

    CERN Document Server

    Wang, Zuojia; Liu, Yongmin

    2015-01-01

    In nature, the beetle Chrysina gloriosa derives its iridescence by selectively reflecting left-handed circularly polarized light only. Here, for the first time, we introduce and demonstrate the optical analogue based on an ultrathin metamaterial, which we term circular dichroic metamirror. A general method to design the circular dichroic metasmirror is presented under the framework of Jones calculus. It is analytically shown that the metamirror can be realized by two layers of anisotropic metamaterial structures, in order to satisfy the required simultaneous breakings of n-fold rotational (n>2) and mirror symmetries. We design an infrared metamirror, which shows perfect reflectance for left-handed circularly polarized light without reversing its handedness, while almost completely absorbs right-handed circularly polarized light. These findings offer new methodology to realize novel chiral optical devices for a variety of applications, including polarimetric imaging, molecular spectroscopy, as well as quantum ...

  7. Chiral optical fields: A unified formulation of helicity scattered from particles and dichroism enhancement

    CERN Document Server

    Nieto-Vesperinas, Manuel

    2016-01-01

    We establish a general unified formulation which, using the optical theorem of electromagnetic helicity, shows that dichorism is a phenomenon arising in any scattering -or diffraction- process, elastic or not, of chiral electromagnetic fields by objects either chiral or achiral. It is shown how this approach paves the way to overcoming well-known limitations of standard circular dichroism, like its weak signal or the difficulties of using it with magnetodielectric particles. Based on the angular spectrum representation of optical fields with only right circular or left circular plane waves, we introduce beams with transverse elliptic polarization and posessing a longitudinal component. Then our formulation for general optical fields shows how to enhance the helicity, (and therefore the dichroism signal), versus the energy of the light scattered or emitted by a particle, or viceversa.

  8. High-Cadence and High-Resolution Halpha Imaging Spectroscopy of a Circular Flare's Remote Ribbon with IBIS

    CERN Document Server

    Deng, Na; Jing, Ju; Chen, Xin; Liu, Chang; Reardon, Kevin; Denker, Carsten; Xu, Yan; Wang, Haimin

    2013-01-01

    We present an unprecedented high-resolution \\ha\\ imaging spectroscopic observation of a C4.1 flare taken with IBIS on 2011 October 22. The flare consists of a main circular ribbon that occurred in a parasitic magnetic configuration and a remote ribbon that was observed by the IBIS. Such a circular-ribbon flare with a remote brightening is predicted in 3D fan-spine reconnection but so far has been rarely observed. During the flare impulsive phase, we define "core" and "halo" structures in the observed ribbon. Examining the \\ha\\ emission spectra averaged in the flare core and halo areas, we find that only those from the flare cores show typical nonthermal electron beam heating characteristics. These characteristics include: broad and centrally reversed emission spectra, excess emission in the red wing with regard to the blue wing (i.e., red asymmetry), and redshifted bisectors of the emission spectra. We also observe rather quick timescales for the heating (30 s) and cooling (14--33 s) in the flare core locatio...

  9. Surface spin-polarized currents generated in topological insulators by circularly polarized synchrotron radiation and their photoelectron spectroscopy indication

    Science.gov (United States)

    Shikin, A. M.; Klimovskikh, I. I.; Filyanina, M. V.; Rybkina, A. A.; Pudikov, D. A.; Kokh, K. A.; Tereshchenko, O. E.

    2016-08-01

    A new method for generating spin-polarized currents in topological insulators has been proposed and investigated. The method is associated with the spin-dependent asymmetry of the generation of holes at the Fermi level for branches of topological surface states with the opposite spin orientation under the circularly polarized synchrotron radiation. The result of the generation of holes is the formation of compensating spin-polarized currents, the value of which is determined by the concentration of the generated holes and depends on the specific features of the electronic and spin structures of the system. The indicator of the formed spin-polarized current can be a shift of the Fermi edge in the photoelectron spectra upon photoexcitation by synchrotron radiation with the opposite circular polarization. The topological insulators with different stoichiometric compositions (Bi1.5Sb0.5Te1.8Se1.2 and PbBi2Se2Te2) have been investigated. It has been found that there is a correlation in the shifts and generated spin-polarized currents with the specific features of the electronic spin structure. Investigations of the graphene/Pt(111) system have demonstrated the possibility of using this method for other systems with a spin-polarized electronic structure.

  10. High-Cadence and High-Resolution Halpha Imaging Spectroscopy of a Circular Flare's Remote Ribbon with IBIS

    Science.gov (United States)

    Deng, Na; Tritschler, A.; Jing, J.; Chen, X.; Liu, C.; Reardon, K. P.; Denker, C.; Xu, Y.; Wang, H.

    2013-07-01

    We present an unprecedented high-resolution halpha imaging spectroscopic observation of a C4.1 flare taken with IBIS on 2011 October 22. The flare consists of a main circular ribbon that occurred in a parasitic magnetic configuration and a remote ribbon that was observed by the IBIS. Such a circular-ribbon flare with a remote brightening is predicted in 3D fan-spine reconnection but so far has been rarely reported. During the flare impulsive phase, we define "core" and "halo" structures in the observed ribbon. Examining the halpha emission spectra averaged in the flare core and halo areas, we find that only those from the flare cores show typical nonthermal electron beam heating characteristics. These characteristics include: broad and centrally reversed emission spectra, excess emission in the red wing with regard to the blue wing (i.e., red asymmetry), and redshifted bisectors of the emission spectra. We also observe rather quick timescales for the heating (30 s) and cooling (14--33 s) in the flare core locations. Therefore, we suggest that the flare cores revealed by IBIS track the sites of electron beam precipitation with exceptional spatial and temporal resolution. The flare cores show two-stage motion (a parallel motion along the ribbon followed by an expansion motion perpendicular to the ribbon) during the two impulsive phases of the flare. Some cores jump quickly (30 km/s) between discrete magnetic elements implying reconnection involving different flux tubes. We observe a very high temporal correlation (>0.9) between the integrated halpha and HXR emission during the flare impulsive phase. A short time delay (4.6 s) is also found in the halpha emission spikes relative to HXR bursts. The ionization timescale of the cool chromosphere and the extra time taken for the electrons to travel to the remote ribbon site may contribute to this delay.

  11. Chiroptical Spectroscopy

    Science.gov (United States)

    Gurst, Jerome E.

    1995-09-01

    A brief review of the literature, and Chemical and Engineering News in particular, reveals that the determination and use of optical activity is of increasing importance in today's commercial and research laboratories. The classical technique is to measure [alpha]D using a manual or recording polarimeter to provide a single value, the specific rotation at 589 nm. A spectropolarimeter can be used to determine optical activity through the UV-Visible spectrum (Optical Rotatory Dispersion [ORD]). At wavelengths far removed from electronic absorption bands, optical activity arises from circular birefringence, or the difference in the refractive index for left- and right-circularly polarized light; i.e., nL - nR does not equal zero for chiral materials. If the optical activity is measured through an absorption band, complex behavior is observed (a Cotton Effect curve). At an absorption band, chiral materials exhibit circular dichroism (CD), or a difference in the absorption of left- and right-circularly polarized light; epsilon L minus epsilon R does not equal zero. If the spectropolarimeter is set for the measurement of CD spectra, one observes what appears to be a UV-Vis spectrum except that some absorption bands are positive while others may be negative. Just as enantiomers have specific rotations that are equal and opposite at 589 nm (sodium D line), rotations are equal and opposite at all wavelengths, and CD measurements are equal and opposite at all wavelengths. Figure 1 shows the ORD curves for the enantiomeric carvones while Figure 2 contains the CD curves. The enantiomer of carvone that has the positive [alpha]D is obtained from caraway seeds and is known to have the S-configuration while the R-enantiomer is found in spearmint oil. Figure 1. ORD of S-(+)- and R-(-)-carvones Figure 2. CD of S-(+)- and R-(-)-carvones While little can be done to correlate stereochemistry with [alpha]D values, chiroptical spectroscopy (ORD and/or CD) often can be used to assign

  12. High-cadence and High-resolution Hα Imaging Spectroscopy of a Circular Flare's Remote Ribbon with IBIS

    Science.gov (United States)

    Deng, Na; Tritschler, Alexandra; Jing, Ju; Chen, Xin; Liu, Chang; Reardon, Kevin; Denker, Carsten; Xu, Yan; Wang, Haimin

    2013-06-01

    We present an unprecedented high-resolution Hα imaging spectroscopic observation of a C4.1 flare taken with the Interferometric Bidimensional Spectrometer (IBIS) in conjunction with the adaptive optics system at the 76 cm Dunn Solar Telescope on 2011 October 22 in the active region NOAA 11324. Such a two-dimensional spectroscopic observation covering the entire evolution of a flare ribbon with high spatial (0.''1 pixel-1 image scale), cadence (4.8 s), and spectral (0.1 Å step size) resolution is rarely reported. The flare consists of a main circular ribbon that occurred in a parasitic magnetic configuration and a remote ribbon that was observed by the IBIS. Such a circular-ribbon flare with a remote brightening is predicted in three-dimensional fan-spine reconnection but so far has been rarely studied. During the flare impulsive phase, we define "core" and "halo" structures in the observed ribbon based on IBIS narrowband images in the Hα line wing and line center. Examining the Hα emission spectra averaged in the flare core and halo areas, we find that only those from the flare cores show typical nonthermal electron beam heating characteristics that have been revealed by previous theoretical simulations and observations of flaring Hα line profiles. These characteristics include broad and centrally reversed emission spectra, excess emission in the red wing with regard to the blue wing (i.e., red asymmetry), and redshifted bisectors of the emission spectra. We also observe rather quick timescales for the heating (~30 s) and cooling (~14-33 s) in the flare core locations. Therefore, we suggest that the flare cores revealed by IBIS track the sites of electron beam precipitation with exceptional spatial and temporal resolution. The flare cores show two-stage motion (a parallel motion along the ribbon followed by an expansion motion perpendicular to the ribbon) during the two impulsive phases of the flare. Some cores jump quickly (30 km s-1) between discrete

  13. Comprehensive Chiroptical Spectroscopy, Applications in Stereochemical Analysis of Synthetic Compounds, Natural Products, and Biomolecules

    CERN Document Server

    Berova, Nina; Nakanishi, Koji; Woody, Robert W

    2012-01-01

    This book provides an introduction to the important methods of chiroptical spectroscopy in general, and circular dichroism (CD) in particular, which are increasingly important in all areas of chemistry, biochemistry, and structural biology. The book can be used as a text for undergraduate and graduate students and as a reference for researchers in academia and industry. Experimental methods and instrumentation are described with topics ranging from the most widely used methods (electronic and vibrational CD) to frontier areas such as nonlinear spectroscopy and photoelectron CD,

  14. 金属硫蛋白及其结构域突变体的紫外和圆二色光谱学研究%Study on the Ultraviolet and Circular Dichroism Spectroscopy of Metallothionein and its Domain Mutants

    Institute of Scientific and Technical Information of China (English)

    周妍娇; 李令媛; 茹炳根

    2000-01-01

    采用pGEX-4T-1融合表达载体高效表达所得的金属硫蛋白及其结构域突变体,包括α结构域,β结构域,d-KKS-d和β-KKS-β(KKS为金属硫蛋白结构域之间的天然连接区氨基酸),经纯化和纯度鉴定后,利用紫外和圆二色光谱进行结构研究.在脱金属的上述蛋白中,固定pH为中性,改变加入Cd2+的比例,或固定Cd2+浓度,逐渐调节pH至中性,观察紫外和圆二色光谱中镉硫金属簇吸收峰的形成.研究结果表明:镉硫金属簇的形成依赖于加入金属的比例和pH值,所有蛋白均于pH3.15以上开始形成明显的吸收峰.紫外图谱中的吸收峰位于254 nm附近,但在圆二色图谱中不同蛋白形成的峰的位置不同,MT,α结构域和α-KKS-α在225 nm和258 nm处有吸收,β结构域在260 nm处有吸收,而β-KKS-β在245 nm处有吸收;向d结构域,β结构域,MT,α-KKS-α和β-KS-β中分别加入4eq,3eq,7eq,8eq和6eq(eq:equivalent,当量)的Cd2+时,吸收峰可达到最大值.同时发现d结构域的吸收峰强于β结构域,而且双结构域突变体的镉硫金属簇则明显强于相应的单结构域突变体,这表明吸收峰的强弱与金属结合力的大小相关,而且结构域之间存在相互作用,从而影响与金属的结合.

  15. Comprehensive chiroptical spectroscopy, instrumentation, methodologies, and theoretical simulations

    CERN Document Server

    Berova, Nina; Nakanishi, Koji

    2011-01-01

    This book provides an introduction to the important methods of chiroptical spectroscopy in general, and circular dichroism (CD) in particular, which are increasingly important in all areas of chemistry, biochemistry, and structural biology. The book can be used as a text for undergraduate and graduate students and as a reference for researchers in academia and industry, with or without the companion volume in this set. Experimental methods and instrumentation are described with topics ranging from the most widely used methods (electronic and vibrational CD) to frontier areas such as nonlinear

  16. Information circulars

    International Nuclear Information System (INIS)

    Information circulars are published from time to time under the symbol INFCIRC/... for the purpose of bringing matters of general interest to the attention of all Members of the Agency. The present revision contains INFCIRCs published up to mid-August 1994. A complete numerical list of information circulars is reproduced with their titles in the Annex

  17. Information circulars

    International Nuclear Information System (INIS)

    The document summarizes the Information Circulars published by the IAEA for the purpose of bringing matters of general interest to the attention of all Members of the Agency. This revision contains INFCIRCs published up to mid-August 1992. A complete numerical lift of Information Circulars with their titles is reproduced in an Annex

  18. Circular Updates

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Circular Updates are periodic sequentially numbered instructions to debriefing staff and observers informing them of changes or additions to scientific and specimen...

  19. Information circulars

    International Nuclear Information System (INIS)

    The document summarizes the information circulars published by the IAEA for the purpose of bringing matters of general interest to the attention of all Members of the Agency. In the main body of the document only those documents which are regarded as likely to be of current interest are listed. A complete numerical list of information circulars with their titles is reproduced in the Annex

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

    Energy Technology Data Exchange (ETDEWEB)

    Schumann, F.O.; Willis, R.F. [Pennsylvania State Univ., University Park, PA (United States); Goodman, K.W. [Lawrence Berkeley National Lab., CA (United States)] [and others

    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. Operational Circulars

    CERN Multimedia

    2003-01-01

    Operational Circular N° 4 - April 2003 Conditions for use by members of the CERN personnel of vehicles belonging to or rented by CERN - This circular has been drawn up. Operational Circular N° 5 - October 2000 Use of CERN computing facilities - Further details on the personal use of CERN computing facilities Operational Circular N° 5 and its Subsidiary Rules http://cern.ch/ComputingRules defines the rules for the use of CERN computing facilities. One of the basic principles governing such use is that it must come within the professional duties of the user concerned, as defined by the user's divisional hierarchy. However, personal use of the computing facilities is tolerated or allowed provided : a) It is in compliance with Operational Circular N° 5 and not detrimental to official duties, including those of other users; b) the frequency and duration is limited and there is a negligible use of CERN resources; c) it does not constitute a political, commercial and/or profit-making activity; d) it is not...

  2. 含有碘代酪氨酸的铜(Ⅱ)三元混配配合物的圆二色光谱研究——碘对甲状腺激素生物活性的结构作用探索%Circular Dichroism Study on Ternary Copper(Ⅱ) Complexes with Diiodotyrosinate-An Approach for Structural Effects of Iodines on Biological Activation of Thyroid Hormones

    Institute of Scientific and Technical Information of China (English)

    刘晓瀛; 张锋

    2001-01-01

    Absorption and circular dichroism (CD) spectra of the ternary copper(Ⅱ) complexes with 3-iodo-L-tyrosine (L-Ityr),L-tyrosine (L-Tyr),or L-homoserine (L-Hser) and amino acids L-AA,where AA represents arginine (Arg),lysine (Lys),asparagine (Asn),glutamine (Gln),or alanine (Ala),have been determined in the d-d region in various ionic strength ( I = 1.0 or 0.1 mol/L KNO3) and solvents (H2O,50% ethanol-H2O,or 50% dioxane-H2O).CD spectra for all the ternary complexes exhibit a maximum at 587~627 nm,and the △ε for Cu(L-Ityr) (L-Arg) and Cu(L-Ityr) (L-Lys) are abnormally negative (-0.479~-0.884).The △ε for Cu(L-Ityr) (L-AA) is obviously more negative than that for Cu(L-Tyr)(L-AA).The possible ligand-ligand interactions in these ternary complexes were discussed,and a structural effect of iodine on the interaction was emphasized.%用圆二色光谱法研究了铜(Ⅱ)与3-碘基-L-酪氨酸(L-Ityr),L-酪氨酸(L-Tyr),或L-高丝氨酸(L-Hser)和L-AA(AA代表精氨酸(Arg),赖氨酸(Lys),天冬酰胺(Asn),谷氨酰胺(Gln),或丙氨酸(Ala)三元混配配合物体系在不同离子强度(I=1.0或0.1mol/L KNO3)和溶剂环境(水,50%(v/v)乙醇-水或50%(v/v)二氧六环-水)条件下配体间相互作用.全部混配配合物体系的圆二色光谱在587~627nm范围均有负的极大吸收,且Cu(L-Ityr)L-Arg)和Cu(L-Ityr)(L-Lys)体系的△ε异常负(-0.479~-0.884);Cu(L-Ityr)(L-AA)体系的△ε明显比Cu(L-Tyr)(L-AA)负.讨论了这些混配配合物中配体间相互作用的规律和碘的结构效应.

  3. Information circulars

    International Nuclear Information System (INIS)

    The document summarizes the Information Circulars published by the IAEA under the symbol INFCIRC/ for the purpose of bringing matters of general interest to the attention of all Members of the Agency. A complete list of INFCIRCs in numerical order with their titles is given in the Annex

  4. Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Hellman, Hal

    1968-01-01

    This booklet discusses spectroscopy, the study of absorption of radiation by matter, including X-ray, gamma-ray, microwave, mass spectroscopy, as well as others. Spectroscopy has produced more fundamental information to the study of the detailed structure of matter than any other tools.

  5. Spectroscopy

    CERN Document Server

    Walker, S

    1976-01-01

    The three volumes of Spectroscopy constitute the one comprehensive text available on the principles, practice and applications of spectroscopy. By giving full accounts of those spectroscopic techniques only recently introduced into student courses - such as Mössbauer spectroscopy and photoelectron spectroscopy - in addition to those techniques long recognised as being essential in chemistry teaching - sucha as e.s.r. and infrared spectroscopy - the book caters for the complete requirements of undergraduate students and at the same time provides a sound introduction to special topics for graduate students.

  6. ADMINISTRATIVE CIRCULARS

    CERN Multimedia

    Division des ressources humaines

    2000-01-01

    N° 2 (Rev. 1) - March 2000Guidelines and procedures concerning recruitment and probation period of staff membersN° 9 (Rev. 2) - March 2000Staff members contractsN° 16 (Rev. 2) - January 2000TrainingN° 30 (Rev. 1) - January 2000Indemnities and reimbursements upon taking up appointment and termination of contractN° 32 - February 2000Principles and procedures governing complaints of harassmentThese circular have been amended (No 2, N° 9, N° 16 and N° 30) or drawn up (N° 32).Copies are available in the Divisional Secretariats.Note:\tAdministrative and operational circulars, as well as the lists of those in force, are available for consultation in the server SRV4_Home in the Appletalk zone NOVELL (as GUEST or using your Novell username and password), volume PE Division Data Disk.The Word files are available in the folder COM, folder Public, folder ADM.CIRC.docHuman Resources DivisionTel. 74128

  7. Protein folding and misfolding shining light by infrared spectroscopy

    CERN Document Server

    Fabian, Heinz

    2012-01-01

    Infrared spectroscopy is a new and innovative technology to study protein folding/misfolding events in the broad arsenal of techniques conventionally used in this field. The progress in understanding protein folding and misfolding is primarily due to the development of biophysical methods which permit to probe conformational changes with high kinetic and structural resolution. The most commonly used approaches rely on rapid mixing methods to initiate the folding event via a sudden change in solvent conditions. Traditionally, techniques such as fluorescence, circular dichroism or visible absorption are applied to probe the process. In contrast to these techniques, infrared spectroscopy came into play only very recently, and the progress made in this field up to date which now permits to probe folding events over the time scale from picoseconds to minutes has not yet been discussed in a book. The aim of this book is to provide an overview of the developments as seen by some of the main contributors to the field...

  8. Orientation of gramicidin A transmembrane channel. Infrared dichroism study of gramicidin in vesicles.

    OpenAIRE

    Nabedryk, E.; Gingold, M P; Breton, J

    1982-01-01

    Polarized infrared spectroscopy has been used to investigate the orientation of gramicidin A incorporated in dimyristoylphosphatidylcholine liposomes. Dichroism measurements of the major lipid (C = O ester, PO2-, CH2) and peptide (amide A, I, II) bands were performed on liposomes (with or without gramicidin) oriented by air-drying. The mean orientation of the lipid groups and of the pi LD helix chain in the gramicidin has been determined. It can be inferred from infrared frequencies of gramic...

  9. X-ray dichroism of rare earth materials

    International Nuclear Information System (INIS)

    The theme of this thesis is the investigation of the strong polarization dependende, or dichroism, that occur in the X-ray absorption spectra of rare earth materials. The rare earth elements distinguish themselves from the other elements through the behaviour of the 4f electrons which form the valence shell. This shell lies deep inside the atom, with the result that influences from the surrounding solid are well screened off by the outer electrons, so that even in the solid the 4f shell behaves very much like a in free atom or ion, and is almost completely spherically symmetric. Perturbations from the solid environment however always disturb this symmetry to some extend, with the result that the absorption spectrum becomes dependent on the mutual orientation of the polarization vector of the radiation and the ion. Earlier the existence of a strong magnetic X-ray dichroism (MXD) in the 3d→4f transitions of rare earths. In this thesis this work is extended, to a small degree theoretically but mainly experimentally. MXD is used in experiments on bulk sample, terbium iron garnet, and on rare earth overlayers on a ferromagnetic surface, Ni(110). The results of the latter study show unequivocally the potential of the MXD technique. The second theme of the thesis concerns experimental developments in soft X-ray spectroscopy. A description is given of a double crystal monochromator beamline that was constructed by our group at LURE, France. Results of the use of an organic crystal - multilayer comination in such a monochromator is described. Also a method is described for the characterization of the resolution of soft X-ray monochromators. Finally a contribution to the characterization of the electron yield technique in the soft X-ray range is given. (author). 296 refs.; 64 figs.; 59 schemes; 9 tabs

  10. Spectroscopy

    DEFF Research Database (Denmark)

    Berg, Rolf W.

    This introductory booklet covers the basics of molecular spectroscopy, infrared and Raman methods, instrumental considerations, symmetry analysis of molecules, group theory and selection rules, as well as assignments of fundamental vibrational modes in molecules.......This introductory booklet covers the basics of molecular spectroscopy, infrared and Raman methods, instrumental considerations, symmetry analysis of molecules, group theory and selection rules, as well as assignments of fundamental vibrational modes in molecules....

  11. Element Specific Versus Integral Structural and Magnetic Properties of Co:ZnO and Gd:GaN Probed with Hard X-ray Absorption Spectroscopy

    Directory of Open Access Journals (Sweden)

    Andreas Ney

    2010-06-01

    Full Text Available Dilute magnetic semiconductors (DMS are envisioned as sources of spin-polarized carriers for future semiconductor devices which simultaneously utilize spin and charge of the carriers. The hope of discovering a DMS with ferromagnetic order up to room temperature still motivates research on suitable DMS materials. Two candidate wide-band gap DMS are Gd:GaN and Co:ZnO. We have used hard X-ray absorption spectroscopy (XAS and in particular X-ray linear dichroism (XLD and X-ray magnetic circular dichroism (XMCD to study both DMS materials with element specificity and compare these findings with results from integral SQUID magnetometry as well as electron paramagnetic resonance (EPR.

  12. Chiroptical Spectroscopy in the Vapor Phase

    Science.gov (United States)

    Lahiri, Priyanka; Long, Benjamin D.; Wiberg, Kenneth B.; Vaccaro, Patrick H.

    2011-06-01

    Electromagnetic radiation propagating through an isotropic chiral medium experiences a complex index of refraction that differs in both real (in-phase) and imaginary (in-quadrature) parts for the right-circular and left-circular polarization states that define the helicity basis. The resulting phenomena of circular birefringence (CB) and circular dichroism (CD) lead to observable effects in the form of dispersive rotation and absorptive elliptization for an impinging beam of plane-polarized light, which commonly are measured under conditions of nonresonant and resonant excitation, respectively. This talk will discuss ongoing efforts designed to elucidate the provenance of electronic optical activity under complementary solvated and isolated conditions, with the latter vapor-phase work made possible by our continuing development of Cavity Ring-Down Polarimetry (CRDP). Molecules of interest include the rigid bicyclic ketone (1R,4R)-norbornenone, where the spatial arrangement of distal alkene and carbonyl moeities gives rise to extraordinarily large specific rotation (CB) parameters that are predicted incongruously by different quantum-chemical methods; the monoterpene constitutional isomers (S)-2-carene and (S)-3-carene, which display surprisingly distinct chiroptical properties; and conjugated ketones such as (S)-verbenone, where CD probes of weak π*←n absorption bands have been performed at vibronic resolution. The disparate nature of gas-phase and condensed-phase optical activity will be highlighted, with complementary ab initio calculations serving to elucidate the structural, chemical, and electronic origins of observed behavior. T. Müller, K. B. Wiberg, P. H. Vaccaro, J. R. Cheeseman, and M. J. Frisch, J. Opt. Soc. Am. B 19, 125 (2002) P. H. Vaccaro, ``Chapter 1.II.10: Optical Rotation and Intrinsic Optical Activity'' in Comprehensive Chiroptical Spectroscopy, N. Berova, P. L. Polavarapu, K. Nakanishi, and R. W. Woody, eds. (John Wiley and Sons, Inc

  13. Spectroscopy Investigation on Conformational Transition of Tea Glycoconjugate from Green Tea

    Institute of Scientific and Technical Information of China (English)

    CHEN,Hai-Xia(陈海霞); ZHANG,Min(张民); XIE,Bi-Jun(谢笔钧)

    2004-01-01

    The conformational transition of a new glycoconjugate,tea glycoconjugate(TGC),was investigated by spectroscopy techniques including circular dichroism(CD)and ultraviolet(UV)spectroscopy.The solution behaviors of TGC inthe mediums of different temperature,pH value,and ions were compared.Results showed that the native conformation of TGC was partially ordered.The CD value and UV absorbance of TGC altered with the change of pH value,temperature,the addition of ions,and also accompanied order-disorder transition.Especially the conditions with temperature higher than the glasstransition temperature(Tg=62℃),higher pH value orlower pH value will have the most impact on the conformation of TGC,which will destroy the hydrogen bonds between the TGC molecules.The results indicated that the outside factors playimportant roles onthe stability of the conformation of TGC.

  14. Circular Dichrosim Studies on the Deinococcus Radiodurans Nudix Hydrolase DR_0079: an Atypical Thermal Melt

    Energy Technology Data Exchange (ETDEWEB)

    Buchko, Garry W.

    2010-07-01

    We have recently determined the solution structure of the hypothetical Deinococcus radiodurans Nudix protein DR0079 [Proteins 56:28-39]. The protein is a monomer and contains the fundamental fold common to the Nudix family, a large mixed b-sheet sandwiched between a-helices. The protein¹s physical properties were further characterized by circular dichroism (CD) spectroscopy. A CD thermal melt indicates an inflection point at ~52ºC. However, unlike typical CD thermal melts, the ellipticity at 220 nm decreases upon passing through the inflection point suggesting that the amount of secondary structure in the protein has increased after heating. NMR spectroscopy and size exclusion chromatography indicates that heating effects the irreversible formation of a large molecular weight complex. After cooling, the ellipiticity at 220 nm increases further, and overall, the CD spectrum at 25ºC shows that heat-treated DR0079 has more ³structure² than non-heat treated DR0079.

  15. Circularity and Lambda Abstraction

    DEFF Research Database (Denmark)

    Danvy, Olivier; Thiemann, Peter; Zerny, Ian

    2013-01-01

    In this tribute to Doaitse Swierstra, we present the rst transformation between lazy circular programs a la Bird and strict cir- cular programs a la Pettorossi. Circular programs a la Bird rely on lazy recursive binding: they involve circular unknowns and make sense equa- tionally. Circular...... unknowns from what is done to them, which we lambda-abstract with functions. The circular unknowns then become dead variables, which we eliminate. The result is a strict circu- lar program a la Pettorossi. This transformation is reversible: given a strict circular program a la Pettorossi, we introduce...

  16. Hydroxypyridyl Imines: Enhancing Chromatographic Separation and Stereochemical Analysis of Chiral Amines via Circular Dichroism.

    Science.gov (United States)

    Joyce, Leo A; Regalado, Erik L; Welch, Christopher J

    2016-09-16

    Imine-bond formation between chiral amines and commercially available 3-hydroxypyridine-2-carboxaldehyde (HCA) was exploited for rapid determination of stereochemical composition. Chiral supercritical fluid chromatography (SFC) screening of the derivatized imine compounds led to the elucidation of multiple combinations of mobile and stationary phases that gave resolution of all members of a series of chiral amines. The first eluting enantiomer was generally the derivative of the (R)-amine enantiomer across the series that was studied, indicating that the imine formed from the (S)-amine has more favorable interaction with the chiral stationary phase of the column. These conditions were then applied to more challenging compounds, namely amino alcohols and diastereomers possessing more than one stereocenter. The approach was utilized to monitor stereoselective biocatalytic transamination and assign the absolute configuration of the enantiomeric products. Finally, hydrolysis of the imine bond of the derivative was shown to generate enantiopure amine starting materials without racemization. This further highlights the value of this approach for creating readily reversed derivatives that enhance chromatographic separation and aid in the determination of absolute configuration.

  17. Circular dichroism in hydrogen multiphoton ionization by a bichromatic field of frequencies {omega} and 3{omega}

    Energy Technology Data Exchange (ETDEWEB)

    Fifirig, Magda [Department of Chemistry, University of Bucharest, Bucharest (Romania); Cionga, Aurelia [Institute of Space Sciences, Bucharest-Magurele (Romania)

    2002-02-28

    The dichroic effects in the multiphoton ionization of the ground state hydrogen atom by a coherent superposition of a laser beam and its third harmonic, are studied via perturbative calculations. The final state of the photoelectrons, which has the energy E=E{sub 1}+3(h/2{pi}){omega} (E{sub 1} the ground state energy and {omega} the laser frequency), is reached by two interfering quantum paths: (a) absorption of one harmonic photon and (b) absorption of three laser photons. In the chosen regime of field intensities, the radiative corrections to the absorption of one harmonic photon may be disregarded. Our numerical results illustrate the influence of the laser frequency, of the relative intensity and of the harmonic phase upon the dichroic signal. (author)

  18. Tunable circular dichroism due to the chiral anomaly in Weyl semimetals

    OpenAIRE

    Hosur, Pavan; Qi, Xiao-Liang

    2014-01-01

    Weyl semimetals are a three dimensional gapless topological phase in which bands intersect at arbitrary points -- the Weyl nodes -- in the Brillouin zone. These points carry a topological quantum number known as the \\emph{chirality} and always appear in pairs of opposite chiralities. The notion of chirality leads to anomalous non-conservation of chiral charge, known as the \\emph{chiral anomaly}, according to which charge can be pumped between Weyl nodes of opposite chiralities by an electroma...

  19. Molecular photoionisation using synchrotron radiation. Photoelectron photoion coincidence and circular dichroism

    CERN Document Server

    Garcia-Macias, G A

    2002-01-01

    The first ionisation potential of the CF sub 3 radical has been determined in this work from the appearance potential of the CF sub 3 sup + fragment, formed in the photofragmentation of CF sub 3 Br. In obtaining this value special care has been taken in removing the contributions from second order light and internal energy of the fragmenting parent ion. The resulting ionisation potential was found to be in very good agreement with a number of recent theoretical calculations. The valence photoelectron spectra of three monoterpenes such as limonene, carvone and camphor have been recorded along with their mass spectra taken in coincidence with energy selected photoelectrons, providing information about state selected parent ion fragmentation channels. A new photoelectron spectrometer based on the Alien box design has been studied by ray-tracing simulations. It will include a two dimensional position sensitive detector system consisting in two micro channel plates in a chevron stack and a delay-line anode to enco...

  20. Coherence specific signal detection via chiral pump-probe spectroscopy.

    Science.gov (United States)

    Holdaway, David I H; Collini, Elisabetta; Olaya-Castro, Alexandra

    2016-05-21

    We examine transient circular dichroism (TRCD) spectroscopy as a technique to investigate signatures of exciton coherence dynamics under the influence of structured vibrational environments. We consider a pump-probe configuration with a linearly polarized pump and a circularly polarized probe, with a variable angle θ between the two directions of propagation. In our theoretical formalism the signal is decomposed in chiral and achiral doorway and window functions. Using this formalism, we show that the chiral doorway component, which beats during the population time, can be isolated by comparing signals with different values of θ. As in the majority of time-resolved pump-probe spectroscopy, the overall TRCD response shows signatures of both excited and ground state dynamics. However, we demonstrate that the chiral doorway function has only a weak ground state contribution, which can generally be neglected if an impulsive pump pulse is used. These findings suggest that the pump-probe configuration of optical TRCD in the impulsive limit has the potential to unambiguously probe quantum coherence beating in the excited state. We present numerical results for theoretical signals in an example dimer system. PMID:27208941

  1. Coherence specific signal detection via chiral pump-probe spectroscopy.

    Science.gov (United States)

    Holdaway, David I H; Collini, Elisabetta; Olaya-Castro, Alexandra

    2016-05-21

    We examine transient circular dichroism (TRCD) spectroscopy as a technique to investigate signatures of exciton coherence dynamics under the influence of structured vibrational environments. We consider a pump-probe configuration with a linearly polarized pump and a circularly polarized probe, with a variable angle θ between the two directions of propagation. In our theoretical formalism the signal is decomposed in chiral and achiral doorway and window functions. Using this formalism, we show that the chiral doorway component, which beats during the population time, can be isolated by comparing signals with different values of θ. As in the majority of time-resolved pump-probe spectroscopy, the overall TRCD response shows signatures of both excited and ground state dynamics. However, we demonstrate that the chiral doorway function has only a weak ground state contribution, which can generally be neglected if an impulsive pump pulse is used. These findings suggest that the pump-probe configuration of optical TRCD in the impulsive limit has the potential to unambiguously probe quantum coherence beating in the excited state. We present numerical results for theoretical signals in an example dimer system.

  2. Circular-rubbing Manipulation

    Institute of Scientific and Technical Information of China (English)

    SHEN Guo-quan; XIAO Yuan-chun

    2003-01-01

    @@ "Mo" literally means "rubbing between two things"and "eliminating". Circular-rubbing is one of the earliest manipulations used in clinical practice. Circular-rubbing differs from pressing actually. Pressing is a static manipulation and acts to inhibit motion; circular-rubbing is a movable manipulation and serves to eliminate stationary. Circular-rubbing can be performed by either the palm or the finger.

  3. Circular polarisation in AGN

    NARCIS (Netherlands)

    Macquart, JP

    2002-01-01

    We discuss the constraints that recent observations place on circular polarisation in AGN. In many sources the circular polarisation is variable on short timescales, indicating that it originates in compact regions of the sources. The best prospects for gleaning further information about circular po

  4. Voltage-controlled magnetic anisotropy in Fe|MgO tunnel junctions studied by x-ray absorption spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Miwa, Shinji, E-mail: miwa@mp.es.osaka-u.ac.jp; Matsuda, Kensho; Tanaka, Kazuhito; Goto, Minori; Suzuki, Yoshishige [Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531 (Japan); Kotani, Yoshinori; Nakamura, Tetsuya [Japan Synchrotron Radiation Research Institute/SPring-8, Sayo, Hyogo 679-5198 (Japan)

    2015-10-19

    In this study, voltage-controlled magnetic anisotropy (VCMA) in Fe|MgO tunnel junctions was investigated via the magneto-optical Kerr effect, soft x-ray absorption spectroscopy, and magnetic circular dichroism spectroscopy. The Fe|MgO tunnel junctions showed enhanced perpendicular magnetic anisotropy under external negative voltage, which induced charge depletion at the Fe|MgO interface. Despite the application of voltages of opposite polarity, no trace of chemical reaction such as a redox reaction attributed to O{sup 2−} migration was detected in the x-ray absorption spectra of the Fe. The VCMA reported in the Fe|MgO-based magnetic tunnel junctions must therefore originate from phenomena associated with the purely electric effect, that is, surface electron doping and/or redistribution induced by an external electric field.

  5. Strong Trinucleotide Circular Codes

    Directory of Open Access Journals (Sweden)

    Christian J. Michel

    2011-01-01

    Full Text Available Recently, we identified a hierarchy relation between trinucleotide comma-free codes and trinucleotide circular codes (see our previous works. Here, we extend our hierarchy with two new classes of codes, called DLD and LDL codes, which are stronger than the comma-free codes. We also prove that no circular code with 20 trinucleotides is a DLD code and that a circular code with 20 trinucleotides is comma-free if and only if it is a LDL code. Finally, we point out the possible role of the symmetric group ∑4 in the mathematical study of trinucleotide circular codes.

  6. Publication of administrative circular

    CERN Multimedia

    HR Department

    2009-01-01

    ADMINISTRATIVE CIRCULAR NO. 23 (REV. 2) – SPECIAL WORKING HOURS Administrative Circular No. 23 (Rev. 2) entitled "Special working hours", approved following discussion in the Standing Concertation Committee on 9 December 2008, will be available on the intranet site of the Human Resources Department as from 19 December 2008: http://cern.ch/hr-docs/admincirc/admincirc.asp It cancels and replaces Administrative Circular No. 23 (Rev. 1) entitled "Stand-by duty" of April 1988. A "Frequently Asked Questions" information document on special working hours will also be available on this site. Paper copies of this circular will shortly be available in Departmental Secretariats. Human Resources Department Tel. 78003

  7. PUBLICATION OF ADMINISTRATIVE CIRCULAR

    CERN Multimedia

    HR Department

    2008-01-01

    ADMINISTRATIVE CIRCULAR NO. 23 (REV. 2) – SPECIAL WORKING HOURS Administrative Circular No. 23 (Rev. 2) entitled "Special working hours", approved following discussion in the Standing Concertation Committee meeting of 9 December 2008, will be available on the intranet site of the Human Resources Department as from 19 December 2008: http://cern.ch/hr-docs/admincirc/admincirc.asp It cancels and replaces Administrative Circular No. 23 (Rev. 1) entitled "Stand-by duty" of April 1988. A "Frequently Asked Questions" information document on special working hours will also be available on this site. Paper copies of this circular will shortly be available in departmental secretariats. Human Resources Department Tel. 78003

  8. Binding of chrysoidine to catalase: spectroscopy, isothermal titration calorimetry and molecular docking studies.

    Science.gov (United States)

    Yang, Bingjun; Hao, Fang; Li, Jiarong; Chen, Dongliang; Liu, Rutao

    2013-11-01

    Chrysoidine is an industrial azo dye and the presence of chrysoidine in water and food has become an environmental concern due to its negative effects on human beings. In this work, the interactions between chrysoidine and bovine liver catalase (BLC) were explored. Obvious loss in catalytic activity was observed after incubation of BLC with chrysoidine, and the inhibition effect of BLC was found to be of the non-competitive type. No profound conformational change of BLC occurs in the presence of chrysoidine as revealed by UV-vis absorption, circular dichroism and fluorescence spectroscopy studies. Isothermal titration calorimetry results indicate that catalase has two sets of binding sites for chrysoidine. Further, molecular docking simulations show that chrysoidine is located within the bottleneck in the main channel of the substrate to the active site of BLC, which explain the activity inhibition of BLC by chrysoidine.

  9. Preferential solvation of lysozyme in dimethyl sulfoxide/water binary mixture probed by terahertz spectroscopy.

    Science.gov (United States)

    Das, Dipak Kumar; Patra, Animesh; Mitra, Rajib Kumar

    2016-09-01

    We report the changes in the hydration dynamics around a model protein hen egg white lysozyme (HEWL) in water-dimethyl sulfoxide (DMSO) binary mixture using THz time domain spectroscopy (TTDS) technique. DMSO molecules get preferentially solvated at the protein surface, as indicated by circular dichroism (CD) and Fourier transform infrared (FTIR) study in the mid-infrared region, resulting in a conformational change in the protein, which consequently modifies the associated hydration dynamics. As a control we also study the collective hydration dynamics of water-DMSO binary mixture and it is found that it follows a non-ideal behavior owing to the formation of DMSO-water clusters. It is observed that the cooperative dynamics of water at the protein surface does follow the DMSO-mediated conformational modulation of the protein. PMID:27372901

  10. Circular Dichrosim in Photoionization of H2 and D2

    International Nuclear Information System (INIS)

    In this work, circular dichroism in H2 (D2) photoionization is studied in detail. We have selected several photon energies for a case study: 19 eV for which only direct ionization to the 1sσg ionization channel is present, 27 eV where autoionization of Q11Σ+u doubly excited states takes place, and 32.5 eV for which autoionization from Q1 and doubly excited states and direct ionization to 1sσg and 2pσu channels strongly interfere. The latter case shows clear evidence of different behavior of the photoionization against radiation helicity.

  11. [Application and development of spectroscopy methodologies in the study on non-covalent interactions].

    Science.gov (United States)

    Li, Rui; Dai, Ben-Cai; Zhao, Yong-De; Lu, Kui

    2009-01-01

    Spectrophotometric method is widely used in the structure determination of biologic macromolecules and non-covalent interactions study for its convenience and speed. In the present paper, spectroscopy methodologies in the study of non-covalent interactions between small-molecule and biomacromolecule is comprehensively reviewed with 25 references. This review article focuses on the applications and development of common spectroscopy methodologies in the study of non-covalent interactions between small molecule and biomacromolecule,including the UV, fluorescence, CD, IR, Raman, resonance light scattering technique and SPR. The advantages and disadvantages of spectroscopy methodologies are also described. UV-Vis absorption spectrum (UV) method is widely used in the study of non-covalent interactions for its convenience and speed. The binding site number, the apparent binding constant and the interaction mode of non-covalent interactions can be obtained by fluorescence spectrum method. Circular dichroism (CD) method is effective way in the study of non-covalent interactions measure. Spectroscopy information about protein secondary structure and conformation can be acquired by infrared spectrometry (IR) method. Raman spectroscopy method is a better way to investigate the conformation change in macromolecules in solution. Non-covalent interactions can be measured by surface plasma resonance (SPR) method under the natural active condition. X-ray diffraction analysis method is better for non-covalent interactions research, but it is difficult to cultivate crystalline complex.

  12. Angle resolved photoemission spectroscopy study on the non-saturate magnetoresistance material WTe2

    Science.gov (United States)

    Jiang, Juan; Niu, Xiaohai; Xie, Binping; Zhang, Tong; Feng, Donglai

    2015-03-01

    By performing high resolution angle-resolved photoemission spectroscopy, we obtain the detailed electronic structure of WTe2, which has an extremely large non-saturated magnetoresistance. Unlike the simple one electron and one hole pocket as expected, we resolved a rather complicated Fermi surface in WTe2. There is a hole pocket around the Brillouin zone center Γ, two hole pockets and two electron pockets along the tungsten chain direction. Thus the large magnetoresistance cannot be simply attributed to the electron-hole compensation, since this is based on a two carrier assumption model, the real case in WTe2 should be more complicated. Surprisingly, the circular dichroism ARPES result shows a strong intensity inversion between the data under the right-circular polarized light and the left-circular polarized light. This, indicates a proper different orbital angular momentum along the tungsten chain direction, which might also related to the different spin angular momentum since there're coupled with each other. Therefore, we propose that to fully understand the large magnetoresistance in WTe2, spin channel should also be involved where backscattering are forbidden under zero field.

  13. External cavity-quantum cascade laser infrared spectroscopy for secondary structure analysis of proteins at low concentrations

    Science.gov (United States)

    Schwaighofer, Andreas; Alcaráz, Mirta R.; Araman, Can; Goicoechea, Héctor; Lendl, Bernhard

    2016-09-01

    Fourier transform infrared (FTIR) and circular dichroism (CD) spectroscopy are analytical techniques employed for the analysis of protein secondary structure. The use of CD spectroscopy is limited to low protein concentrations (5 mg ml-1). Here we introduce a quantum cascade laser (QCL)-based IR transmission setup for analysis of protein and polypeptide secondary structure at concentrations as low as 0.25 mg ml-1 in deuterated buffer solution. We present dynamic QCL-IR spectra of the temperature-induced α-helix to β-sheet transition of poly-L-lysine. The concentration dependence of the α-β transition temperature between 0.25 and 10 mg ml-1 was investigated by QCL-IR, FTIR and CD spectroscopy. By using QCL-IR spectroscopy it is possible to perform IR spectroscopic analysis in the same concentration range as CD spectroscopy, thus enabling a combined analysis of biomolecules secondary structure by CD and IR spectroscopy.

  14. Circular statistics in R

    CERN Document Server

    Pewsey, Arthur; Ruxton, Graeme D

    2013-01-01

    Circular Statistics in R provides the most comprehensive guide to the analysis of circular data in over a decade. Circular data arise in many scientific contexts whether it be angular directions such as: observed compass directions of departure of radio-collared migratory birds from a release point; bond angles measured in different molecules; wind directions at different times of year at a wind farm; direction of stress-fractures in concretebridge supports; longitudes of earthquake epicentres or seasonal and daily activity patterns, for example: data on the times of day at which animals are c

  15. Applications of circularly polarized photons at the ALS with a bend magnet source

    Energy Technology Data Exchange (ETDEWEB)

    1992-02-01

    The purpose of this workshop is to focus attention on, and to stimulate the scientific exploitation of, the natural polarization properties of bend-magnet synchrotron radiation at the ALS -- for research in biology, materials science, physics, and chemistry. The topics include: The Advanced Light Source; Magnetic Circular Dichroism and Differential Scattering on Biomolecules; Tests of Fundamental Symmetries; High {Tc} Superconductivity; Photoemission from Magnetic and Non-magnetic Solids; Studies of Highly Correlated Systems; and Instrumentation for Photon Transport and Polarization Measurements.

  16. Applications of circularly polarized photons at the ALS with a bend magnet source

    International Nuclear Information System (INIS)

    The purpose of this workshop is to focus attention on, and to stimulate the scientific exploitation of, the natural polarization properties of bend-magnet synchrotron radiation at the ALS -- for research in biology, materials science, physics, and chemistry. The topics include: The Advanced Light Source; Magnetic Circular Dichroism and Differential Scattering on Biomolecules; Tests of Fundamental Symmetries; High Tc Superconductivity; Photoemission from Magnetic and Non-magnetic Solids; Studies of Highly Correlated Systems; and Instrumentation for Photon Transport and Polarization Measurements

  17. Circularly symmetric light scattering from nanoplasmonic spirals.

    Science.gov (United States)

    Trevino, Jacob; Cao, Hui; Dal Negro, Luca

    2011-05-11

    In this paper, we combine experimental dark-field imaging, scattering, and fluorescence spectroscopy with rigorous electrodynamics calculations in order to investigate light scattering from planar arrays of Au nanoparticles arranged in aperiodic spirals with diffuse, circularly symmetric Fourier space. In particular, by studying the three main types of Vogel's spirals fabricated by electron-beam lithography on quartz substrates, we demonstrate polarization-insensitive planar light diffraction in the visible spectral range. Moreover, by combining dark-field imaging with analytical multiparticle calculations in the framework of the generalized Mie theory, we show that plasmonic spirals support distinctive structural resonances with circular symmetry carrying orbital angular momentum. The engineering of light scattering phenomena in deterministic structures with circular Fourier space provides a novel strategy for the realization of optical devices that fully leverage on enhanced, polarization-insensitive light-matter coupling over planar surfaces, such as thin-film plasmonic solar cells, plasmonic polarization devices, and optical biosensors. PMID:21466155

  18. Administrative & Operational Circulars - Reminder

    CERN Multimedia

    HR Department

    2011-01-01

    All Administrative and Operational Circulars are available on the intranet site of the Human Resources Department at the following address: http://cern.ch/hr-docs/admincirc/admincirc.asp Department Head Office  

  19. Circular words and applications

    Directory of Open Access Journals (Sweden)

    Benoît Rittaud

    2011-08-01

    Full Text Available We define the notion of circular words, then consider on such words a constraint derived from the Fibonacci condition. We give several results on the structure of these circular words, then mention possible applications to various situations: periodic expansion of numbers in numeration systems, "gcd-property" of integer sequences, partition of the prefix of the fixed point of the Fibonacci substitution, spanning trees of a wheel. Eventually, we mention some open questions.

  20. A chiral rhenium complex with predicted high parity violation effects: synthesis, stereochemical characterization by VCD spectroscopy and quantum chemical calculations

    CERN Document Server

    Saleh, Nidal; Roisnel, Thierry; Guy, Laure; Bast, Radovan; Saue, Trond; Darquié, Benoît; Crassous, Jeanne

    2015-01-01

    With their rich electronic, vibrational, rotational and hyperfine structure, molecular systems have the potential to play a decisive role in precision tests of fundamental physics. For example, electroweak nuclear interactions should cause small energy differences between the two enantiomers of chiral molecules, a signature of parity symmetry breaking. Enantioenriched oxorhenium(VII) complexes S-(-)- and R-(+)-3 bearing a chiral 2-methyl-1-thio-propanol ligand have been prepared as potential candidates for probing molecular parity violation effects via high resolution laser spectroscopy of the Re=O stretching. Although the rhenium atom is not a stereogenic centre in itself, experimental vibrational circular dichroism (VCD) spectra revealed a surrounding chiral environment, evidenced by the Re=O bond stretching mode signal. The calculated VCD spectrum of the R enantiomer confirmed the position of the sulfur atom cis to the methyl, as observed in the solid-state X-ray crystallographic structure, and showed the ...

  1. Fe3S4 and Fe3O4 magnetic nanocrystals: magneto-optical and Mössbauer spectroscopy study

    Science.gov (United States)

    Lin, C.-R.; Tseng, Y.-T.; Ovchinnikov, S. G.; Ivantsov, R. D.; Edelman, I. S.; Fedorov, A. S.; Kuzubov, A. A.; Fedorov, D. A.; Starchikov, S. S.; Lyubutin, I. S.

    2014-04-01

    Iron oxide magnetite (Fe3O4) should be a reasonable analog for conception and understanding of the magnetic properties of iron sulfide greigite (Fe3S4)—one of the most required magnetic materials having numerous applications but being far from the complete understanding now. We present here a comparative study of the Mössbauer effect (ME) and the magnetic circular dichroism (MCD) spectroscopy of Fe3O4 and Fe3S4 nanoparticles. The ME spectrum parameters of Fe3S4 are shown to distinguish strongly from that of Fe3O4, and the MCD spectrum shapes are shown to be absolutely different for two compounds. To clarify the origin of the Fe3S4 MCD spectrum we have performed ab initio band structure calculations and identified the MCD spectrum features with the transitions between calculated energy states.

  2. Multiband Circular Polarizer Based on Fission Transmission of Linearly Polarized Wave for X-Band Applications

    Directory of Open Access Journals (Sweden)

    Farman Ali Mangi

    2016-01-01

    Full Text Available A multiband circular polarizer based on fission transmission of linearly polarized wave for x-band application is proposed, which is constructed of 2 × 2 metallic strips array. The linear-to-circular polarization conversion is obtained by decomposing the linearly incident x-polarized wave into two orthogonal vector components of equal amplitude and 90° phase difference between them. The innovative approach of “fission transmission of linear-to-circular polarized wave” is firstly introduced to obtain giant circular dichroism based on decomposition of orthogonal vector components through the structure. It means that the incident linearly polarized wave is converted into two orthogonal components through lower printed metallic strips layer and two transmitted waves impinge on the upper printed strips layer to convert into four orthogonal vector components at the end of structure. This projection and transmission sequence of orthogonal components sustain the chain transmission of electromagnetic wave and can achieve giant circular dichroism. Theoretical analysis and microwave experiments are presented to validate the performance of the structure. The measured results are in good agreement with simulation results. In addition, the proposed circular polarizer exhibits the optimal performance with respect to the normal incidence. The right handed circularly polarized wave is emitted ranging from 10.08 GHz to 10.53 GHz and 10.78 GHz to 11.12 GHz, while the left handed circular polarized wave is excited at 10.54 GHz–10.70 GHz and 11.13 GHz–11.14 GHz, respectively.

  3. Energy-loss magnetic chiral dichroism study of epitaxial MnAs film on GaAs(001)

    Energy Technology Data Exchange (ETDEWEB)

    Fu, X.; Warot-Fonrose, B.; Arras, R.; Serin, V. [CEMES-CNRS UPR 8011, Univ. Toulouse, F-31055 Toulouse (France); Demaille, D.; Eddrief, M. [Sorbonne Universités, UPMC Univ. Paris 6, UMR 7588, INSP, 4 Place Jussieu, F-75005 Paris (France); CNRS, UMR 7588, Institut des Nanosciences de Paris, 4 Place Jussieu, F-75005 Paris (France); Etgens, V. [Sorbonne Universités, UPMC Univ. Paris 6, UMR 7588, INSP, 4 Place Jussieu, F-75005 Paris (France); CNRS, UMR 7588, Institut des Nanosciences de Paris, 4 Place Jussieu, F-75005 Paris (France); Institut VeDeCoM – UVSQ, 78000 Versailles (France)

    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. Compact waveguide circular polarizer

    Energy Technology Data Exchange (ETDEWEB)

    Tantawi, Sami G.

    2016-08-16

    A multi-port waveguide is provided having a rectangular waveguide that includes a Y-shape structure with first top arm having a first rectangular waveguide port, a second top arm with second rectangular waveguide port, and a base arm with a third rectangular waveguide port for supporting a TE.sub.10 mode and a TE.sub.20 mode, where the end of the third rectangular waveguide port includes rounded edges that are parallel to a z-axis of the waveguide, a circular waveguide having a circular waveguide port for supporting a left hand and a right hand circular polarization TE.sub.11 mode and is coupled to a base arm broad wall, and a matching feature disposed on the base arm broad wall opposite of the circular waveguide for terminating the third rectangular waveguide port, where the first rectangular waveguide port, the second rectangular waveguide port and the circular waveguide port are capable of supporting 4-modes of operation.

  5. Antennas on circular cylinders

    DEFF Research Database (Denmark)

    Knudsen, H. L.

    1959-01-01

    antenna in a circular cylinder. By a procedure similar to the one used by Silver and Saunders, expressions have been derived for the field radiated from an arbitrary surface current distribution on a cylinder surface coaxial with a perfectly conducting cylinder. The cases where the space between the two......On the basis of the results obtained by Silver and Saunders [4] for the field radiated from an arbitrary slot in a perfectly conducting circular cylinder, expressions have been derived for the field radiated by a narrow helical slot, with an arbitrary aperture field distribution, in a circular...... cylindrical surfaces have the sane characteristic constants and different constants are treated separately. Extensive numerical computations of the field radiated from the slot antennas described here are being carried out, but no numerical results are yet available...

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

    Energy Technology Data Exchange (ETDEWEB)

    Merkulov, V. S., E-mail: merkul@physics.by [National Academy of Sciences of Belarus, Material Science Applied Research Center (Belarus)

    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.

  7. Around the circular law

    CERN Document Server

    Bordenave, Charles

    2011-01-01

    These expository notes are centered around the circular law theorem, which states that the empirical spectral distribution of a n \\times n random matrix with i.i.d. entries of variance 1/n tends to the uniform law on the unit disc of the complex plane as the dimension n tends to infinity. This phenomenon is the non-Hermitian counterpart of the semi circular limit for Wigner random Hermitian matrices, and the quarter circular limit for Marchenko-Pastur random covariance matrices. We present a proof in a Gaussian case, due to Silverstein, based on a formula by Ginibre, and a proof of the universal case by revisiting the approach of Tao and Vu, based on the Hermitization of Girko, the logarithmic potential, and the control of the small singular values. Beyond the finite variance model, we also consider the case where the entries have heavy tails, by using the objective method of Aldous and Steele borrowed from randomized combinatorial optimization. The limiting law is then no longer the circular law and is relat...

  8. Wiimote Experiments: Circular Motion

    Science.gov (United States)

    Kouh, Minjoon; Holz, Danielle; Kawam, Alae; Lamont, Mary

    2013-01-01

    The advent of new sensor technologies can provide new ways of exploring fundamental physics. In this paper, we show how a Wiimote, which is a handheld remote controller for the Nintendo Wii video game system with an accelerometer, can be used to study the dynamics of circular motion with a very simple setup such as an old record player or a…

  9. Effects of dimerization on the photoelectron angular distribution parameters from chiral camphor enantiomers obtained with circularly polarized vacuum-ultraviolet radiation

    Science.gov (United States)

    Nahon, Laurent; Garcia, Gustavo A.; Soldi-Lose, Héloïse; Daly, Steven; Powis, Ivan

    2010-09-01

    As an intermediate state of matter between the free monomeric gas phase and the solid state, clusters may exhibit a specific electronic structure and photoionization dynamics that can be unraveled by different types of electron spectroscopies. From mass-selected ion yield scans measured for photoionization of (R)-camphor, the ionization potentials (IPs) of the monomer (8.66±0.01 eV), and of the homochiral dimer (⩽8.37±0.01 eV) and trimer (⩽8.30±0.01 eV) were obtained. These spectra, combined with threshold photoelectron spectroscopy and velocity map ion imaging, allow us to show that the camphor monomer and dimer photoionization channels are decoupled, i.e., that the highest occupied molecular orbital (HOMO) of the dimer does not undergo a dissociative ionization process that would lead to a spurious contribution to the monomer ion channel. Therefore mass selection, as achieved in our imaging photoelectron-photoion coincidence experiments, leads to size selection of the nascent monomer or dimer species. Since both the monomer and dimer are chiral, their photoelectron angular distribution (PAD) not only involves the usual β anisotropy parameter but also a chiral asymmetry parameter b1 that can generate a forward-backward asymmetry in the PAD. This has been investigated using circularly polarized light (CPL) to record the photoelectron circular dichroism (PECD) in the near-threshold vacuum-ultraviolet (VUV) photoionization region. Analysis of size-selected electron images recorded with left- and right-handed CPL shows that over the first 1.5 eV above the HOMO orbital ionization potentials (IPs), the β parameter is not affected by the dimerization process, while the chiral b1 parameter shows clear differences between the monomer and the dimer, confirming that PECD is a subtle long-range probe of the molecular potential.

  10. Influence of interstitial solutions (H, N) on cerium electronic state in Ce-Fe intermetallic compounds: X-ray Absorption Spectroscopy (XAS) study

    International Nuclear Information System (INIS)

    It is presented an x-ray absorption spectroscopy (XAS) investigation performed at the L-edges of the rare-earth and at the K-edge of iron in the R-Fe intermetallic compounds (La, Ce)2Fe14BHχand Ce2Fe17(H,N)χ, to elucidate the role of the interstitial doping into the electronic and magnetic properties of these systems. Comparison with x-ray circular magnetic dichroism (XCMD) experiments has been carried out to clarify the localization of 4f magnetic moment at the Ce sites upon hydriding. Both XAS and XCMD results evidence the interplay between the structural and magnetic changes, that are associated to the modification of the hybridization between the Fe(3d) and Ce(5d) bands

  11. Spectroscopy, calorimetry and molecular simulation studies on the interaction of catalase with copper ion.

    Science.gov (United States)

    Hao, Fang; Jing, Mingyang; Zhao, Xingchen; Liu, Rutao

    2015-02-01

    In this research, the binding mechanism of Cu(2+) to bovine liver catalase (BLC) was studied by fluorescence spectroscopy, ultraviolet-visible (UV-vis) absorption spectroscopy, circular dichroism (CD) spectroscopy, isothermal titration calorimetry (ITC) and molecular docking methods. The cellar experiment was firstly carried out to investigate the inhibition effect of catalase. During the fluorescence quenching study, after correcting the inner filter effect (IFE), the fluorescence of BLC was found to be quenched by Cu(2+). The quenching mechanism was determined by fluorescence lifetime measurement, and was confirmed to be the dynamic mode. The secondary structure content of BLC was changed by the addition of Cu(2+), as revealed by UV-vis absorption and CD spectra, which further induces the decrease in BLC activity. Molecular simulation study indicates that Cu(2+) is located between two β-sheets and two random coils of BLC near to the heme group, and interacts with His 74 and Ser 113 residues near a hydrophilic area. The decrease of α-helix and the binding of His 74 are considered to be the major reason for the inhibition of BLC activity caused by Cu(2+). The ITC results indicate that the binding stoichiometry of Cu(2+) to catalase is 11.4. Moreover, the binding of Cu(2+) to BLC destroyed H-bonds, which was confirmed by the CD result.

  12. Circular arc structures

    KAUST Repository

    Bo, Pengbo

    2011-07-01

    The most important guiding principle in computational methods for freeform architecture is the balance between cost efficiency on the one hand, and adherence to the design intent on the other. Key issues are the simplicity of supporting and connecting elements as well as repetition of costly parts. This paper proposes so-called circular arc structures as a means to faithfully realize freeform designs without giving up smooth appearance. In contrast to non-smooth meshes with straight edges where geometric complexity is concentrated in the nodes, we stay with smooth surfaces and rather distribute complexity in a uniform way by allowing edges in the shape of circular arcs. We are able to achieve the simplest possible shape of nodes without interfering with known panel optimization algorithms. We study remarkable special cases of circular arc structures which possess simple supporting elements or repetitive edges, we present the first global approximation method for principal patches, and we show an extension to volumetric structures for truly threedimensional designs. © 2011 ACM.

  13. Characterization of Two Soybean (Clycine max. L) LEA IV Proteins by Circular Dichroism and Fourier Transform Infrared Spectrometry

    NARCIS (Netherlands)

    Shih, M.D.; Hsieh, T.Y.; Lin, T.P.; Hsing, Y.I.; Hoekstra, F.A.

    2010-01-01

    Late embryogenesis-abundant (LEA) proteins, accumulating to a high level during the late stages of seed development, may play a role as osmoprotectants. However, the functions and mechanisms of LEA proteins remained to be elucidated. Five major groups of LEA proteins have been described. In the pres

  14. Probing the structure of glucan lyases – the lytic members of GH31 - by sequence analysis, circular dichroism and proteolysis

    DEFF Research Database (Denmark)

    Ernst, Heidi; Lo Leggio, Leila; Yu, Shukun;

    2005-01-01

    Glucan lyase (GL) is a polysaccharide lyase with unique characteristics. It is involved in an alternative pathway for the degradation of alpha-glucans, the anhydrofructose pathway. Sequence similarity suggests that this lytic enzyme belongs to glycoside hydrolase family 31, for which until very r...

  15. Circularly polarized antennas

    CERN Document Server

    Gao, Steven; Zhu, Fuguo

    2013-01-01

    This book presents a comprehensive insight into the design techniques for different types of CP antenna elements and arrays In this book, the authors address a broad range of topics on circularly polarized (CP) antennas. Firstly, it introduces to the reader basic principles, design techniques and characteristics of various types of CP antennas, such as CP patch antennas, CP helix antennas, quadrifilar helix antennas (QHA), printed quadrifilar helix antennas (PQHA), spiral antenna, CP slot antennas, CP dielectric resonator antennas, loop antennas, crossed dipoles, monopoles and CP horns. Adva

  16. 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

    Energy Technology Data Exchange (ETDEWEB)

    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.

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

    Science.gov (United States)

    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. Synchrotron radiation: a new tool for biophysical spectroscopy in the visible and ultraviolet

    Energy Technology Data Exchange (ETDEWEB)

    Sutherland, J C

    1978-01-01

    Spectroscopy in the ultraviolet, visible and near infrared regions of the electromagnetic spectrum is extremely important in the study of biological materials. These lectures consider the applications of synchrotron radiation (SR) to this region. They are limited to measurements which do not make use of the time structure inherent in SR. Comparisons of SR with conventional sources suggests that the greatest improvements will be realized in the far and vacuum ultraviolet regions--wavelengths less than about 300 nm. Consideration of the transitions of the valence electrons of most organic and biologically important materials indicate that wavelengths less than about 120 nm will not be especially informative. In addition, spectroscopic experiments at wavelengths less than 105 nm become more difficult because of the loss of window materials and surfaces with high normal incidence reflectance. The characteristic visible and ultraviolet absorption bands of proteins, nucleic acids and sugars are reviewed. Important spectroscopic techniques such as absorption, natural and magnetic circular dichroism, fluorescence and various fluorescence polarization spectroscopies are described and their potential use in the far and vacuum ultraviolet (120 to 300 nm) using synchrotron sources is discussed.

  19. Secondary Structure Prediction of Protein Constructs Using Random Incremental Truncation and Vacuum-Ultraviolet CD Spectroscopy.

    Directory of Open Access Journals (Sweden)

    Mária Pukáncsik

    Full Text Available A novel uracil-DNA degrading protein factor (termed UDE was identified in Drosophila melanogaster with no significant structural and functional homology to other uracil-DNA binding or processing factors. Determination of the 3D structure of UDE is excepted to provide key information on the description of the molecular mechanism of action of UDE catalysis, as well as in general uracil-recognition and nuclease action. Towards this long-term aim, the random library ESPRIT technology was applied to the novel protein UDE to overcome problems in identifying soluble expressing constructs given the absence of precise information on domain content and arrangement. Nine constructs of UDE were chosen to decipher structural and functional relationships. Vacuum ultraviolet circular dichroism (VUVCD spectroscopy was performed to define the secondary structure content and location within UDE and its truncated variants. The quantitative analysis demonstrated exclusive α-helical content for the full-length protein, which is preserved in the truncated constructs. Arrangement of α-helical bundles within the truncated protein segments suggested new domain boundaries which differ from the conserved motifs determined by sequence-based alignment of UDE homologues. Here we demonstrate that the combination of ESPRIT and VUVCD spectroscopy provides a new structural description of UDE and confirms that the truncated constructs are useful for further detailed functional studies.

  20. Structural study of human growth hormone-releasing factor fragment (1?29) by vibrational spectroscopy

    Science.gov (United States)

    Carmona, P.; Molina, M.; Lasagabaster, A.

    1995-05-01

    The conformational structure of fragment 1-29 of human growth hormone releasing factor, hGHRF (1-29), in aqueous solution and in the solid state is investigated by infrared and Raman spectroscopy. The polypeptide backbone is found to be unordered in the solid state. However, the spectra of the peptide prepared as 5% (w/w) aqueous solutions show that approximately 28% of the peptide is involved in intermolecular β-sheet aggregation. The remainder of the peptide exists largely as disordered and β-sheet conformations with a small portion of α-helices. Tyrosine residues are found to be exposed to the solvent. The secondary structures are quantitatively examined through infrared spectroscopy, the conformational percentages being near those obtained by HONDAet al. [ Biopolymers31, 869 (1991)] using circular dichroism. The fast hydrogen/deuterium exchange in peptide groups and the absence of any NMR sign indicative of ordered structure [ G. M. CLOREet al., J. Molec. Biol.191, 553 (1986)] support that the solution conformations of the non-aggregated peptide interconvert in dynamic equilibrium. Some physiological advantages that may derive from this conformational flexibility are also discussed

  1. Secondary Structure Prediction of Protein Constructs Using Random Incremental Truncation and Vacuum-Ultraviolet CD Spectroscopy

    Science.gov (United States)

    Pukáncsik, Mária; Orbán, Ágnes; Nagy, Kinga; Matsuo, Koichi; Gekko, Kunihiko; Maurin, Damien; Hart, Darren; Kézsmárki, István; Vertessy, Beata G.

    2016-01-01

    A novel uracil-DNA degrading protein factor (termed UDE) was identified in Drosophila melanogaster with no significant structural and functional homology to other uracil-DNA binding or processing factors. Determination of the 3D structure of UDE is excepted to provide key information on the description of the molecular mechanism of action of UDE catalysis, as well as in general uracil-recognition and nuclease action. Towards this long-term aim, the random library ESPRIT technology was applied to the novel protein UDE to overcome problems in identifying soluble expressing constructs given the absence of precise information on domain content and arrangement. Nine constructs of UDE were chosen to decipher structural and functional relationships. Vacuum ultraviolet circular dichroism (VUVCD) spectroscopy was performed to define the secondary structure content and location within UDE and its truncated variants. The quantitative analysis demonstrated exclusive α-helical content for the full-length protein, which is preserved in the truncated constructs. Arrangement of α-helical bundles within the truncated protein segments suggested new domain boundaries which differ from the conserved motifs determined by sequence-based alignment of UDE homologues. Here we demonstrate that the combination of ESPRIT and VUVCD spectroscopy provides a new structural description of UDE and confirms that the truncated constructs are useful for further detailed functional studies. PMID:27273007

  2. Aptamer-based biosensor for label-free detection of ethanolamine by electrochemical impedance spectroscopy.

    Science.gov (United States)

    Liang, Gang; Man, Yan; Jin, Xinxin; Pan, Ligang; Liu, Xinhui

    2016-09-14

    A label-free sensing assay for ethanolamine (EA) detection based on G-quadruplex-EA binding interaction is presented by using G-rich aptamer DNA (Ap-DNA) and electrochemical impedance spectroscopy (EIS). The presence of K(+) induces the Ap-DNA to form a K(+)-stabilized G-quadruplex structure which provides binding sites for EA. The sensing mechanism was further confirmed by circular dichroism (CD) spectroscopy and EIS measurement. As a result, the charge transfer resistance (RCT) is strongly increased as demonstrated by using the ferro/ferricyanide ([Fe(CN)6](3-/4-)) as a redox probe. Under the optimized conditions, a linear relationship between ΔRCT and EA concentration was obtained over the range of 0.16 nM and 16 nM EA, with a detection limit of 0.08 nM. Interference by other selected chemicals with similar structure was negligible. Analytical results of EA spiked into tap water and serum by the sensor suggested the assay could be successfully applied to real sample analysis. With the advantages of high sensitivity, selectivity and simple sensor construction, this method is potentially suitable for the on-site monitoring of EA contamination.

  3. The Circular Camera Movement

    DEFF Research Database (Denmark)

    Hansen, Lennard Højbjerg

    2014-01-01

    It has been an accepted precept in film theory that specific stylistic features do not express specific content. Nevertheless, it is possible to find many examples in the history of film in which stylistic features do express specific content: for instance, the circular camera movement is used...... repeatedly to convey the feeling of a man and a woman falling in love. This raises the question of why producers and directors choose certain stylistic features to narrate certain categories of content. Through the analysis of several short film and TV clips, this article explores whether...... or not there are perceptual aspects related to specific stylistic features that enable them to be used for delimited narrational purposes. The article further attempts to reopen this particular stylistic debate by exploring the embodied aspects of visual perception in relation to specific stylistic features...

  4. Circular PVDF Airborne Transducer

    Institute of Scientific and Technical Information of China (English)

    JIAO Li-hua; XU Li-mei; HONG Hu

    2007-01-01

    With the required increased audio pressure of the parametric ultrasonic transducer array and the difficulty to theoretically analyse the complex ultrasonic structure in audio beam application, an computafionally efficient model is desired to describe the characteristic of the parametric ultrasonic transducer array for the system design and optimization. By applying the symmetry boundary conditions at the mid-plane in the thickness direction, a finite element model based on the half thickness simplification is presented to analyze the parametric circular transducer which is designed by gluing the poly Vinylidene fluoride film (PVDF). The validity of the proposed model is confirmed by a comparison of finite element aalysis results with the theoretical value and experimental data, which show that they are making a good agreement with each other.

  5. A Physico-Chemical Study of Some Areas of Fundamental Significance to Biophysics

    Energy Technology Data Exchange (ETDEWEB)

    Kumar, Devendra; McGlynn, S. P.

    1999-04-01

    This report covers: Radiation Signatures; Electronic Structure of Steroids, Vitamins, and others; Laser Optogalvanic Effect; Vacuum Ultraviolet Spectroscopy, including Electron Scattering, Photochemistry, and Magnetic Circular Dichroism; and Ozone.

  6. Operational circular No. 1 (Rev. 1) – Operational circulars

    CERN Multimedia

    HR Department

    2011-01-01

    Operational Circular No. 1 (Rev. 1) is applicable to members of the personnel and other persons concerned. Operational Circular No. 1 (Rev. 1) entitled "Operational circulars", approved following discussion at the Standing Concertation Committee meeting on 4 May 2011, is available on the intranet site of the Human Resources Department: https://hr-docs.web.cern.ch/hr-docs/opcirc/opcirc.asp It cancels and replaces Operational Circular No. 1 entitled "Operational Circulars” of December 1996. This new version clarifies, in particular, that operational circulars do not necessarily arise from the Staff Rules and Regulations, and the functional titles have been updated to bring them into line with the current CERN organigram. Department Head Office  

  7. Circular chemiresistors for microchemical sensors

    Science.gov (United States)

    Ho, Clifford K.

    2007-03-13

    A circular chemiresistor for use in microchemical sensors. A pair of electrodes is fabricated on an electrically insulating substrate. The pattern of electrodes is arranged in a circle-filling geometry, such as a concentric, dual-track spiral design, or a circular interdigitated design. A drop of a chemically sensitive polymer (i.e., chemiresistive ink) is deposited on the insulating substrate on the electrodes, which spreads out into a thin, circular disk contacting the pair of electrodes. This circularly-shaped electrode geometry maximizes the contact area between the pair of electrodes and the polymer deposit, which provides a lower and more stable baseline resistance than with linear-trace designs. The circularly-shaped electrode pattern also serves to minimize batch-to-batch variations in the baseline resistance due to non-uniform distributions of conductive particles in the chemiresistive polymer film.

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

    Science.gov (United States)

    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.

  9. Circularly Polarized Persistent Room-Temperature Phosphorescence from Metal-Free Chiral Aromatics in Air.

    Science.gov (United States)

    Hirata, Shuzo; Vacha, Martin

    2016-04-21

    Circularly polarized room-temperature phosphorescence (RTP) with persistent emission characteristics was observed from metal-free chiral binaphthyl structures. Enantiomers of the binaphthyl compounds doped into an amorphous hydroxylated steroid matrix produced blue fluorescence and yellow persistent RTP in air. The lifetime and quantum yield of the yellow persistent RTP were 0.67 s and 2.3%, respectively. The dissymmetry factors of circular dichroism (CD) in the first absorption band, circularly polarized fluorescence (CPF), and circularly polarized persistent RTP were |1.1 × 10(-3)|, |4.5 × 10(-4)|, and |2.3 × 10(-3)|, respectively. A comparison between the experimental data and calculations by time-dependent density functional theory for transient CD spectra confirmed that the binaphthyl conformations in the lowest singlet excited state (S1) and the lowest triplet state (T1) were different. The large difference in the dissymmetry factors for the CPF and the circularly polarized persistent RTP was likely caused by this conformational change between S1 and T1. PMID:27058743

  10. Circularly Polarized Persistent Room-Temperature Phosphorescence from Metal-Free Chiral Aromatics in Air.

    Science.gov (United States)

    Hirata, Shuzo; Vacha, Martin

    2016-04-21

    Circularly polarized room-temperature phosphorescence (RTP) with persistent emission characteristics was observed from metal-free chiral binaphthyl structures. Enantiomers of the binaphthyl compounds doped into an amorphous hydroxylated steroid matrix produced blue fluorescence and yellow persistent RTP in air. The lifetime and quantum yield of the yellow persistent RTP were 0.67 s and 2.3%, respectively. The dissymmetry factors of circular dichroism (CD) in the first absorption band, circularly polarized fluorescence (CPF), and circularly polarized persistent RTP were |1.1 × 10(-3)|, |4.5 × 10(-4)|, and |2.3 × 10(-3)|, respectively. A comparison between the experimental data and calculations by time-dependent density functional theory for transient CD spectra confirmed that the binaphthyl conformations in the lowest singlet excited state (S1) and the lowest triplet state (T1) were different. The large difference in the dissymmetry factors for the CPF and the circularly polarized persistent RTP was likely caused by this conformational change between S1 and T1.

  11. Future Circular Colliders

    CERN Document Server

    AUTHOR|(CDS)2108454; Zimmermann, Frank

    2015-01-01

    In response to a request from the 2013 Update of the European Strategy for Particle Physics, the global Future Circular Collider (FCC) study is preparing the foundation for a next-generation large-scale accelerator infrastructure in the heart of Europe. The FCC study focuses on the design of a 100-TeV hadron collider (FCC-hh), to be accommodated in a new ∼100 km tunnel near Geneva. It also includes the design of a high-luminosity electron-positron collider (FCC-ee), which could be installed in the same tunnel as a potential intermediate step, and a lepton-hadron collider option (FCC-he). The scope of the FCC study comprises accelerators, technology, infrastructure, detectors, physics, concepts for worldwide data services, international governance models, and implementation scenarios. Among the FCC core technologies figure 16-T dipole magnets, based on Nb3Sn superconductor, for the FCC-hh hadron collider, and a highly efficient superconducting radiofrequency system for the FCC-ee lepton collider. The interna...

  12. Towards Future Circular Colliders

    CERN Document Server

    AUTHOR|(CDS)2108454; Zimmermann, Frank

    2016-01-01

    The Large Hadron Collider (LHC) at CERN presently provides proton-proton collisions at a centre-of-mass (c.m.) energy of 13 TeV. The LHC design was started more than 30 years ago, and its physics programme will extend through the second half of the 2030’s. The global Future Circular Collider (FCC) study is now preparing for a post-LHC project. The FCC study focuses on the design of a 100-TeV hadron collider (FCC-hh) in a new ∼100 km tunnel. It also includes the design of a high-luminosity electron-positron collider (FCC-ee) as a potential intermediate step, and a lepton-hadron collider option (FCC-he). The scope of the FCC study comprises accelerators, technology, infrastructure, detectors, physics, concepts for worldwide data services, international governance models, and implementation scenarios. Among the FCC core technologies figure 16-T dipole magnets, based on $Nb_3Sn$ superconductor, for the FCC-hh hadron collider, and a highly efficient superconducting radiofrequency system for the FCC-ee lepton c...

  13. Future Circular Colliders

    CERN Document Server

    AUTHOR|(CDS)2108454; Zimmermann, Frank

    2015-01-01

    In response to a request from the 2013 Update of the European Strategy for Particle Physics, the global Future Circular Collider (FCC) study is preparing the foundation for a next-generation large-scale accelerator infrastructure in the heart of Europe. The FCC study focuses on the design of a 100-TeV hadron collider (FCC-hh), to be accommodated in a new ∼100 km tunnel near Geneva. It also includes the design of a high-luminosity electron-positron collider (FCC-ee), which could be installed in the same tunnel as a potential intermediate step, and a lepton-hadron collider option (FCC-he). The scope of the FCC study comprises accelerators, technology, infrastructure, detector, physics, concepts for worldwide data services, international governance models, and implementation scenarios. Among the FCC core technologies figure 16-T dipole magnets, based on Nb3Sn superconductor, for the FCC-hh hadron collider, and a highly efficient superconducting radiofrequency system for the FCC-ee lepton collider. The internat...

  14. Soft X-ray magnetic dichroism of (Ca,Sr)RuO{sub 3}: Evidence for strain-dependent magnetism

    Energy Technology Data Exchange (ETDEWEB)

    Assmann, Andrea; Uebe, Stephan; Wissinger, Markus; Loehneysen, Hilbert von [Karlsruhe Institute of Technology, Institut fuer Festkoerperphysik (Germany); Karlsruhe Institute of Technology, Physikalisches Institut (Germany); Merz, Michael; Fuchs, Dirk; Nagel, Peter; Schuppler, Stefan [Karlsruhe Institute of Technology, Institut fuer Festkoerperphysik (Germany)

    2010-07-01

    The 4d transition metal oxide Ca{sub 1-x}Sr{sub x}RuO{sub 3} exhibits ferromagnetic order in the doping range 0.4circular dichroism at the Ru M{sub 2,3} and O K edges. It turns out that at 20 K, the magnetic moments strongly depend on the strain: while the spin moment of samples on LSAT almost vanishes, a distinct moment is found for (Ca,Sr)RuO{sub 3} films deposited on STO and DSO. Furthermore, a significant magnetic anisotropy is observed, with the spin moments mainly oriented perpendicular to the substrate plane. Implications are discussed.

  15. The role of the magnetically induced anisotropy of the pair correlation function in the dichroism of magnetic fluids

    Energy Technology Data Exchange (ETDEWEB)

    Socoliuc, V., E-mail: vsocoliuc@acad-tim.tm.edu.ro [“Petru Poni” Institute of Macromolecular Chemistry, 41A Grigore Ghica Voda Alley, 700487 Iasi (Romania); Laboratory of Magnetic Fluids, Center for Fundamental and Advanced Technical Research, Romanian Academy-Timisoara Branch, Bv.M. Viteazu 24, Timisoara RO-300223 (Romania); Popescu, L.B. [Institute for Space Sciences, 409 Atomistilor, Magurele 077125 (Romania)

    2013-12-15

    Experimental evidence is presented that the susceptibility for magnetically induced dichroism in concentrated magnetic fluids decays with further increasing of the magnetic nanoparticle concentration. The analysis of the predictions derived from our dichroism model, based on the pair correlation function developed by Elfimova and Ivanov (2010), showed that the observed phenomenon can be explained by the manner in which the symmetry of the pair correlation function changes with increasing magnetic field intensity and sample concentration. The increase of the dichroism with increasing concentration in diluted samples (0.2–1%) is mainly caused by the pair correlations in the first coordination layer, predominantly along the magnetic field direction. In the 1–3% concentration range, the first coordination layer becomes increasingly isotropic while pair correlations in the second coordination layer grow transversally to the magnetic field direction. Thus, with the increase of the concentration above 2%, the dichroism decreases as a combined effect of the changes in the symmetry of the pair correlations in the first and the second coordination layers. The proposed dichroism model predicts the possibility of negative magnetically induced dichroism in highly concentrated perfect colloidal dispersions of small spherical magnetic nanoparticles. - Highlights: • Experiment: the magnetically induced dichroism is inhibited in concentrated magnetic fluids. • Theory: dichroism model based on long range interparticle correlations. • The symmetry features of the pair correlation function explains the experimental findings. • The proposed dichroism model predicts the possibility of negative magnetically induced dichroism.

  16. Circularly-Polarized Microstrip Antenna

    Science.gov (United States)

    Stanton, P. H.

    1985-01-01

    Microstrip construction compact for mobile applications. Circularly polarized microstrip antenna made of concentric cylindrical layers of conductive and dielectric materials. Coaxial cable feedlines connected to horizontal and vertical subelements from inside. Vertical subelement acts as ground for horizontal subelement.

  17. A configurational and conformational study of aframodial and its diasteriomers via experimental and theoretical VA and VCD spectroscopies

    DEFF Research Database (Denmark)

    Jalkanen, Karl J.; Gale, J.D.; Lassen, Peter Rygaard;

    2008-01-01

    In this work we present the experimental and theoretical vibrational absorption (VA) and the theoretical vibrational circular dichroism (VCD) spectra for aframodial. In addition, we present the theoretical VA and VCD spectra for the diasteriomers of aframodial. Aframodial has four chiral centers ...

  18. Binding mechanism of trans-N-caffeoyltyramine and human serum albumin: Investigation by multi-spectroscopy and docking simulation.

    Science.gov (United States)

    Ma, Xiaoli; Yan, Jin; Xu, Kailin; Guo, Luiqi; Li, Hui

    2016-06-01

    trans-N-Caffeoyltyramine (TNC), which was isolated from the Cortex Lycii in our laboratory, is a phenolic amide compound with multiple pharmacological activities. The interaction between TNC and human serum albumin (HSA) was studied by Nuclear magnetic resonance (NMR) relaxation experiment, fluorescence spectroscopy, and docking simulation. NMR methodology is based on the analysis of selective and non-selective spin-lattice relaxation rate enhancements of TNC protons in the presence of the HSA. Result indicated that the interaction occurred between HSA and TNC, and changed the proton magnetic environment of TNC. Fluorescence spectroscopy confirmed that TNC displayed a strong capability to quench the fluorescence of HSA, and the acting forces for binding were hydrogen bonds and van der Waals forces. Furthermore, the circular dichroism, synchronous, and three-dimensional fluorescence spectra, which were employed to determine the conformation of protein, revealed that binding of TNC with HSA could induce conformational changes in HSA. In addition, the molecular modeling results exhibited that TNC mainly bonded to site I in sub-domain IIA of HSA. PMID:27131098

  19. Spectroscopy and Fluorescence Lifetime Imaging Microscopy To Probe the Interaction of Bovine Serum Albumin with Graphene Oxide.

    Science.gov (United States)

    Kuchlyan, Jagannath; Kundu, Niloy; Banik, Debasis; Roy, Arpita; Sarkar, Nilmoni

    2015-12-29

    The interaction of graphene oxide (GO) with bovine serum albumin (BSA) in aqueous buffer solution has been investigated with various spectroscopic and imaging techniques. At single molecular resolution this interaction has been performed using fluorescence correlation spectroscopy (FCS) and fluorescence lifetime imaging microscopy (FLIM) techniques. The conformational dynamics of BSA on GO's influence have been explored by FCS and circular dichroism (CD) spectroscopy. For the FCS studies BSA was labeled covalently by a fluorophore, Alexa Fluor 488. On the addition of GO in phosphate buffer of 10 mM at pH 7.4 the diffusion time (τD) and the hydrodynamic radius (Rh) of BSA increase due to adsorption of BSA. Conformational relaxation time components of native BSA drastically vary with the addition of GO, signifying the change of conformational dynamics of BSA after addition of GO. The adsorption isotherm also indicates significant adsorption of BSA on the GO surface. Adsorption of BSA on the GO surface has shown in direct images of atomic force microscopy (AFM) and FLIM. Fluorescence quenching study of BSA with addition of GO also indicates that there is strong interaction between BSA and GO. PMID:26646418

  20. Novel type of red-shifted chlorophyll a antenna complex from Chromera velia: II. Biochemistry and spectroscopy.

    Science.gov (United States)

    Bína, David; Gardian, Zdenko; Herbstová, Miroslava; Kotabová, Eva; Koník, Peter; Litvín, Radek; Prášil, Ondřej; Tichý, Josef; Vácha, František

    2014-06-01

    A novel chlorophyll a containing pigment-protein complex expressed by cells of Chromera velia adapted to growth under red/far-red illumination [1]. Purification of the complex was achieved by means of anion-exchange chromatography and gel-filtration. The antenna is shown to be an aggregate of ~20kDa proteins of the light-harvesting complex (LHC) family, unstable in the isolated form. The complex possesses an absorption maximum at 705nm at room temperature in addition to the main chlorophyll a maximum at 677nm producing the major emission band at 714nm at room temperature. The far-red absorption is shown to be the property of the isolated aggregate in the intact form and lost upon dissociation. The purified complex was further characterized by circular dichroism spectroscopy and fluorescence spectroscopy. This work thus identified the third different class of antenna complex in C. velia after the recently described FCP-like and LHCr-like antennas. Possible candidates for red antennas are identified in other taxonomic groups, such as eustigmatophytes and the relevance of the present results to other known examples of red-shifted antenna from other organisms is discussed. This work appears to be the first successful isolation of a chlorophyll a-based far-red antenna complex absorbing above 700nm unrelated to LHCI.

  1. Individual and collective modes of surface magnetoplasmon in thiolate-protected silver nanoparticles studied by MCD spectroscopy.

    Science.gov (United States)

    Yao, Hiroshi; Shiratsu, Taisuke

    2016-06-01

    Large magneto-optical (MO) responses at the energy of localized surface plasmon resonance (LSPR), namely, surface magnetoplasmons, are demonstrated for the first time in thiolate-protected silver nanoparticles with magnetic circular dichroism (MCD) spectroscopy. The samples examined are decanethiol (DT)-, azobenzenethiol (ABT)-, and ABT/DT mixed-monolayer-protected Ag nanoparticles. ABT-protected Ag nanoparticles are somewhat aggregated and thus exhibit a broad, collective mode of plasmonic absorption, whereas other samples with highly-dispersed nanoparticles show an individual mode of LSPR absorption. In all Ag nanoparticles, a derivative-like MCD signal is observed under an applied magnetic field of 1.6 T, which can be explained in terms of two circular modes of magnetoplasmon caused by the increase (or decrease) in the Lorentz force imparted on the free electrons that oscillate in the left (or right) circular orbits in the nanosphere. For the Ag nanoparticles exhibiting an individual LSPR mode, in particular, simultaneous deconvolution analysis of UV-vis absorption and MCD spectra reveal that (i) the amplitude of the magnetoplasmonic component with lower frequency (ω-), resulting from the reduction in the confinement strength of collective electrons by the Lorentz force, is stronger than that with a higher frequency (ω+); (ii) the accurate shift or cyclotron frequency between two magnetoplasmonic modes (ωc = ω+-ω-) is size-dependent, and presents a very large value with implications for the apparent enhancement of the local magnetic-field in the Ag nanoparticles. These results strongly suggest that the Ag-thiolate layer or Ag-S bonding on the nanoparticle surface plays a significant role in the MO enhancement. PMID:27188783

  2. Circularly polarized open-loop antenna

    OpenAIRE

    Li, Rong-Lin; Fusco, Vincent F.; Nakano, Hisamatsu

    2003-01-01

    A printed circular open-loop antenna is introduced as a simple structure for producing circular polarization; the antenna is fed with a coaxial probe. By introducing a gap within the circular loop a traveling-wave current is excited and thus circularly polarized radiation can be achieved. An optimized circularly polarized antenna is designed through numerical analysis using a so-called parametric method of moment technique. Experimental verification of the new antenna is presented. The antenn...

  3. Insights into Hydrocarbon-rich Environments from Studies of Protein Dynamics, Thermodynamics, and Spectroscopy

    Science.gov (United States)

    Magyar, J. S.; Asous, N. K.; Barth, S. J.; Benzik, E.; Chou, J.; Dalchand, N.; Gallagher, G. E.; Montero, K. S.; Lone, S. K.; Salerno, G. J.

    2015-12-01

    Extraordinary amounts of information are now available from genomic and metagenomic analyses of a wide variety of environments of geological and biological interest. Using such genomic information as a starting point, we are interested in looking at microbial systems at the molecular level, using the tools and approaches of inorganic chemistry, physical chemistry, and molecular biology. From these studies, spanning the molecular to the global, we gain insights into relationships between microbial life and the geochemical environment in which it lives. In our work to date, we have focused on hydrocarbon-rich environments, including the La Brea Tar Pits and the Gulf of Mexico. Starting from genomic information, we have identified proteins of interest, cloned synthetic genes into E. coli, overexpressed and purified the proteins, and characterized them by UV-visible absorption, circular dichroism, and NMR spectroscopies; X-ray crystallography; and electrochemistry. Using as examples our recent studies of a metal-uptake protein from a methanogenic archaeon native to the La Brea Tar Pits, and of electron-transfer and hydrocarbon-degrading proteins from cold marine ecosystems, we describe how new combinations of genomics, molecular biology, and bioinorganic chemistry can provide novel insights into geobiological processes.

  4. Study of the interaction between 5-sulfosalicylic acid and bovine serum albumin by fluorescence spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Juan, E-mail: zhangjuano13@126.com [Department of Chemistry, School of Basic Medical Sciences, Ningxia Medical University, Yinchuan City, Ningxia Province 750004 (China); Yan, Qianshun; Liu, Jianping; Lu, Xiaohong; Zhu, Yanshu [Department of Chemistry, School of Basic Medical Sciences, Ningxia Medical University, Yinchuan City, Ningxia Province 750004 (China); Wang, Jie; Wang, Shujing [Medical Science Research Center, Ningxia Medical University, Yinchuan City, Ningxia Province 750004 (China)

    2013-02-15

    The interaction between 5-sulfosalicylic acid (SSA) and bovine serum albumin (BSA) at pH 7.40 was studied by fluorescence and UV-vis absorption spectroscopy at different temperatures. The results revealed that SSA caused the fluorescence quenching of BSA through a static quenching procedure. The binding constant K was measured by fluorescence quenching method. The thermodynamic parameters, {Delta}H and {Delta}S, were calculated to be 23.16 kJ mol{sup -1}>0 and 162.37 J mol{sup -1} K{sup -1}>0, respectively, which suggested that the hydrophobic force played a major role in the reaction of SSA on BSA. The distance r between donor (BSA) and acceptor (SSA) was obtained according to the Foerster non-radiation energy transfer theory. The results of synchronous fluorescence spectra, three-dimensional fluorescence spectra and far-UV circular dichroism spectra showed that the interaction between BSA and SSA induced conformational changes in BSA. - Highlights: Black-Right-Pointing-Pointer Interaction of BSA with SSA was investigated by FL, UV-vis and CD spectra. Black-Right-Pointing-Pointer {Delta}H, {Delta}G, {Delta}S, K{sub q}, K{sub sv}, K and r were calculated. Black-Right-Pointing-Pointer Hydrophobic interaction played a major role in the reaction. Black-Right-Pointing-Pointer Conformation of BSA was changed in the presence of SSA.

  5. Study of the interaction between 5-sulfosalicylic acid and bovine serum albumin by fluorescence spectroscopy

    International Nuclear Information System (INIS)

    The interaction between 5-sulfosalicylic acid (SSA) and bovine serum albumin (BSA) at pH 7.40 was studied by fluorescence and UV–vis absorption spectroscopy at different temperatures. The results revealed that SSA caused the fluorescence quenching of BSA through a static quenching procedure. The binding constant K was measured by fluorescence quenching method. The thermodynamic parameters, ΔH and ΔS, were calculated to be 23.16 kJ mol−1>0 and 162.37 J mol−1 K−1>0, respectively, which suggested that the hydrophobic force played a major role in the reaction of SSA on BSA. The distance r between donor (BSA) and acceptor (SSA) was obtained according to the Förster non-radiation energy transfer theory. The results of synchronous fluorescence spectra, three-dimensional fluorescence spectra and far-UV circular dichroism spectra showed that the interaction between BSA and SSA induced conformational changes in BSA. - Highlights: ► Interaction of BSA with SSA was investigated by FL, UV–vis and CD spectra. ► ΔH, ΔG, ΔS, Kq, Ksv, K and r were calculated. ► Hydrophobic interaction played a major role in the reaction. ► Conformation of BSA was changed in the presence of SSA.

  6. Single-molecule spectroscopy of the temperature-induced collapse of unfolded proteins.

    Science.gov (United States)

    Nettels, Daniel; Müller-Späth, Sonja; Küster, Frank; Hofmann, Hagen; Haenni, Dominik; Rüegger, Stefan; Reymond, Luc; Hoffmann, Armin; Kubelka, Jan; Heinz, Benjamin; Gast, Klaus; Best, Robert B; Schuler, Benjamin

    2009-12-01

    We used single-molecule FRET in combination with other biophysical methods and molecular simulations to investigate the effect of temperature on the dimensions of unfolded proteins. With single-molecule FRET, this question can be addressed even under near-native conditions, where most molecules are folded, allowing us to probe a wide range of denaturant concentrations and temperatures. We find a compaction of the unfolded state of a small cold shock protein with increasing temperature in both the presence and the absence of denaturant, with good agreement between the results from single-molecule FRET and dynamic light scattering. Although dissociation of denaturant from the polypeptide chain with increasing temperature accounts for part of the compaction, the results indicate an important role for additional temperature-dependent interactions within the unfolded chain. The observation of a collapse of a similar extent in the extremely hydrophilic, intrinsically disordered protein prothymosin alpha suggests that the hydrophobic effect is not the sole source of the underlying interactions. Circular dichroism spectroscopy and replica exchange molecular dynamics simulations in explicit water show changes in secondary structure content with increasing temperature and suggest a contribution of intramolecular hydrogen bonding to unfolded state collapse.

  7. Enzyme stability, thermodynamics and secondary structures of α-amylase as probed by the CD spectroscopy.

    Science.gov (United States)

    Kikani, B A; Singh, S P

    2015-11-01

    An amylase of a thermophilic bacterium, Bacillus sp. TSSC-3 (GenBank Number, EU710557) isolated from the Tulsi Shyam hot spring reservoir (Gujarat, India) was purified to the homogeneity in a single step on phenyl sepharose 6FF. The molecular weight of the enzyme was 25kD, while the temperature and pH optima for the enzyme catalysis were 80°C and 7, respectively. The purified enzyme was highly thermostable with broad pH stability and displayed remarkable resistance against surfactants, chelators, urea, guanidine HCl and various solvents as well. The stability and changes in the secondary structure of the enzyme under various extreme conditions were determined by the circular dichroism (CD) spectroscopy. The stability trends and the changes in the α-helices and β-sheets were analyzed by Mean Residual Ellipticity (MRE) and K2D3. The CD data confirmed the structural stability of the enzyme under various harsh conditions, yet it indicated reduced α-helix content and increased β-sheets upon denaturation. The thermodynamic parameters; deactivation rate constant, half-life, changes in entropy, enthalpy, activation energy and Gibb's free energy indicated that the enzyme-substrate reactions were highly stable. The overall profile of the enzyme: high thermostability, alkalitolerance, calcium independent nature, dextrose equivalent values and resistance against chemical denaturants, solvents and surfactants suggest its commercial applications.

  8. Interaction study of ciprofloxacin with human telomeric DNA by spectroscopy and molecular docking

    Science.gov (United States)

    Li, Huihui; Bu, Xiaoyang; Lu, Jia; Xu, Chongzheng; Wang, Xianlong; Yang, Xiaodi

    2013-04-01

    The interaction of ciprofloxacin (CIP) with human telomeric DNA was studied in vitro using multi-spectroscopy and molecular modeling methods. The hypochromic effect with a red shift in ultraviolet (UV) absorption indicated the occurrence of the interaction between CIP and DNA. The fluorescence quenching of CIP was observed with the addition of DNA and was proved to be the static quenching. The binding constant was found to be 9.62 × 104 L mol-1. Electrospray ionization mass spectrometry (ESI-MS) result further confirmed the formation of 1:1 non-covalent complex between DNA and CIP. Combined with the UV melting results, circular dichroism (CD) results confirmed the existence of groove binding mode, as well as conformational changes of DNA. Molecular docking studies illustrated the visual display of the CIP binding to the GC region in the minor groove of DNA. Specific hydrogen bonds and van der Waals forces were demonstrated as main acting forces between CIP and guanine bases of DNA.

  9. Recent developments in the electronic spectroscopy of amides and alpha-helical polypeptides.

    Science.gov (United States)

    Woody, Robert W; Koslowski, Axel

    2002-12-10

    Recent experimental and theoretical advances in understanding the electronic excited states of simple amides are reviewed. Polarized reflection spectroscopy of single crystals of N-acetylglycine shows that the direction of the first pipi* (NV(1)) transition dipole moment of a secondary amide differs by approximately 15 degrees from that of a primary amide. Ab initio calculations on simple amides support this conclusion. Ab initio studies of di- and tri-amides demonstrate that several inter-amide charge-transfer (CT) transitions occur in the 150-175-nm region, between the NV(1) and NV(2) transitions. When the correct dipole transition moment direction for peptides is used in calculations of the circular dichroism of the alpha-helix, the results are much improved over those from earlier calculations that used the direction for primary amides. Studies that consider the mixing of the NV(1) transition with CT transitions are reviewed. These indicate that such mixing is likely to have a significant effect on the absorption and CD spectra of the alpha-helix and other types of peptide conformation. Nevertheless, the independent systems model gives a reasonable first approximation to the absorption and CD spectra of the alpha-helix. PMID:12488025

  10. Comparative Studies of Interactions between Fluorodihydroquinazolin Derivatives and Human Serum Albumin with Fluorescence Spectroscopy

    Directory of Open Access Journals (Sweden)

    Yi Wang

    2016-10-01

    Full Text Available In the present study, 3-(fluorobenzylideneamino-6-chloro-1-(3,3-dimethylbutanoyl-phenyl-2,3-dihydroquinazolin-4(1H-one (FDQL derivatives have been designed and synthesized to study the interaction between fluorine substituted dihydroquinazoline derivatives with human serum albumin (HSA using fluorescence, circular dichroism and Fourier transform infrared spectroscopy. The results indicated that the FDQL could bind to HSA, induce conformation and the secondary structure changes of HSA, and quench the intrinsic fluorescence of HSA through a static quenching mechanism. The thermodynamic parameters, ΔH, ΔS, and ΔG, calculated at different temperatures, revealed that the binding was through spontaneous and hydrophobic forces and thus played major roles in the association. Based on the number of binding sites, it was considered that one molecule of FDQL could bind to a single site of HSA. Site marker competition experiments indicated that the reactive site of HSA to FDQL mainly located in site II (subdomain IIIA. The substitution by fluorine in the benzene ring could increase the interactions between FDQL and HSA to some extent in the proper temperature range through hydrophobic effect, and the substitution at meta-position enhanced the affinity greater than that at para- and ortho-positions.

  11. Implementing circularity using partial evaluation

    DEFF Research Database (Denmark)

    Lawall, Julia Laetitia

    2001-01-01

    Complex data dependencies can often be expressed concisely by defining a variable in terms of part of its own value. Such a circular reference can be naturally expressed in a lazy functional language or in an attribute grammar. In this paper, we consider circular references in the context...... of an imperative C-like language, by extending the language with a new construct, persistent variables. We show that an extension of partial evaluation can eliminate persistent variables, producing a staged C program. This approach has been implemented in the Tempo specializer for C programs, and has proven useful...

  12. Podokinetic circular vection: characteristics and interaction with optokinetic circular vection.

    Science.gov (United States)

    Becker, W; Kliegl, K; Kassubek, J; Jürgens, R

    2016-07-01

    Stabilising horizontal body orientation in space without sight on a rotating platform by holding to a stationary structure and circular 'treadmill' stepping in the opposite direction can elicit an illusion of self-turning in space (Bles and Kapteyn in Agressologie 18:325-328, 1977). Because this illusion is analogous to the well-known illusion of optokinetic circular vection (oCV), we call it 'podokinetic circular vection' (pCV) here. Previous studies using eccentric stepping on a path tangential to the rotation found that pCV was always contraversive relative to platform rotation. In contrast, when our subjects stepped at the centre of rotation about their vertical axis, we observed an inverted, ipsiversive pCV as a reproducible trait in many of our subjects. This ipCV occurred at the same latency as the pCV of subjects reporting the actually expected contraversive direction, but had lower gain. In contrast to pCV, the nystagmus accompanying circular treadmill stepping had the same direction in all individuals (slow phase in the direction of platform motion). The direction of an individual's pCV predicted the characteristics of the CV resulting from combined opto- and podokinetic stimulation (circular treadmill stepping while viewing a pattern rotating together with the platform): in individuals with contraversive pCV, latency shortened and both gain and felt naturalness increased in comparison with pure oCV, whereas the opposite (longer latency, reduced gain and naturalness) occurred in individuals with ipCV. Taken together, the reproducibility of ipCV, the constant direction of nystagmus and the fact that pCV direction predicts the outcome of combined stimulation suggest that ipCV is an individual trait of many subjects during compensatory stepping at the centre of rotation. A hypothetical model is presented of how ipCV possibly could arise. PMID:26965438

  13. Circular RNA expands its territory.

    Science.gov (United States)

    Bao, Chunyang; Lyu, Dongbin; Huang, Shenglin

    2016-03-01

    Circular RNAs (circRNAs) represent a novel class of widespread non-coding RNAs in eukaryotes. They are unusually stable RNA molecules with cell type-specific expression patterns, and are predominantly present in the cytoplasm. We recently demonstrated the existence of abundant circRNAs in exosomes and suggest a potential application of exosomal circRNAs for cancer detection. PMID:27308606

  14. Circular polarization observed in bioluminescence

    NARCIS (Netherlands)

    Wijnberg, Hans; Meijer, E.W.; Hummelen, J.C.; Dekkers, H.P.J.M.; Schippers, P.H.; Carlson, A.D.

    1980-01-01

    While investigating circular polarization in luminescence, and having found it in chemiluminescence, we have studied bioluminescence because it is such a widespread and dramatic natural phenomenon. We report here that left and right lanterns of live larvae of the fireflies, Photuris lucicrescens and

  15. SUM-RULES FOR MAGNETIC DICHROISM IN RARE-EARTH 4F-PHOTOEMISSION

    NARCIS (Netherlands)

    THOLE, BT; VANDERLAAN, G

    1993-01-01

    We present new sum rules for magnetic dichroism in spin polarized photoemission from partly filled shells which give the expectation values of the orbital and spin magnetic moments and their correlations in the ground state. We apply this to the 4f photoemission of rare earths, where the polarizatio

  16. A new highly adaptable design of shear-flow device for orientation of macromolecules for Linear Dichroism (LD) measurement

    KAUST Repository

    Lundahl, P. Johan

    2011-01-01

    This article presents a new design of flow-orientation device for the study of bio-macromolecules, including DNA and protein complexes, as well as aggregates such as amyloid fibrils and liposome membranes, using Linear Dichroism (LD) spectroscopy. The design provides a number of technical advantages that should make the device inexpensive to manufacture, easier to use and more reliable than existing techniques. The degree of orientation achieved is of the same order of magnitude as that of the commonly used concentric cylinders Couette flow cell, however, since the device exploits a set of flat strain-free quartz plates, a number of problems associated with refraction and birefringence of light are eliminated, increasing the sensitivity and accuracy of measurement. The device provides similar shear rates to those of the Couette cell but is superior in that the shear rate is constant across the gap. Other major advantages of the design is the possibility to change parts and vary sample volume and path length easily and at a low cost. © 2011 The Royal Society of Chemistry.

  17. Convex mappings on some circular domains

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    In this paper,we consider some circular domains.And we give an extension theorem for some normalized biholomorphic convex mapping on some circular domains.Especially,we discover the normalized biholomorphic convex mapping on some circular domains have the form f(z) =(f1(z1),...,fn(zn)),where fj:D → C are normalized biholomorphic convex mapping.

  18. Energy dissipation in circular tube

    Directory of Open Access Journals (Sweden)

    A.D. Girgidov

    2012-01-01

    Full Text Available Energy dissipation distribution along the circular tube radius is important in solving such problems as calculation of heat transfer by the air flow through building envelope; calculation of pressure loss in spiral flows; calculation of cyclones with axial and tangential supply of dust-containing gas.Two types of one-dimensional radially axisymmetric flows in circular tube were considered: axial flow and rotation about the axis (Rankine vortex. Relying on two- and four-layer description of axial turbulent flow energy dissipation was calculated in each layer.Similar calculation for Rankine vortex with viscous sublayer at the tube surface was provided. By employing the dissipation minimum principle the boundary radius between rigid rotation and free vortex is calculated. Approximation of the velocity distribution in Rankine vortex is proposed.

  19. Control of a Circular Jet

    CERN Document Server

    Gohil, Trushar B; Muralidhar, K

    2010-01-01

    The present study report direct numerical simulation (DNS) of a circular jet and the effect of a large scale perturbation at the jet inlet. The perturbation is used to control the jet for increased spreading. Dual-mode perturbation is obtained by combining an axisymmetric excitation with the helical. In the fluid dynamics videos, an active control of the circular jet at a Reynolds number of 2000 for various frequency ratios (both integer and non-integer) has been demonstrated. When the frequency ratio is fixed to 2, bifurcation of the jet on a plane is evident. However, for a non-integer frequency ratio, the axisymmetric jet is seen to bloom in all directions.

  20. Capacitance of circular patch resonator

    Energy Technology Data Exchange (ETDEWEB)

    Miano, G.; Verolino, L. [Dip. di Ingegneria Elettrica, Ist. Nazionale di Fisica Nucleare, Naples (Italy); Panariello, G. [Dip. di Ingegneria Elettronica, Naples (Italy); Vaccaro, V.G. [Ist. Nazionale di Fisica Nucleare, Naples (Italy). Dipt. di Scienze Fisiche

    1995-11-01

    In this paper the capacitance of the circular microstrip patch resonator is computed. It is shown that the electrostatic problem can be formulated as a system of dual integral equations, and the most interesting techniques of solutions of these systems are reviewed. Some useful approximated formulas for the capacitance are derived and plots of the capacitance are finally given in a wide range of dielectric constants.

  1. Total positive curvature of circular DNA

    DEFF Research Database (Denmark)

    Bohr, Jakob; Olsen, Kasper Wibeck

    2013-01-01

    micro-DNAs longer than the minimum length must be concave, a result that is consistent with typical atomic force microscopy images of plasmids. Predictions for the total positive curvature of circular micro-DNAs are given as a function of length, and comparisons with circular DNAs from the literature...... molecules, e.g., plasmids, it is shown to have implications for the total positive curvature integral. For small circular micro-DNAs it follows as a consequence of Fenchel's inequality that there must exist a minimum length for the circular plasmids to be double stranded. It also follows that all circular...

  2. Circular Polarization in Pulsar Integrated Profiles: Updates

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    We update the systematic studies of circular polarization in integrated pulse profiles by Han et al. Data of circular polarization profiles are compiled. Sense reversals can occur in core or cone components, or near the intersection between components. The correlation between the sense of circular polarization and the sense of position angle variation for conal-double pulsars is confirmed with a much large database. Circular polarization of some pulsars has clear changes with frequency.Circular polarization of millisecond pulsars is marginally different from that of normal pulsars.

  3. Effect of ethanol-water mixture on the structure and dynamics of lysozyme: A fluorescence correlation spectroscopy study

    Science.gov (United States)

    Chattoraj, Shyamtanu; Mandal, Amit Kumar; Bhattacharyya, Kankan

    2014-03-01

    Effect of ethanol-water mixture on the hydrodynamic radius (rH) and conformational dynamics of lysozyme has been studied by circular dichroism, emission spectra, and fluorescence correlation spectroscopy. For this purpose, the protein lysozyme is covalently labeled near the active site with a fluorescent probe, alexa 488. The ethanol molecules are sequestered near the hydrophobic tryptophan residues as indicated by the blue shift of the emission maximum of tryptophan. It is observed that both size (rH) and time constant of conformational relaxation (τR) of lysozyme oscillate with increase in ethanol concentration. The rH of the protein fluctuates from 19 Å in the native state, to a minimum of 13 Å, and a maximum of 29 Å. It is proposed that the oscillating behavior arises from competition between mutual interaction among protein, ethanol, and water. The fluorescence intensity fluctuates because of quenching of the fluorescence of the probe (alexa) by the free amino group of certain residues (e.g., tryptophan). Rate of inter-conversion (folding dynamics) between the open (fluorescent) and closed (non-fluorescent) form has been determined and is found to exhibit similar oscillation with variation in ethanol content.

  4. Temperature-dependent structural change of D-penicillamine-capped chiral gold nanoparticles investigated by infrared spectroscopy

    Science.gov (United States)

    Ock, Kwang-Su; Dembereldorj, Uuriintuya; Park, Jin; Ganbold, Erdene-Ochir; Kim, Semi; Shin, Hang-Cheol; Joo, Sang-Woo

    2013-02-01

    The structure and stability of D-penicillamine-capped gold nanoparticles (D-Pen Au NPs) were studied using spectroscopic tools. The synthesis of D-Pen Au NPs was examined using high-resolution transmission electron microscopy (HR-TEM), UV-vis absorption spectroscopy, and circular dichroism (CD). Temperature-dependent reversible structural changes of D-Pen Au NPs were observed using infrared spectroscopic tools. The three thiol, carboxyl, and amino binding groups of D-Pen were presumed to interact with Au NP surfaces on the basis of the infrared spectral features. D-Pen appeared to form quite a stable structure and desorb at a high temperature above 453 K on Au NPs. Our deconvolution analysis indicated the νs(COO-) and νas(COO-) carboxylate bands at ˜1392 and ˜1560 cm-1 appeared to be weakened, whereas the amino band at ˜1595 cm-1 remained strong in increasing the temperature from 293 to 373 K. On the other hand, the intensities of the zwitter ionic bands at ˜999, ˜1117, and ˜1631 cm-1 for NH3+ appeared to decrease presumably due to the deprotonation process at 373 K. Our infrared spectroscopic study suggests that the deprotonated amino groups bind stronger, whereas the intra-carboxylate bonds become weaker as the temperature increase. Such structural changes of D-Pen Au NPs appeared to be reversible between 293 and 373 K.

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

    Science.gov (United States)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Mishra, S.; Gammon, W.J.; Pappas, D.P. [Virginia Commonwealth Univ., Richmond, VA (United States)] [and others

    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.

  7. Conformational alterations induced by novel green 16-E2-16 gemini surfactant in xanthine oxidase: Biophysical insights from tensiometry, spectroscopy, microscopy and molecular modeling.

    Science.gov (United States)

    Akram, Mohd; Bhat, Imtiyaz Ahmad; Bhat, Waseem Feeroze; Kabir-ud-Din

    2015-11-01

    Herein we report the interaction of a biodegradable gemini surfactant, ethane-1,2-diyl bis(N,N-dimethyl-N-hexadecylammoniumacetoxy) dichloride (16-E2-16) with bovine milk xanthine oxidase (XO), employing tensiometry, fluorescence spectroscopy, UV spectroscopy, far-UV circular dichroism spectroscopy (CD), Fourier transform infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and computational molecular modeling. Surface tension results depict substantial changes in the micellar as well as interfacial parameters (CMC, ΠCMC, γCMC, Γmax, Amin, ΔGmic° and ΔGads°) of 16-E2-16 gemini surfactant upon XO combination, deciphering the interaction of XO with the gemini surfactant. Fluorescence measurements reveal that 16-E2-16 gemini surfactant causes quenching in the xanthine oxidase (XO) fluorescence spectra via static procedure and the values of various evaluated binding parameters (KSV, Kb, kq, ΔGb° and n) describe that 16-E2-16 effectively binds to XO. Three dimensional fluorescence, 8-anilino-1-naphthalene sulfonic acid (ANS) binding, F1F3 ratio, UV, CD, FTIR, SEM and TEM results delineate changes in the secondary structure of xanthine oxidase. Molecular docking results provide complement to the steady-state fluorescence findings and support the view that quenching occurs due to non-polar environment experienced by aromatic residues of the enzyme. The results of this study can help scientists to tune the conformation of an enzyme (XO) with biocompatible amphiphilic microstructures, which will help to unfold further understanding in the treatment modes of various diseases like gout, hyperuricemia, liver and brain necrosis. PMID:26057098

  8. Degradation of electron-induced dichroism in glassy As2S3-Sb2S3

    Directory of Open Access Journals (Sweden)

    Balitska V. O.

    2000-12-01

    Full Text Available Experimental results on time degradation of electron-induced dichroism in vitreous chalcogenide semiconductors As2S3-Sb2S3 are discussed. The adequate model for the quantitative description of this process can be developed on the basis of monomolecular relaxation function proper to annihilation of dipol-like coordination defects created on the basis of radiation-induced broken covalent chemical bonds

  9. Degradation of electron-induced dichroism in glassy As2S3-Sb2S3

    OpenAIRE

    Balitska V. O.; Shpotyuk O. I.; Vakiv M. M.

    2000-01-01

    Experimental results on time degradation of electron-induced dichroism in vitreous chalcogenide semiconductors As2S3-Sb2S3 are discussed. The adequate model for the quantitative description of this process can be developed on the basis of monomolecular relaxation function proper to annihilation of dipol-like coordination defects created on the basis of radiation-induced broken covalent chemical bonds

  10. Deterministic Circular Self Test Path

    Institute of Scientific and Technical Information of China (English)

    WEN Ke; HU Yu; LI Xiaowei

    2007-01-01

    Circular self test path (CSTP) is an attractive technique for testing digital integrated circuits(IC) in the nanometer era, because it can easily provide at-speed test with small test data volume and short test application time. However, CSTP cannot reliably attain high fault coverage because of difficulty of testing random-pattern-resistant faults. This paper presents a deterministic CSTP (DCSTP) structure that consists of a DCSTP chain and jumping logic, to attain high fault coverage with low area overhead. Experimental results on ISCAS'89 benchmarks show that 100% fault coverage can be obtained with low area overhead and CPU time, especially for large circuits.

  11. Robust, angstrom level circularity profilometry

    Science.gov (United States)

    Glenn, Paul

    1990-01-01

    A noncontacting approach is presented which involves measuring the local circumferential curvature of the test piece by simultaneously measuring its circumferential slope at two slightly displaced locations. A pair of sensing beams is scanned along the circumference, and a profile of curvature is built, from which the circularity profile is deduced. The sensing of curvature makes the approach insensitive to all types of vibration and drift and runout errors in the relative rotation. The special qualities of the approach are summarized which make it well suited to measuring cylindrical optics and enable it to accommodate radii as small as twenty millimeters.

  12. Physics at Future Circular Colliders

    Science.gov (United States)

    Kotwal, Ashutosh

    2016-03-01

    The Large Hadron Collider has been a grand success with the discovery of the Higgs boson, with bright prospects for additional discoveries since the recent increase in collider energy and the anticipated large datasets. Big open questions such as the nature of dark matter, the origin of the matter-antimatter asymmetry in the Universe, and the theoretical puzzle of the finely-tuned parameters in the Higgs sector, demand new physics principles that extend the established Standard Model paradigm. Future circular colliders in a substantially larger tunnel can house both a high luminosity electron-positron collider for precision measurements of Higgs and electroweak parameters, as well as a very high energy proton-proton collider which can directly manifest particles associated with these new physics principles. We discuss the physics goals of these future circular colliders, and the prospects for elucidating fundamental new laws of nature that will significantly extend our understanding of the Universe. Detailed studies of the discovery potential in specific benchmark models will be presented, with implications for detector design.

  13. Theoretical investigation on single-molecule chiroptical spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Wakabayashi, M. [Tokyo Institute of Technology, School and Graduate School of Bioscience and Biotechnology, 4259 Nagatsuta-cho, Midori-ku, Yokohama, Kanagawa (Japan); Yokojima, S. [Tokyo University of Pharmacy and Life Sciences, 1423-1 Horinouchi, Hachiouji-shi, Tokyo (Japan); Fukaminato, T. [Research Institute for Electronic Science, Hokkaido University, N20, W10, Kita-ku, Sapporo 001-0020 (Japan); Ogata, K.; Nakamura, S. [Research Cluster for Innovation, Nakamura Lab, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan)

    2013-12-10

    Some experimental results of chiroptical response of single molecule have already reported. In those experiments, dissymmetry parameter, g was used as an indicator of the relative circular dichroism intensity. The parameter for individual molecules was measured. For the purpose of giving an interpretation or explanation to the experimental result, the dissymmetry parameter is formulated on the basis of Fermi’s golden rule. Subsequently, the value of individual molecules is evaluated as a function of the direction of light propagation to the orientationary fixed molecules. The ground and excited wavefunction of electrons in the molecule and transition moments needed are culculated using the density functional theory.

  14. CIRCULAR ECONOMY IN ROMANIA WITHIN EUROPEAN CONTEXT

    OpenAIRE

    Cornelia Marcela Danu; Valentin Nedeff

    2015-01-01

    In the present paper we have approached some conceptual and coordinated marks of the societal reality connected to the circular economy. Generated by „the limits of certainty” regarding the future of the world business, the operationalization of the circular economy has become a part of the EU strategies and started the various stages of implementation as an active process in all countries. We have highlighted the opportunities and the risks related to the circular economy, the European dimen...

  15. A COMPACT CIRCULARLY POLARIZED SLOTTED MICROSTRIP ANTENNA

    OpenAIRE

    V. Jebaraj; K.R.S. Ravi Kumar; D. Mohanageetha

    2014-01-01

    Slot antennas are often used at UHF and microwave frequencies. In slot antenna for RFID reader applications the frequency ranges from 902-923MHz to achieve circular polarization. The shapes and size of the slot, as well as the driving frequency, determine the radiation distribution pattern. The proposed compact size circularly polarized slotted microstrip antenna are summarized with design rules. The circularly polarized radiation in square patch antenna can be obtained by perturbation techni...

  16. Reconfigurable Monopole Antennas With Circular Polarization

    OpenAIRE

    Panahi, Afshin

    2015-01-01

    This thesis presents research on printed circularly-polarized monopole antennas and their application in reconfigurable monopole antennas. The proposed circularly-polarised monopole antennas benefit from advantages such as small size, low-cost, low-profile and simple designs. The first part of this thesis introduces three printed circularly-polarized monopole antennas for global navigation satellite systems and Wi-Fi applications. The primary focus is on the ground plane which is used as a ra...

  17. Molecular alignment using circularly polarized laser pulses

    CERN Document Server

    Smeenk, C T L

    2013-01-01

    We show that circularly polarized femtosecond laser pulses produce field-free alignment in linear and planar molecules. We study the rotational wavepacket evolution of O$_2$ and benzene created by circularly polarized light. For benzene, we align the molecular plane to the plane of polarization. For O$_2$, we demonstrate that circular polarization yields a net alignment along the laser propagation axis at certain phases of the evolution. Circular polarization gives us the ability to control alignment of linear molecules outside the plane of polarization, providing new capabilities for molecular imaging.

  18. La raó circular

    OpenAIRE

    Pinyol i Bori, Francesc

    2007-01-01

    És un text epistemològic sobre les qüestions cognitives circulars que apareixen: a) Quan el subjecte forma part de l'objecte estudiat; b) En la recerca de les bases del coneixement; c) Al voler justificar la inducció; d) En algunes interpretacions filosòfiques i científiques. S'hi explica l'estat del punt a) el més problemàtic, i s'aclareixen els altres tres punts: els b) i c) pel fet científic que l'evolució cognitiva humana ha anat acoblada a l'evolució biològica, la qual ha generat els a p...

  19. Circular Loudspeaker Array with Controllable Directivity

    DEFF Research Database (Denmark)

    Møller, Martin; Olsen, Martin; Agerkvist, Finn T.;

    2010-01-01

    Specific directivity patterns for circular arrays of loudspeakers can be achieved by utilizing the concept of phase-modes, which expands the directivity pattern into a series of circular harmonics. This paper investigates the applicability of this concept applied on a loudspeaker array on a...

  20. Exon circularization in mammalian nuclear extracts.

    Science.gov (United States)

    Pasman, Z; Been, M D; Garcia-Blanco, M A

    1996-06-01

    Correct ligation of exons in pre-mRNA splicing requires splice site juxtaposition (splice site pairing), usually involving a 5' splice site and a downstream 3' splice site. Splicing of a 5' splice site to an upstream 3' splice site, however, is predicted to result in a circular RNA. This mode of splice site pairing across the axon has been hypothesized to account for rare RNAs containing scrambled exons (Nigro JM et al., 1991, Celt 64:607-613; Cocquerelle C et al., 1992, EMBO J 11:1 095-1098). Additionally, this mode of splice site pairing has been postulated to explain the formation of SRY circular transcripts in mouse testis (Capel B et al., 1993, Celt 73:1019- 1030). Here we show that splice site pairing across the exon can result in exon circularization in vitro. These results indicate that spliceosome-mediated axon circularization indeed can account for the formation of scrambled exons and circular RNAs. Exon circularization efficiency decreased dramatically as the length of the exon was increased from 95 nt to 274 nt. Circularization of this longer exon was restored, however, when intronic complementary sequences were included in the RNA substrate. These complementary sequences could form a stem that served to bring the splice sites into proximity and thereby promote splice site pairing. Therefore, the splicing of this structured RNA recapitulated SRY-like exon circularization in vitro.

  1. Microstrip Antenna Generates Circularly Polarized Beam

    Science.gov (United States)

    Huang, J.

    1986-01-01

    Circular microstrip antenna excited with higher order transverse magnetic (TM) modes generates circularly polarized, conical radiation patterns. Found both theoretically and experimentally that peak direction of radiation pattern is varied within wide angular range by combination of mode selection and loading substrate with materials of different dielectric constants.

  2. EPR and NMR spectroscopies provide input on the coordination of Cu(I) and Ag(I) to a disordered methionine segment.

    Science.gov (United States)

    Shenberger, Yulia; Gottlieb, Hugo E; Ruthstein, Sharon

    2015-06-01

    Methionine motifs are methionine-rich metal-binding segments found in many human, yeast, and bacterial proteins involved in the transportation of copper ion to other cellular pathways, and in protecting copper from oxidation. Methionine motifs are found to bind Ag(I) and Cu(I) ions. Proteins or peptides that can bind different metal ions should have the ability to differentiate between them, to be able to shuttle them to various pathways in the cell. This study utilizes electron paramagnetic resonance spectroscopy together with circular dichroism and nuclear magnetic resonance to probe structural changes in the methionine segment upon coordinating Cu(I) and Ag(I) metal ions. The data collected here indicate that methionine segments experience structural changes while coordinating Cu(I) and Ag(I), however, the differences between the coordination of Cu(I) vs. Ag(I) to the methionine segment are mild. Since Cu(I) and Ag(I) metal ions are pretty similar in their nature and charge, the minor structural changes reported here are significant towards the understanding of the differences in the transport mechanism of these two metal ions in prokaryotic and eukaryotic cells.

  3. Optical spectroscopy of La3Ga5SiO14 disordered crystals doped with Fe3+ ions

    Science.gov (United States)

    Alyabyeva, L.; Burkov, V.; Mill, B.

    2015-05-01

    The circular dichroism, absorption and luminescence spectra of langasite (La3Ga5SiO14) doped with iron ions (Fe) are investigated at temperatures T of 300 and 8 K. Analysis of the data obtained reveals the Fe ions are trivalent. The Fe3+ impurity ions substitute Ga3+ ions and occupy 3f tetrahedral sites. Luminescence from the 4T1 excited state of the dopant was detected at 8 K.

  4. Band structure of Heusler compounds studied by photoemission and tunneling spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Arbelo Jorge, Elena

    2011-07-01

    Heusler compounds are key materials for spintronic applications. They have attracted a lot of interest due to their half-metallic properties predicted by band structure calculations. The aim of this work is to evaluate experimentally the validity of the predictions of half metallicity by band structure calculations for two specific Heusler compounds, Co{sub 2}FeAl{sub 0.3}Si{sub 0.7} and Co{sub 2}MnGa. Two different spectroscopy methods for the analysis of the electronic properties were used: Angular Resolved Ultraviolet Photoemission Spectroscopy (ARUPS) and Tunneling Spectroscopy. Heusler compounds are prepared as thin films by RF-sputtering in an ultra high vacuum system. For the characterization of the samples, bulk and surface crystallographic and magnetic properties of Co{sub 2}FeAl{sub 0.3}Si{sub 0.7} and Co{sub 2}MnGa are studied. X-ray and electron diffraction reveal a bulk and surface crossover between two different types of sublattice order (from B2 to L2{sub 1}) with increasing annealing temperature. X-ray magnetic circular dichroism results show that the magnetic properties in the surface and bulk are identical, although the magnetic moments obtained are 5 % below from the theoretically predicted. By ARUPS evidence for the validity of the predicted total bulk density of states (DOS) was demonstrated for both Heusler compounds. Additional ARUPS intensity contributions close to the Fermi energy indicates the presence of a specific surface DOS. Moreover, it is demonstrated that the crystallographic order, controlled by annealing, plays an important role on broadening effects of DOS features. Improving order resulted in better defined ARUPS features. Tunneling magnetoresistance measurements of Co{sub 2}FeAl{sub 0.3}Si{sub 0.7} and Co{sub 2}MnGa based MTJ's result in a Co{sub 2}FeAl{sub 0.3}Si{sub 0.7} spin polarization of 44 %, which is the highest experimentally obtained value for this compound, although it is lower than the 100 % predicted. For Co

  5. CIRCULAR ECONOMY IN ROMANIA WITHIN EUROPEAN CONTEXT

    Directory of Open Access Journals (Sweden)

    Cornelia Marcela Danu

    2015-07-01

    Full Text Available In the present paper we have approached some conceptual and coordinated marks of the societal reality connected to the circular economy. Generated by „the limits of certainty” regarding the future of the world business, the operationalization of the circular economy has become a part of the EU strategies and started the various stages of implementation as an active process in all countries. We have highlighted the opportunities and the risks related to the circular economy, the European dimension and, in particular, the Romanian one of this process, the role of the triad: consumer-company-natural environment, while implementing the circular economy. Circular economy is both a new approach of the societal life, based on changing the mentalities of the individuals having the role of decision makers at the company level and public administration and the decision makers – consumers, as well as a policy meant to be made operational across all entities: governmental, entrepreneurial, individually – human.

  6. Nanofocusing in circular sector-like nanoantennas

    DEFF Research Database (Denmark)

    Zenin, Volodymyr; Pors, Anders Lambertus; Han, Zhanghua;

    2014-01-01

    Gold circular sector-like nanoantennas (with a radius of 500 nm and a taper angle of 60°, 90°, and 120°) on glass are investigated in a near-infrared wavelength range (900 - 2100 nm). Amplitude- and phase-resolved near-field images of circular sector-like antenna modes at telecom wavelength feature...... a concentric circular line of phase contrast, demonstrating resonant excitation of a standing wave of counter-propagating surface plasmons, travelling between a tip and opposite circular edge of the antenna. Transmission spectra obtained in the range 900 - 2100 nm are in good agreement with numerical...... circular sector-like nanoantennas very promising for implementing bowtie antennas and attractive for many applications....

  7. Circular motion in NUT space-time

    CERN Document Server

    Jefremov, Paul

    2016-01-01

    We consider circular motion in the NUT (Newman-Unti-Tamburino) space-time. Among other things, we determine the location of circular time-like geodesic orbits, in particular of the innermost stable circular orbit (ISCO) and of the marginally bound circular orbit. Moreover, we discuss the von Zeipel cylinders with respect to the stationary observers and with respect to the Zero Angular Momentum Observers (ZAMOs). We also investigate the relation of von Zeipel cylinders to inertial forces, in particular in the ultra-relativistic limit. Finally, we generalise the construction of thick accretion tori ("Polish doughnuts") which are well known on the Schwarzschild or Kerr background to the case of the NUT metric. We argue that, in principle, a NUT source could be distinguished from a Schwarzschild or Kerr source by observing the features of circular matter flows in its neighbourhood.

  8. Elliptical dichroism as an optical mechanism of planar chirality in 2D metamaterials

    CERN Document Server

    Zhukovsky, S V; Galynsky, V M

    2009-01-01

    We employ a homogenization technique based on the Lorentz electronic theory to show that planar chiral structures (PCSs) can be described by an effective dielectric tensor similar to that of biaxial elliptically dichroic crystals. Such a crystal is shown to behave like a PCS insofar as it exhibits its characteristic optical properties (co-rotating elliptical polarization eigenstates and asymmetric transmission for left/right-handed incident wave polarization). Elliptical dichroism is thus proposed as a general optical mechanism behind planar chirality in a PCS of any geometry.

  9. Inversed linear dichroism in F K-edge NEXAFS spectra of fluorinated planar aromatic molecules

    DEFF Research Database (Denmark)

    de Oteyza, D. G.; Sakko, A.; El-Sayed, A.;

    2012-01-01

    orbitals with significant density of states on the fluorine atoms show different symmetry from those mainly located on C and N atoms. As a result, the angle-dependent linear dichroism in NEXAFS F K-edge spectra is inversed with respect to that in the C and N K-edges. In addition, the significant overlap...... in energy of π* and σ* orbitals throughout the F K-edge spectrum hampers its use for analysis of molecular orientations from angle-dependent NEXAFS measurements....

  10. Preparation of circular Rydberg states in helium using the crossed-fields method

    Science.gov (United States)

    Zhelyazkova, V.; Hogan, S. D.

    2016-08-01

    Helium atoms have been prepared in the circular |n =55 ,ℓ =54 , mℓ=+54 > Rydberg state using the crossed electric and magnetic fields method. The atoms, initially traveling in pulsed supersonic beams, were photoexcited from the metastable 1 s 2 s S31 level to the outermost, mℓ=0 Rydberg-Stark state with n =55 in the presence of a strong electric field and weak perpendicular magnetic field. Following excitation, the electric field was adiabatically switched off causing the atoms to evolve into the circular state with mℓ=+54 defined with respect to the magnetic-field quantization axis. The circular states were detected by ramped electric-field ionization along the magnetic-field axis. The dependence of the circular state production efficiency on the strength of the excitation electric field, and the electric-field switch-off time was studied, and microwave spectroscopy of the circular-to-circular |55 ,54 ,+54 >→|56 ,55 ,+55 > transition at ˜38.5 GHz was performed.

  11. Preparation of circular Rydberg states in helium using the crossed fields method

    CERN Document Server

    Zhelyazkova, V

    2016-01-01

    Helium atoms have been prepared in the circular $|n=55,\\ell=54,m_{\\ell}=+54\\rangle$ Rydberg state using the crossed electric and magnetic fields method. The atoms, initially travelling in pulsed supersonic beams, were photoexcited from the metastable $1s2s\\,^3S_1$ level to the outermost, $m_{\\ell}=0$ Rydberg-Stark state with $n=55$ in the presence of a strong electric field and weak perpendicular magnetic field. Following excitation, the electric field was adiabatically switched off causing the atoms to evolve into the circular state with $m_{\\ell}=+54$ defined with respect to the magnetic field quantization axis. The circular states were detected by ramped electric field ionization along the magnetic field axis. The dependence of the circular state production efficiency on the strength of the excitation electric field, and the electric-field switch-off time was studied, and microwave spectroscopy of the circular-to-circular $|55,54,+54\\rangle\\rightarrow|56,55,+55\\rangle$ transition at $\\sim38.5$~GHz was perf...

  12. Vitrified chiral-nematic liquid crystalline films for selective reflection and circular polarization

    Energy Technology Data Exchange (ETDEWEB)

    Katsis, D.; Chen, P.H.M.; Mastrangelo, J.C.; Chen, S.H. [Univ. of Rochester, NY (United States); Blanton, T.N. [Eastman Kodak Co., Rochester, NY (United States)

    1999-06-01

    Nematic and left-handed chiral-nematic liquid crystals comprising methoxybiphenylbenzoate and (S)-(-)-1-phenylethylamine pendants to a cyclohexane core were synthesized and characterized. Although pristine samples were found to be polycrystalline, thermal quenching following heating to and annealing at elevated temperatures permitted the molecular orders characteristic of liquid crystalline mesomorphism to be frozen in the glassy state. Left at room temperature for 6 months, the vitrified liquid crystalline films showed no evidence of recrystallization. An orientational order parameter of 0.65 was determined with linear dichroism of a vitrified nematic film doped with Exalite 428 at a mole fraction of 0.0025. Birefringence dispersion of a blank vitrified nematic film was determined using a phase-difference method complemented by Abbe refractometry. A series of vitrified chiral-nematic films were prepared to demonstrate selective reflection and circular polarization with a spectral region tunable from blue to the infrared region by varying the chemical composition. The experimentally measured circular polarization spectra were found to agree with the Good-Karali theory in which all four system parameters were determined a priori: optical birefringence, average refractive index, selective reflection wavelength, and film thickness.

  13. Towards circularly polarized (sub-) femtosecond XUV pulses for ultrafast pump-probe experiments

    Energy Technology Data Exchange (ETDEWEB)

    Schmidt, Juergen; Chew, Soo Hoon; Kranjec, Mihael; Kleineberg, Ulf [LMU Muenchen, Physik-Department, Garching (Germany); Guggenmos, Alexander; Hofstetter, Michael [MPQ fuer Quantenoptik, Garching (Germany)

    2012-07-01

    Circularly polarized (CP) XUV radiation has been demonstrated to be a useful probe for the experimental investigation of electronic effects in magnetic materials such as magnetic circular dichroism, spin-polarized photoemission, magneto-optical Kerr-effect and others. On the laboratory scale, High Harmonic (HH) gas jet sources which inherently provide coherent and ultrashort linearly polarized XUV pulses in the sub-fs domain, suitable to study ultrafast dynamics, have emerged. In our setup we aim at incorporating in-house fabricated broadband transmission multilayer phase shifters into a laser driven 10kHz repetition rate HH Source in the 50-70eV photon energy range. To our knowledge only little investigation on such polarizers intended for use in HH radiation has been made so far. We examine our phase shifters regarding tunability of energy range, phase retardation, transmission efficiency and spectral bandwidth. For this purpose we use a home-made XUV flat-field spectrometer and a multilayer mirror based polarization analyzer. Combining the expected CP pulses with our TOF-PEEM and ARPES spectrometer will pave the way towards time resolved measurements of exchange-coupled electron dynamics.

  14. A solid-state dedicated circularly polarized luminescence spectrophotometer: Development and application

    Science.gov (United States)

    Harada, Takunori; Hayakawa, Hiroshi; Watanabe, Masayuki; Takamoto, Makoto

    2016-07-01

    A new solid-state dedicated circularly polarized luminescence (CPL) instrument (CPL-200CD) was successfully developed for measuring true CPL spectra for optically anisotropic samples on the basis of the Stokes-Mueller matrix approach. Electric components newly installed in the CPL-200CD include a pulse motor-driven sample rotation holder and a 100 kHz lock-in amplifier to achieve the linearly polarized luminescence measurement, which is essential for obtaining the true CPL signal for optically anisotropic samples. An acquisition approach devised for solid-state CPL analysis reduces the measurement times for a data set by ca. 98% compared with the time required in our previous method. As a result, the developed approach is very effective for samples susceptible to light-induced degradation. The theory and implementation of the method are described, and examples of its application to a CPL sample with macroscopic anisotropies are provided. An important advantage of the developed instrument is its ability to obtain molecular information for both excited and ground states because circular dichroism measurements can be performed by switching the monochromatic light to white light without rearrangement of the sample.

  15. A study of magnetic properties of hard and soft magnetic materials by Lorentz transmission electron microscopy and magnetic x-ray circular dichroism

    CERN Document Server

    Pickford, R A

    2001-01-01

    iron spin and orbital magnetic moments were found to decrease with increasing iron content. In collaboration with CEA Saclay, Paris, a set of cobalt elements were patterned by electron beam lithography. The elements were designed to isolate domain walls and to monitor their movement in an applied field. The shape anisotropy of the element was found to be too large for the insitu magnetic field to flip the magnetisation. The domain walls found in the as received magnetic state were associated with defects in the structure of the element. The magnetisation process was compared to micromagnetic simulations, A further study of magnetic elements was made to study the competition of anisotropy in patterned cobalt dots. The shape anisotropy was calculated and the crystalline anisotropy of the cobalt film was measured. The dots (rectangles) were patterned so that the shape anisotropy was comparable to the crystalline anisotropy of the cobalt. The dots were patterned at 45 degrees to the crystalline anisotropy. This t...

  16. Formation of local native-like tertiary structures in the slow refolding reaction of human carbonic anhydrase II as monitored by circular dichroism on tryptophan mutants.

    Science.gov (United States)

    Andersson, D; Freskgård, P O; Jonsson, B H; Carlsson, U

    1997-04-15

    In the present study, near-UV CD kinetic measurements on mutants, in which one Trp residue had been replaced, were performed to probe the development of asymmetric environments around specific Trp residues during the refolding of human carbonic anhydrase II (HCAII). In addition, the formation of the active site was probed by the binding of a fluorescent sulfonamide inhibitor. The development of the individual Trp CD spectra during refolding was obtained by subtracting the CD spectrum of the mutant lacking one Trp from that of HCAII at different time points. The same method was used for the particular Trp residues to obtain the kinetic CD traces monitored at a specific wavelength (270 nm). Trp residues 16, 97, and 245 were analyzed. Trp16 probes the N-terminal domain (amino acid residues 1-25), and this part is forming its tertiary structure slower than the major domain (amino acid residues 26-260) of the protein molecule, which contains the active site and a dominating beta-sheet. An essentially native structure of the major domain seems to act as a template for the correct folding of the N terminus. Trp97 is located in a hydrophobic cluster comprising beta-strands 3-5 in the protein core. Previously, we have shown that this region is remarkably stable and compact, and stopped-flow fluorescence data indicate that Trp97 is buried in an apolar compact cluster within a few milliseconds [Svensson, M., Jonasson, P., Freskgård, P.-O., Jonsson, B.-H., Lindgren, M., Martensson, L.-G., Gentile, M., Bóren, K., & Carlsson, U. (1995) Biochemistry 34, 8606-8620; Jonasson, P., Aronsson, G., Carlsson, U., & Jonsson, B.-H. (1997) Biochemistry 36 (in press)]. Here it is shown that the development of the native tertiary structure at Trp97 occurs in the minute time domain. Trp245 is located in a long loop between the N-terminal domain and the core structure. Although this Trp has attained native-like fluorescence properties within the dead time of the CD experiment, it assumes a native-like asymmetric environment even slower than Trp97. Thus, the investigated Trp residues develop their native CD bands at different rates, showing that formation of native-like tertiary structure is occurring with varying rates in different regions of the protein. PMID:9109672

  17. Characterization of the 1st and 2nd EF-hands of NADPH oxidase 5 by fluorescence, isothermal titration calorimetry, and circular dichroism

    Directory of Open Access Journals (Sweden)

    Wei Chin-Chuan

    2012-04-01

    Full Text Available Abstract Background Superoxide generated by non-phagocytic NADPH oxidases (NOXs is of growing importance for physiology and pathobiology. The calcium binding domain (CaBD of NOX5 contains four EF-hands, each binding one calcium ion. To better understand the metal binding properties of the 1st and 2nd EF-hands, we characterized the N-terminal half of CaBD (NCaBD and its calcium-binding knockout mutants. Results The isothermal titration calorimetry measurement for NCaBD reveals that the calcium binding of two EF-hands are loosely associated with each other and can be treated as independent binding events. However, the Ca2+ binding studies on NCaBD(E31Q and NCaBD(E63Q showed their binding constants to be 6.5 × 105 and 5.0 × 102 M-1 with ΔHs of -14 and -4 kJ/mol, respectively, suggesting that intrinsic calcium binding for the 1st non-canonical EF-hand is largely enhanced by the binding of Ca2+ to the 2nd canonical EF-hand. The fluorescence quenching and CD spectra support a conformational change upon Ca2+ binding, which changes Trp residues toward a more non-polar and exposed environment and also increases its α-helix secondary structure content. All measurements exclude Mg2+-binding in NCaBD. Conclusions We demonstrated that the 1st non-canonical EF-hand of NOX5 has very weak Ca2+ binding affinity compared with the 2nd canonical EF-hand. Both EF-hands interact with each other in a cooperative manner to enhance their Ca2+ binding affinity. Our characterization reveals that the two EF-hands in the N-terminal NOX5 are Ca2+ specific. Graphical abstract

  18. Contribution to the study of TRH (thyrotropin-releasing hormone) conformation using circular dichroism. Physico-chemical studies, radioactive labelling and biological applications

    International Nuclear Information System (INIS)

    In an attempt to reach a better understanding at the molecular level of phenomena connected with the action of TRF the conformation and radioactive labelling of this hormone were investigated. The specific detection of a hormone at its action site is only possible if labelled substances of very high specific activity are used. TRF was tritium labelled by three methods: direct catalytic exchange; catalytic dehalogenation of mono- and di-iodo TRF; catalytic denitrogenation of mono-azo-TRF. Whatever the method used the tritiated TRF has a very high specific activity and keeps all its biological properties. Biological activity measurements carried out on labelled TRF, in vivo in rats and in vitro on a TRF-sensitive prolactine cell clone, are described. TRF tritiated by the above methods is shown to have the same biological activity as standard TRF. Some results are given concerning the application of labelled TRF to research on the hormone action mechanism. The tritiated TRF distribution kinetics were examined in vivo and in vitro. The kinetics of hormone fixation on the antehypophysary tissue match those of in vivo release of the plasma thyreotropic hormone, confirming the relationships between the hormone fixation on its target tissue and its biological effect. Finally an outline is given of work on the interaction of tritiated TRF with prolactine cell receptors and on the penetration of intact tritiated TRF into these cells. In addition the radioimmunological analysis of TRF was developed by the use of 125I-mono-iodo-TRF at high specific activity (above 2000 Ci/mmole)

  19. Circular Dichroism and Fluorescence Spectroscopic Study of RNA-protein Folding Patterns in Human hnRNP A3 and Their Implications in Human Autoimmune Diseases

    Institute of Scientific and Technical Information of China (English)

    E.SüLEYMANO(G)LU

    2004-01-01

    In human cells, the heterogeneous nuclear ribonucleoproteins (hnRNP) are represented by a group of polypeptides, with various molecular properties, comprizing the most abundant constituents of the cell nucleus. Autoantibodies to hnRNPs have been reported in patients suffering from different rheumatic dieseases since 1980s. Experimental evidence indicates that hnRNP complexes undergo substantial structural changes during mRNA formation and export. However, how this contributes to disease development still has to be elucidated. Here some preliminary physicochemical features of RNA-protein folding and stability patterns of newly characterized hnRNP A3 with further functional implications in development of systemic human autoimmune states are reported.

  20. LDA+DMFT calculations of X-ray absorption and x-ray circular dichroism spectra: Role of valence-band correlations

    Energy Technology Data Exchange (ETDEWEB)

    Sipr, Ondrej; Simunek, Antonin [Institute of Physics AS CR, Cukrovarnicka 10, Prague (Czech Republic); Minar, Jan; Ebert, Hubert [Universitaet Muenchen (Germany)

    2010-07-01

    L{sub 2,3}-edge XAS and XMCD spectra of 3d elements are calculated via a self-consistent LDA+DMFT method (including thus valence-band correlations). It is found that the asymmetry of the calculated XAS white lines increases upon inclusion of the correlations for Fe and Co but not for Ni. The change in the height of the L{sub 3} and L{sub 2} peaks in the XMCD spectra is in a good agreement with the change of the orbital magnetic moment caused by adding the valence-band correlations. As a whole, adding valence-band correlations improves the agreement between the theory and experiment but visible differences still remain. Therefore, a core hole is additionally accounted for via the final state approximation and the impact of such a procedure is assessed.

  1. A new approach to determine the stereospecificity in lipase catalysed hydrolysis using circular dichroism (CD): lipases produce optically active diglycerides from achiral triglycerides.

    Science.gov (United States)

    Uzawa, H; Nishida, Y; Ohrui, H; Meguro, H

    1990-04-30

    We describe a sensitive CD method for determining the stereospecificity in lipase (E.C.3.1.1.3) catalysed hydrolysis of triacyl glycerols into diacyl glycerols. The diglycerols were converted to chiral tert-butyldimethylsilylated 1,2- or 2,3-di-O-benzoyl-sn-glycerol (5 or 5'), and their CD was measured. This approach showed for the first time that lipases produce optically active diacyl glycerides from achiral tripalmitin and tribenzoyl glyceride with a variable extent of enantioselectivity depending on the acyl groups and the enzymes.

  2. Numerical determination of non-Langmuirian adsorption isotherms of ibuprofen enantiomers on Chiralcel OD column using ultraviolet-circular dichroism dual detector.

    Science.gov (United States)

    Li, Hui; Jiang, Xiaoxiao; Xu, Wei; Chen, Yongtao; Yu, Weifang; Xu, Jin

    2016-02-26

    Competitive adsorption isotherm of ibuprofen enantiomers on Chiralcel OD stationary phase at 298K was determined by the application of inverse method. Transport dispersive (TD) chromatography model was used to describe mass balances of the enatiomers. Axial dispersion and mass transfer coefficients were estimated from a series of linear pulse experiments. It was found that the overloaded elution profile of total concentration of racemic ibuprofen cannot be satisfactorily fitted by substituting bi-Langmuir model, the most widely used isotherm model for enantiomers, into TD model and tuning the isotherm parameters. UV-CD dual detector setup was then applied to obtain the individual overloaded elution profiles of both enantiomers. The more informative experimental data revealed non-Langmuirian adsorption behavior of ibuprofen enantiomers on chiralcel OD stationary phase. Two analytical binary isotherm models, both accounting for adsorbate-adsorbate interactions and having the feature of inflection points, were then evaluated. A comparison between quadratic model and Moreau model showed that the former gives better fitting results. The six parameters involved in quadratic model were determined stepwisely. Three of them were first obtained by fitting overloaded elution profiles of S-ibuprofen. The other three were then acquired by fitting overloaded elution profiles of both enantiomers recorded by UV-CD dual detector for racemic ibuprofen. A further attempt was also made at reducing the number of quadratic model parameters.

  3. Modelling the circular polarisation of Earth-like exoplanets: constraints on detecting homochirality

    Science.gov (United States)

    Hogenboom, Michael; Stam, Daphne; Rossi, Loic; Snik, Frans

    2016-04-01

    polarisation signals for both spatially resolved and spatially unresolved planets, using various atmospheric and surface properties and across a range of phase angles. As a test, the calculated degree of circular polarisation resulting from the multiple scattering of light in an atmosphere with varying properties was compared with results presented by Kawata te{circatmos} and was found to be in agreement. Initial modelling of the atmospheric scattering of light by a planetary disk has shown a presence of degree of circular polarisation in the order of 10-4. This represents a static case with one cloudy hemisphere, one cloudless hemisphere and a Lambertian surface. Results containing varied patchy cloud patterns shall also be presented in a bid to reflect the random nature of planetary cloud cover. We will also present the calculated degree of circular polarisation of planets with various cloud coverage and a circularly polarising surface in order to discover the influence of organisms on the numerical results. {1} {hansen} J. E. {Hansen} and L. D. {Travis}. {Light scattering in planetary atmospheres}. {Space Science Reviews}, 16:527-610, October 1974. {circplanets} J. C. {Kemp} and R. D. {Wolstencroft}. {Circular Polarization: Jupiter and Other Planets}. {Nature}, 232:165-168, July 1971. {chiralbailey} J. {Bailey}. {Circular Polarization and the Origin of Biomolecular Homochirality}. In G. {Lemarchand} and K. {Meech}, editors, {Bioastronomy 99}, volume 213 of {Astronomical Society of the Pacific Conference Series}, 2000. {circpolchar} L. {Nagdimunov}, L. {Kolokolova}, and D. {Mackowski}. {Characterization and remote sensing of biological particles using circular polarization}. {Journal of Quantitative Spectroscopy and Radiative Transfer}, 131:59-65, December 2013. dehaan} J. F. {de Haan}, P. B. {Bosma}, and J. W. {Hovenier}. {The adding method for multiple scattering calculations of polarized light}. {Astronomy and Astrophysics}, 183:371-391, September 1987. {circatmos} Y

  4. Process engineering in circular economy

    Institute of Scientific and Technical Information of China (English)

    Lothar Reh

    2013-01-01

    Driven by increasing global population and by growing demand for individual wealth,the consumption of energy and raw materials as well as the steadily growing CO2 concentration in atmosphere pose great challenges to process engineering.This complex multi-scale discipline deals with the transformation of mass by energy to manifold products in different industrial fields under economical and ecological sustainable conditions.In growing circular economy,process engineering increasingly plays an important role in recovering valuable components from very diffuse material flows leaving the user stocks following widely variable time periods of use.As well it is engaged in thermal recovery of energy therefrom and in environmentally safe disposal of residual solid wastes whose recovery economically is not feasible.An efficient recovery of materials and energy following the laws of entropy is a must.A complex network of mass,energy,transportation and information flows has to be regarded with growing traded quantities of used goods even on global level.Important constraints in time,however,exist for a necessary realization of innovative new processes and communal mobility and industrial infrastructure on medium and large scale.Based on reasonable long term and highly reliable statistics from industrial organizations representing steel and paper industry,some limits and trends of possible developments in processing of those industries with long recycling experience will be discussed.

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

    CERN Document Server

    Chen, S J; Ni, W T; Chen, Sheng-Jui; Mei, Hsien-Hao; Ni, Wei-Tou

    2006-01-01

    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. A 3.5-m high-finesse (around 30,000) Fabry-Perot prototype detector extendable to 7-m has been built and tested. We use X-pendulums and automatic control schemes developed by the gravitational-wave detection community for mirror suspension and cavity control. To polarize the vacuum, we use a 2.3-T dipole permanent magnet, with 27-mm-diameter clear borehole and 0.6-m field length,. In the experiment, the magnet is rotated at 5-10 rev/s to generate time-dependent polarization signal with twice the rotation frequency. Our...

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

    Science.gov (United States)

    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.

  7. Uniformity Tests in Circular Data: Review

    Directory of Open Access Journals (Sweden)

    Ismet DOGAN

    2015-10-01

    Full Text Available Circular data are a large class of directional data, which are interest in many fields. Examples include phenomena that are periodic in time, including those dependent on hours of the day (hospital visits, times of birth, etc. or days of the year (unemployment or sales variations. The elementary but also fundamental property of circular data is that the beginning and end of the scale coincide: for example, 0° = 360°. An immediate implication is that the arithmetic mean is likely to be a poor summary: the mean of 1° and 359° cannot sensibly be 180°. The solution is use the vector mean direction as circular mean. The statistical analysis of angular or circular data differs from the analysis of linear data. Unlike linear distributions, which are often two-tailed and infinite, circular distributions exhibit finite closure because a circular data set comes back on itself, and therefore, 0° and 360° are actually the same point on a circle. Circular statistics is concerned mainly with observations which are unit vectors in the plane. Thus the sample space is typically a circle or a sphere, so that standart methods for analysing univariate or multivariate measurement data can?t be used. Special circular methods are required take into account the structure of these sample spaces. In most circular statistical analyses, the null hypothesis is a uniform distribution in which all directions occur with equal probability. In this study, eight different testing methods improved for uniformity in angular data have been introduced and these methods were compared with each other by using the information obtained from the literature.

  8. Entanglement of quantum circular states of light

    Science.gov (United States)

    Horoshko, D. B.; De Bièvre, S.; Kolobov, M. I.; Patera, G.

    2016-06-01

    We present a general approach to calculating the entanglement of formation for superpositions of two-mode coherent states, placed equidistantly on a circle in phase space. We show that in the particular case of rotationally invariant circular states the Schmidt decomposition of two modes, and therefore the value of their entanglement, are given by analytical expressions. We analyze the dependence of the entanglement on the radius of the circle and number of components in the superposition. We also show that the set of rotationally invariant circular states creates an orthonormal basis in the state space of the harmonic oscillator, and this basis is advantageous for representation of other circular states of light.

  9. Circular polarization memory in polydisperse scattering media

    CERN Document Server

    Macdonald, Callum M; Meglinski, Igor

    2015-01-01

    We investigate the survival of circularly polarized light in random scattering media. The surprising persistence of this form of polarization has a known dependence on the size and refractive index of scattering particles, however a general description regarding polydisperse media is lacking. Through analysis of Mie theory, we present a means of calculating the magnitude of circular polarization memory in complex media, with total generality in the distribution of particle sizes and refractive indices. Quantification of this memory effect enables an alternate pathway towards recovering particle size distribution, based on measurements of diffusing circularly polarized light.

  10. Induction of molecular chirality by circularly polarized light in cyclic azobenzene with a photoswitchable benzene rotor.

    Science.gov (United States)

    Hashim, P K; Thomas, Reji; Tamaoki, Nobuyuki

    2011-06-20

    New phototriggered molecular machines based on cyclic azobenzene were synthesized in which a 2,5-dimethoxy, 2,5-dimethyl, 2,5-difluorine or unsubstituted-1,4-dioxybenzene rotating unit and a photoisomerizable 3,3'-dioxyazobenzene moiety are bridged together by fixed bismethylene spacers. Depending upon substitution on the benzene moiety and on the E/Z conformation of the azobenzene unit, these molecules suffer various degrees of restriction on the free rotation of the benzene rotor. The rotation of the substituted benzene rotor within the cyclic azobenzene cavity imparts planar chirality to the molecules. Cyclic azobenzene 1, with methoxy groups at both the 2- and 5-positions of the benzene rotor, was so conformationally restricted that free rotation of the rotor was prevented in both the E and Z isomers and the respective planar chiral enantiomers were resolved. In contrast, compound 2, with 2,5-dimethylbenzene as the rotor, demonstrated the property of a light-controlled molecular brake, whereby rotation of the 2,5-dimethylbenzene moiety is completely stopped in the E isomer (brake ON, rotation OFF), while the rotation is allowed in the Z isomer (brake OFF, rotation ON). The cyclic azobenzene 3, with fluorine substitution on the benzene rotor, was in the brake OFF state regardless of E/Z photoisomerization of the azobenzene moiety. More interestingly, for the first time, we demonstrated the induction of molecular chirality in a simple monocyclic azobenzene by circular-polarized light. The key characteristics of cyclic azobenzene 2, that is, stability of the chiral structure in the E isomer, fast racemization in the Z isomer, and the circular dichroism of enantiomers of both E and Z isomers, resulted in a simple reversible enantio-differentiating photoisomerization directly between the E enantiomers. Upon exposure to r- or l-circularly polarized light at 488 nm, partial enrichment of the (S)- or (R)-enantiomers of 2 was observed. PMID:21567494

  11. Dual frequency launcher for circularly polarized antenna

    Science.gov (United States)

    Chen, Ming H.

    1989-10-01

    A dual frequency antenna feed is formed from a central, circular waveguide connected to the flat boundry of circular, disk-shaped resonant cavity. A second circular waveguide is connected one end of a disk-shaped resonant cavity. Energy of one frequency enters and exits the cavity along the common axis of the waveguides. Energy of the second frequency is introduced to the same resonant cavity by way of a plurality of bandpass filters, also connected to the cavity. This energy enters by way of slots in the cylindrical walls of the cavity. The central circular waveguide is propagating at one frequency but cut off at the second frequency. These bandpass filters are at this pass band for the second frequency, but at the rejection band for the first frequency. Therefore, the isolation between these two input ports are obtained.

  12. A Conceptual Framework for Circular Design

    Directory of Open Access Journals (Sweden)

    Mariale Moreno

    2016-09-01

    Full Text Available Design has been recognised in the literature as a catalyst to move away from the traditional model of take-make-dispose to achieve a more restorative, regenerative and circular economy. As such, for a circular economy to thrive, products need to be designed for closed loops, as well as be adapted to generate revenues. This should not only be at the point of purchase, but also during use, and be supported by low-cost return chains and reprocessing structures, as well as effective policy and regulation. To date, most academic and grey literature on the circular economy has focused primarily on the development of new business models, with some of the latter studies addressing design strategies for a circular economy, specifically in the area of resource cycles and design for product life extension. However, these studies primarily consider a limited spectrum of the technical and biological cycles where materials are recovered and restored and nutrients (e.g., materials, energy, water are regenerated. This provides little guidance or clarity for designers wishing to design for new circular business models in practice. As such, this paper aims to address this gap by systematically analysing previous literature on Design for Sustainability (DfX (e.g., design for resource conservation, design for slowing resource loops and whole systems design and links these approaches to the current literature on circular business models. A conceptual framework is developed for circular economy design strategies. From this conceptual framework, recommendations are made to enable designers to fully consider the holistic implications for design within a circular economy.

  13. Dual-band Omnidirectional Circularly Polarized Antenna

    OpenAIRE

    Narbudowicz, Adam; Bao, Xiulong; Ammann, Max

    2013-01-01

    A dual-band omnidirectional circularly polarized antenna is proposed. The antenna comprises back-to-back microstrip patches fed by a coplanar waveguide. A very low frequency ratio of 1.182 has been achieved, which can be easily tuned by adjusting four lumped capacitors incorporated into the antenna. An analysis of the omnidirectional circular polarization mechanism as well the dual band operation is provided and confirmed by numerical and experimental data. Key parameters to tune the resonant...

  14. On the circular polarization of pulsar radiation

    OpenAIRE

    Lyubarskii, Y. E.; Petrova, S. A.

    1999-01-01

    We consider the polarization behaviour of radio waves propagating through an ultrarelativistic highly magnetized electron-positron plasma in a pulsar magnetosphere. The rotation of magnetosphere gives rise to the wave mode coupling in the polarization-limiting region. The process is shown to cause considerable circular polarization in the linearly polarized normal waves. Thus, the circular polarization observed for a number of pulsars, despite the linear polarization of the emitted normal wav...

  15. Unleashing the Power of the Circular Economy

    Energy Technology Data Exchange (ETDEWEB)

    Kok, L.; Wurpel, G.; Ten Wolde, A. [IMSA Amsterdam, Amsterdam (Netherlands)

    2013-04-15

    The concept of circular economy is an economic and industrial system that focuses on the reusability of products and raw materials, reduces value destruction in the overall system and aims at value creation within each tier of the system. This report for Circle Economy (CE) outlines the general direction and concrete steps that must be taken to accomplish a breakthrough to a circular economy. It also provides a knowledge base behind the concept, connecting it to sustainability.

  16. Construction of Circular Economy Industrial System

    Institute of Scientific and Technical Information of China (English)

    Cao Man; Ye Wenhu

    2007-01-01

    It is difficult to realize the transformation from traditional economy industrial system to circular economy industrial system.Regarding primary raw materials as the indicators,the industrial system has been specified according to the divergence among the indicators and the circular utilization modes.In comparison with the association among industrial systems,the relationship among industrial sub-systems is named as industrial cross-linking in this paper.The industrial system which could completely utilize and recycle the indicators should be increased and strengthened,and the circular economy industrial system with complete industrial association and industrial cross-linking should also be constructed.Taking the development of circular agricultural system basing on the traditional agricultural system as an example,the traditional agricultural products are regarded as the indicators which have been divided into foodstuff and crop straws which are used to produce food and articlesfor use,like fertilizer,energy and papers etc.The way to construct the circular agricultural industrial system is to increase the industrial systems that could utilize the products generated from crop straws,feces and other castoffs and transform the wastewater and other trucks into environmental friendly products.It has also been pointed out that the construction of circular economy industrial system is conducive to the foundation of circular industrial economics and the establishment of the construction layout of circular economy and the application schemes.Suggestions to the theoretical and practical work of the next step have also been brought forward in this paper.

  17. Broadband circularly polarized planar antenna using partially covered circular wide-slot and L-probe

    OpenAIRE

    Fukusako, Takeshi; Sakami, Ryo; Iwata, Kazuki; フクサコ, タケシ; サカミ, リョウ; イワタ, カズキ; 福迫, 武; 酒見, 遼; 岩田, 一樹

    2008-01-01

    The novel structure of a unique circularly polarized broadband antenna that combines an L-shaped probe with a partially covered circular slot has been presented. A principle that can be used to generate CP using the proposed structure has been presented using an L-shaped probe and a modified circular wide slot. Using the above, a 3 -dB AR bandwidth of 58% and matching bandwidth of 57% were obtained at 3.2 GHz.

  18. Thermochromic properties of the ferroelectric ?-doped ?: study of the temperature-induced dichroism

    Science.gov (United States)

    Valiente, Rafael; Rodríguez, Fernando

    1999-03-01

    A new thermochromic material formed by doping 0953-8984/11/12/014/img3 into the ferroelectric 0953-8984/11/12/014/img4 crystal is presented. The change of colour from green (room temperature) to red (low temperature) under polarized light observation is accompanied by a strong temperature-induced dichroism at low temperature. The origin of these phenomena is investigated through the polarized charge transfer spectra associated with 0953-8984/11/12/014/img3 complexes formed in the title compound, and their dependence on temperature in the 10-300 K range. Attention is paid to correlating the optical spectra with the local structure around 0953-8984/11/12/014/img3. The results are compared with those obtained in the tribromide 0953-8984/11/12/014/img7 and 0953-8984/11/12/014/img8, and the tetrabromide 0953-8984/11/12/014/img9 and 0953-8984/11/12/014/img10 crystals, where 0953-8984/11/12/014/img3 forms 0953-8984/11/12/014/img12 complexes of nearly 0953-8984/11/12/014/img13 symmetry, and tetrahedral distorted 0953-8984/11/12/014/img14 complexes of 0953-8984/11/12/014/img15 symmetry, respectively. An interesting feature is the presence of a strongly polarized absorption band at 15 800 0953-8984/11/12/014/img16 in 0953-8984/11/12/014/img17, which is responsible for the observed dichroism and thermochromism. The existence of this band is associated with the formation of highly distorted 0953-8984/11/12/014/img14 complexes in the monoclinic 0953-8984/11/12/014/img19 host crystal. The enhancement of dichroism exhibited by this crystal with decreasing temperature is noteworthy. The analysis of the spectra reveals that this unusual thermal behaviour can be explained in terms of thermally activated reorientations rather than structural changes of the 0953-8984/11/12/014/img3 complex.

  19. Theoretical Simulations and Ultrafast Pump-probe Spectroscopy Experiments in Pigment-protein Photosynthetic Complexes

    Energy Technology Data Exchange (ETDEWEB)

    Buck, D.R.

    2000-09-12

    Theoretical simulations and ultrafast pump-probe laser spectroscopy experiments were used to study photosynthetic pigment-protein complexes and antennae found in green sulfur bacteria such as Prosthecochloris aestuarii, Chloroflexus aurantiacus, and Chlorobium tepidum. The work focused on understanding structure-function relationships in energy transfer processes in these complexes through experiments and trying to model that data as we tested our theoretical assumptions with calculations. Theoretical exciton calculations on tubular pigment aggregates yield electronic absorption spectra that are superimpositions of linear J-aggregate spectra. The electronic spectroscopy of BChl c/d/e antennae in light harvesting chlorosomes from Chloroflexus aurantiacus differs considerably from J-aggregate spectra. Strong symmetry breaking is needed if we hope to simulate the absorption spectra of the BChl c antenna. The theory for simulating absorption difference spectra in strongly coupled photosynthetic antenna is described, first for a relatively simple heterodimer, then for the general N-pigment system. The theory is applied to the Fenna-Matthews-Olson (FMO) BChl a protein trimers from Prosthecochloris aestuarii and then compared with experimental low-temperature absorption difference spectra of FMO trimers from Chlorobium tepidum. Circular dichroism spectra of the FMO trimer are unusually sensitive to diagonal energy disorder. Substantial differences occur between CD spectra in exciton simulations performed with and without realistic inhomogeneous distribution functions for the input pigment diagonal energies. Anisotropic absorption difference spectroscopy measurements are less consistent with 21-pigment trimer simulations than 7-pigment monomer simulations which assume that the laser-prepared states are localized within a subunit of the trimer. Experimental anisotropies from real samples likely arise from statistical averaging over states with diagonal energies shifted by

  20. PLANAR MOTION OF A SLIGHTLY DISTORTED CIRCULAR CYLINDER AROUND ANOTHER CIRCULAR ONE

    Institute of Scientific and Technical Information of China (English)

    SUN Ren; CHWANG Allen T.

    2004-01-01

    Accurate prediction of the motion of a body moving around another one in an unbounded fluid and determi-nation of the hydrodynamic interaction between them are im-portant in the coastal and offshore engineering. For two-dimensional cases, most of the previous studies were focused on the interaction between circular cylinders without considering the non-circular situation. To break through the limitation of"circular" bodies, in the present paper the boundary perturbation method was employed to investigate the motion of a slightly distorted circular cylinder around a circular one. An approximate complex velocity potential in terms of double infinite series expanded at two singular points was derived using the method of continued fractions. The hydrodynamic interaction between two cylinders was computed by solving the dynamical equations of motion. In a relative coordinate system moving with the uniform stream, the kinetic energy of the fluid was expressed as a function of fifteen added masses. Approximate analytical solutions of added masses in the series form were obtained and applied to determine the trajectories of the slightly distorted circular cylinder around a fixed circular one. Numerical results show that the presence of the circular cylinder affects the planar motion of the slightly distorted cirular cylinder and the initial configuration of the slightly distorted circular cylinder has a decisive influence on the development of its rotational motion.

  1. Nanocomposites Polarizing by Absorption: Dichroism in the Near-Infrared Region (NIR

    Directory of Open Access Journals (Sweden)

    Lorenz Bonderer

    2014-03-01

    Full Text Available We describe the preparation of nanocomposites which exhibit dichroism in the near infrared region (NIR. These materials consist of crosslinked poly(dimethylsiloxane (PDMS and gold nanoparticles, coated with 1-dodecanethiol or tert-tetradecanethiol. The alkanethiols improve dispersibility of the gold particles, and accordingly composites were manufactured by diffusion of the particles into swollen self-supporting PDMS elastomer films. After drying, the films were exposed to solvents for one minute, stretched in wet state, dried again and annealed. This procedure led to formation of oriented linear gold particle assemblies within stretched polymer. If the aspect ratio of the particle assemblies is high, the absorption of polarized light in the NIR region is expected to depend on the angle between the polarization plane and the orientation direction of the particle assemblies, and this was observed to be the case.

  2. Spin polarization and magnetic dichroism in core-level photoemission from ferromagnets

    Energy Technology Data Exchange (ETDEWEB)

    Menchero, J G [Univ. of California, Berkeley, CA (United States). Dept. of Physics

    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.

  3. Dichroism, chirality, and polarization eigenstates in Babinet nanoslot-dimer membrane metamaterials

    DEFF Research Database (Denmark)

    Zhukovsky, Sergei; Chigrin, Dmitry N.; Kremers, Christian;

    2013-01-01

    We present a detailed theoretical description of the optical properties of planar metamaterials comprising a metal membrane patterned with openings (microslots) arranged in closely located couples (dimers). Using the covariant coupled-dipole approach, the effective material tensors of such a meta......We present a detailed theoretical description of the optical properties of planar metamaterials comprising a metal membrane patterned with openings (microslots) arranged in closely located couples (dimers). Using the covariant coupled-dipole approach, the effective material tensors...... of such a metamaterial are recovered, and contributions responsible for elliptical dichroism and optical activity are identified. Polarization conversion properties of II-shaped and V-shaped dimers are determined and explained in terms of elliptically polarized eigenmodes of the metamaterial. Good agreement with direct...

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

    Energy Technology Data Exchange (ETDEWEB)

    Paul, Nibedita; Devi, Manasi; Mohanta, Dambarudhar [Nanoscience and Soft Matter Laboratory, Department of Physics, Tezpur University, PO Napaam, Tezpur 784 028, Assam (India); Saha, Abhijit [UGC-DAE Consortium for Scientific Research, Kolkata Centre, III/LB-8 Bidhannagar, Kolkata 700 098 (India)

    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.

  5. Terahertz spectroscopy

    DEFF Research Database (Denmark)

    Jepsen, Peter Uhd

    2009-01-01

    In this presentation I will review methods for spectroscopy in the THz range, with special emphasis on the practical implementation of the technique known ad THz time-domain spectroscopy (THz-TDS). THz-TDS has revived the old field of far-infrared spectroscopy, and enabled a wealth of new...... activities that promise commercial potential for spectroscopic applications in the THz range. This will be illustrated with examples of spectroscopy of liquids inside their bottles as well as sensitive, quantitative spectroscopy in waveguides....

  6. OPERATIONAL CIRCULAR NO 6 - JUNE 2001 'CERN SCIENTIFIC DOCUMENTS'

    CERN Multimedia

    Human Resources Division

    2001-01-01

    This new operational circular has been drawn up. It cancels and replaces Administrative Circular N° 29 entitled "Principles and procedures governing CERN publications and reports and other publications arising from CERN work". Copies are available from Divisional Secretariats. Note : Administrative and operational circulars, as well as the lists of those in force, are available for consultation on WWW : ADMINISTRATIVE CIRCULARSOPERATIONAL CIRCULARS

  7. Liquid chromatography with mass spectrometry enantioseparation of pomalidomide on cyclodextrin-bonded chiral stationary phases and the elucidation of the chiral recognition mechanisms by NMR spectroscopy and molecular modeling.

    Science.gov (United States)

    Szabó, Zoltán-István; Szőcs, Levente; Horváth, Péter; Komjáti, Balázs; Nagy, József; Jánoska, Ádám; Muntean, Daniela-Lucia; Noszál, Béla; Tóth, Gergő

    2016-08-01

    A sensitive and validated liquid chromatography with mass spectrometry method was developed for the enantioseparation of the racemic mixture of pomalidomide, a novel, second-generation immunomodulatory drug, using β-cyclodextrin-bonded stationary phases. Four cyclodextrin columns (β-, hydroxypropyl-β-, carboxymethyl-β-, and sulfobutyl-β-cyclodextrin) were screened and the effects of eluent composition, flow rate, temperature, and organic modifier on enantioseparation were studied. Optimized parameters, offering baseline separation (resolution = 2.70 ± 0.02) were the following: β-cyclodextrin stationary phase, thermostatted at 15°C, and mobile phase consisting of methanol/0.1% acetic acid 10:90 v/v, delivered with 0.8 mL/min flow rate. For the optimized parameter at multiple reaction monitoring mode 274.1-201.0 transition with 20 eV collision energy and 100 V fragmentor voltage the limit of detection and limit of quantitation were 0.75 and 2.00 ng/mL, respectively. Since enantiopure standards were not available, elution order was determined upon comparison of the circular dichroism signals of the separated pomalidomide enantiomers with that of enantiopure thalidomide. The mechanisms underlying the chiral discrimination between the enantiomers were also investigated. Pomalidomide-β-cyclodextrin inclusion complex was characterized using nuclear magnetic resonance spectroscopy and molecular modeling. The thermodynamic aspects of chiral separation were also studied. PMID:27279456

  8. Liquid chromatography with mass spectrometry enantioseparation of pomalidomide on cyclodextrin-bonded chiral stationary phases and the elucidation of the chiral recognition mechanisms by NMR spectroscopy and molecular modeling.

    Science.gov (United States)

    Szabó, Zoltán-István; Szőcs, Levente; Horváth, Péter; Komjáti, Balázs; Nagy, József; Jánoska, Ádám; Muntean, Daniela-Lucia; Noszál, Béla; Tóth, Gergő

    2016-08-01

    A sensitive and validated liquid chromatography with mass spectrometry method was developed for the enantioseparation of the racemic mixture of pomalidomide, a novel, second-generation immunomodulatory drug, using β-cyclodextrin-bonded stationary phases. Four cyclodextrin columns (β-, hydroxypropyl-β-, carboxymethyl-β-, and sulfobutyl-β-cyclodextrin) were screened and the effects of eluent composition, flow rate, temperature, and organic modifier on enantioseparation were studied. Optimized parameters, offering baseline separation (resolution = 2.70 ± 0.02) were the following: β-cyclodextrin stationary phase, thermostatted at 15°C, and mobile phase consisting of methanol/0.1% acetic acid 10:90 v/v, delivered with 0.8 mL/min flow rate. For the optimized parameter at multiple reaction monitoring mode 274.1-201.0 transition with 20 eV collision energy and 100 V fragmentor voltage the limit of detection and limit of quantitation were 0.75 and 2.00 ng/mL, respectively. Since enantiopure standards were not available, elution order was determined upon comparison of the circular dichroism signals of the separated pomalidomide enantiomers with that of enantiopure thalidomide. The mechanisms underlying the chiral discrimination between the enantiomers were also investigated. Pomalidomide-β-cyclodextrin inclusion complex was characterized using nuclear magnetic resonance spectroscopy and molecular modeling. The thermodynamic aspects of chiral separation were also studied.

  9. Determination of the cation site distribution of the spinel in multiferroic CoFe{sub 2}O{sub 4}/BaTiO{sub 3} layers by X-ray photoelectron spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Aghavnian, T. [CEA/Saclay, DSM/IRAMIS/SPEC, CNRS UMR 3680, F-91191 Gif-sur-Yvette (France); Synchrotron SOLEIL, L’Orme des Merisiers Saint-Aubin, F-91192 Gif-sur-Yvette (France); Moussy, J.-B.; Stanescu, D. [CEA/Saclay, DSM/IRAMIS/SPEC, CNRS UMR 3680, F-91191 Gif-sur-Yvette (France); Belkhou, R. [Synchrotron SOLEIL, L’Orme des Merisiers Saint-Aubin, F-91192 Gif-sur-Yvette (France); Jedrecy, N. [Sorbonne Universités, UPMC Univ Paris 06, UMR 7588, INSP, F-75005 Paris (France); Magnan, H. [CEA/Saclay, DSM/IRAMIS/SPEC, CNRS UMR 3680, F-91191 Gif-sur-Yvette (France); Ohresser, P. [Synchrotron SOLEIL, L’Orme des Merisiers Saint-Aubin, F-91192 Gif-sur-Yvette (France); Arrio, M.-A.; Sainctavit, Ph. [IMPMC, F-75015 Paris (France); Barbier, A., E-mail: abarbier@cea.fr [CEA/Saclay, DSM/IRAMIS/SPEC, CNRS UMR 3680, F-91191 Gif-sur-Yvette (France)

    2015-07-15

    Highlights: • We grow epitaxial and well characterized CoFe{sub 2}O{sub 4}/BaTiO{sub 3} thin films. • We studied the spinel cation site distribution in CoFe{sub 2}O{sub 4}/BaTiO{sub 3} thin films. • We quantitatively determine the spinel inversion parameter by XMCD and XPS. • We propose a reproducible XPS fit method based on physical principles. - Abstract: The properties of CoFe{sub 2}O{sub 4}/BaTiO{sub 3} artificial multiferroic multilayers strongly depend on the crystalline structure, the stoichiometry and the cation distribution between octahedral (Oh) and tetrahedral (Td) sites (inversion factor). In the present study, we have investigated epitaxial CoFe{sub 2}O{sub 4} layers grown on BaTiO{sub 3}, with different Co/Fe ratios. We determined the cation distribution in our samples by X-ray magnetic circular dichroism (XMCD), a well accepted method to do so, and by X-ray photoelectron spectroscopy (XPS), using a fitting method based on physical considerations. We observed that our XPS approach converged on results consistent with XMCD measurements made on the same samples. Thus, within a careful decomposition based on individual chemical environments it is shown that XPS is fully able to determine the actual inversion factor.

  10. Researches on Relationship between Circular Agriculture and Industrial Diversity

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    First, this paper establishes the conceptual model of circular agriculture, conducts systematic analysis on the circular agriculture on the basis of conceptual model, and discusses the characteristics of closeness and openness of circular agriculture and relationship between closeness and openness of circular agriculture. Second, this paper introduces the industrial diversity related to circular agriculture, defines the concept of industry and the concept of industries related to agriculture, and illustrates the related industries that are conducive to circular agriculture and the related industries that are not conducive to circular agriculture. Finally, this paper analyzes the mutual relationship between circular agriculture and industrial diversity as follows: in the system of circular agriculture, the industrial diversity can transform the wastes in upstream industries into resources in downstream industries; the industrial diversity creates possibility for recycling of agricultural byproducts; the industrial diversity is conducive to the diversification of industries related to circular agriculture.

  11. Site-specific thermodynamic stability and unfolding of a de novo designed protein structural motif mapped by 13C isotopically edited IR spectroscopy.

    Science.gov (United States)

    Kubelka, Ginka S; Kubelka, Jan

    2014-04-23

    The mechanism of protein folding remains poorly understood, in part due to limited experimental information available about partially folded states. Isotopically edited infrared (IR) spectroscopy has emerged as a promising method for studying protein structural changes with site-specific resolution, but its full potential to systematically probe folding at multiple protein sites has not yet been realized. We have used (13)C isotopically edited IR spectroscopy to investigate the site-specific thermal unfolding at seven different locations in the de novo designed helix-turn-helix protein αtα. As one of the few stable helix-turn-helix motifs, αtα is an excellent model for studying the roles of secondary and tertiary interactions in folding. Circular dichroism (CD) experiments on the full αtα motif and its two peptide fragments show that interhelical tertiary contacts are critical for stabilization of the secondary structure. The site-specific thermal unfolding probed by (13)C isotopically edited IR is likewise consistent with primarily tertiary stabilization of the local structure. The least thermally stable part of the αtα motif is near the turn where the interhelical contacts are rather loose, while the motif's center with best established core packing has the highest stability. Similar correlation between the local thermal stability and tertiary contacts was found previously for a naturally occurring helix-turn-helix motif. These results underline the importance of native-like tertiary stabilizing interactions in folding, in agreement with recent state-of-the art folding simulations as well as simplified, native-centric models.

  12. Structural and thermodynamic analysis of the binding of tRNA(phe) by the putative anticancer alkaloid chelerythrine: Spectroscopy, calorimetry and molecular docking studies.

    Science.gov (United States)

    Basu, Pritha; Payghan, Pavan V; Ghoshal, Nanda; Suresh Kumar, Gopinatha

    2016-08-01

    The interaction of the putative anticancer alkaloid chelerythrine with tRNA(phe) was characterized by spectroscopy, calorimetry and molecular docking studies. The charged iminium form of chelerythrine binds with tRNA(phe) in a cooperative mode with a binding affinity value of (4.06±0.01)×10(5)M(-1). The neutral alkanolamine form does not bind to tRNA(phe) but in the presence of high concentration of tRNA(phe) this form gets converted to the iminium form and then binds with tRNA(phe). The partial intercalative mode of binding of chelerythrine to the tRNA(phe) was characterized from the steady state anisotropy, iodide ion-induced fluorescence quenching and viscosity measurements. Chelerythrine binding induced conformational perturbations in tRNA(phe) as observed from the circular dichroism spectroscopy. The strong binding was also supported by the ethidium bromide displacement assay. The binding was favoured by both enthalpy and entropy contributions. Although the binding was dependent on the [Na(+)], non-electrostatic forces contributed predominantly to the Gibbs energy change. The negative value of the heat capacity change proposed the involvement of hydrophobic forces in the binding. Molecular docking study was carried out to decipher the details of the recognition of tRNA(phe) by chelerythrine. The study provided insights about the chelerythrine binding pockets on tRNA(phe) and marked the necessary interactions for binding of chelerythrine molecule. Partially intercalative mode of the alkaloid binding was supported by docking studies. In total, docking studies corroborated well with our experiential observations. The structural and thermodynamic results of chelerythrine binding to tRNA(phe) may be helpful to develop new RNA therapeutic agents. PMID:27289446

  13. Circular design - A manual on how to integrate circular design in buildings

    NARCIS (Netherlands)

    Mac-lean, M.; Van Splunter, M.; Sun, X.

    2014-01-01

    This "designers' manual" is made during the TIDO-course AR0531 Innovation and Sustainability Circular design is based on two sustainability concepts: Cradle to Cradle® and circular economy. The former is more dogmatic and specific for the manufacturing and design industry, while the latter presents

  14. The clusters-in-a-liquid approach for solvation: New insights from the conformer specific gas phase spectroscopy and vibrational optical activity spectroscopy

    Science.gov (United States)

    Xu, Yunjie; Perera, Angelo; Thomas, Javix; Poopari, Mohammad

    2016-02-01

    Vibrational optical activity spectroscopies, namely vibrational circular dichroism (VCD) and Raman optical activity (ROA), have been emerged in the past decade as a powerful spectroscopic tool for stereochemical information of a wide range of chiral compounds in solution directly. More recently, their applications in unveiling solvent effects, especially those associated with water solvent, have been explored. In this review article, we first select a few examples to demonstrate the unique sensitivity of VCD spectral signatures to both bulk solvent effects and explicit hydrogen-bonding interactions in solution. Second, we discuss the induced solvent chirality, or chiral transfer, VCD spectral features observed at the water bending band region in detail. From these chirality transfer spectral data, the related conformer specific gas phase spectroscopic studies of small chiral hydration clusters, and the associated matrix isolation VCD experiments of hydrogen-bonded complexes in cold rare gas matrices, a general picture of solvation in aqueous solution emerges. In such an aqueous solution, some small chiral hydration clusters, rather than the chiral solutes themselves, are the dominant species and are the ones who contribute mainly to the experimentally observed VCD features. We then review a series of VCD studies of amino acids and their derivatives in aqueous solution under different pHs to emphasize the importance of the inclusion of the bulk solvent effects. These experimental data and the associated theoretical analyses are the foundation for the proposed “clusters-in-a-liquid” approach to account for solvent effects effectively. We present several approaches to identify and build such representative chiral hydration clusters. Recent studies which applied molecular dynamics simulations and the subsequent snapshot averaging approach to generate the ROA, electronic CD, and optical rotatory dispersion spectra are also reviewed. Challenges associated with the

  15. Environmental issues elimination through circular economy

    Science.gov (United States)

    Špirková, M.; Pokorná, E.; Šujanová, J.; Samáková, J.

    2016-04-01

    Environmental efforts of European Union are currently going towards circular economy. Tools like Extended Producer Responsibility and Eco-design were established. The circular economy deals with resources availability issue on one hand and waste management on the other hand. There are few pioneering companies all over the world with some kind of circular economy practice. Generally the concept is not very wide-spread. The paper aims to evaluate possibility of transition towards circular economy in Slovak industrial companies. They need to have an active approach to material treatment of their products after usage stage. Innovation is another important pre-condition for the transition. Main problem of current cradle to grave system is landfilling of valuable materials after one cycle of usage. Their potential value for next manufacturing cycles is lost. Companies may do not see connection between waste management and material resource prices and volatility of supplies. Municipalities are responsible for municipal waste collection and treatment in Slovakia. The circular economy operates by cradle to cradle principle. Company manages material flow until the material comes back to the beginning of manufacturing process by itself or by another partners. Stable material supplies with quite low costs are provided this way. It is necessary to deal with environmental problems in phase of product design. Questionnaire survey results show on one hand low involvement of industrial companies in waste management area, however on the other hand they are open to environmental innovations in future.

  16. A broadband, circular-polarization selective surface

    Science.gov (United States)

    Momeni Hasan Abadi, Seyed Mohamad Amin; Behdad, Nader

    2016-06-01

    We introduce a new technique for designing wideband circular-polarization selective surfaces (CPSSs) based on anisotropic miniaturized element frequency selective surfaces. The proposed structure is a combination of two linear-to-circular polarization converters sandwiching a linear polarizer. This CPSS consists of a number of metallic layers separated from each other by thin dielectric substrates. The metallic layers are in the form of two-dimensional arrays of subwavelength capacitive patches and inductive wire grids with asymmetric dimensions and a wire grid polarizer with sub-wavelength period. The proposed device is designed to offer a wideband circular-polarization selection capability allowing waves with left-hand circular polarization to pass through while rejecting those having right-hand circular polarization. A synthesis procedure is developed that can be used to design the proposed CPSS based on its desired band of operation. Using this procedure, a prototype of the proposed CPSS operating in the 12-18 GHz is designed. Full-wave electromagnetic simulations are used to predict the response of this structure. These simulation results confirm the validity of the proposed design concept and synthesis procedure and show that proposed CPSS operates within a fractional bandwidth of 40% with a co-polarization transmission discrimination of more than 15 dB. Furthermore, the proposed design is shown to be capable of providing an extremely wide field of view of ±60°.

  17. A COMPACT CIRCULARLY POLARIZED SLOTTED MICROSTRIP ANTENNA

    Directory of Open Access Journals (Sweden)

    V. Jebaraj

    2014-12-01

    Full Text Available Slot antennas are often used at UHF and microwave frequencies. In slot antenna for RFID reader applications the frequency ranges from 902-923MHz to achieve circular polarization. The shapes and size of the slot, as well as the driving frequency, determine the radiation distribution pattern. The proposed compact size circularly polarized slotted microstrip antenna are summarized with design rules. The circularly polarized radiation in square patch antenna can be obtained by perturbation technique with different shapes of slot in the orthogonal direction. A single feed configuration based symmetric slotted microstrip antenna is adapted to realize the compact circularly polarized microstrip antennas. Based on the perimeter, the size of the slot on microstrip slot antenna are studied and compared. The Operating frequency of the antenna is 912MHz that can be tuned by varying the perimeter of the slot while the keeping the circularly polarized radiation unchanged. The schematic and layout are configured by using Advanced Design System (ADS. Return loss, Resonant Frequency, Axial Ratio (AR, and Gain were determined for the proposed system using ADS. A measured 3dB Axial Ratio (AR bandwidth around 6MHz with 16MHz impedance bandwidth has been achieved for the antenna on a RO3004C substrate with dielectric constant 3.38.

  18. Circular Ribbon Flares and Homologous Jets

    CERN Document Server

    Wang, Haimin

    2012-01-01

    Solar flare emissions in the chromosphere often appear as elongated ribbons on both sides of the magnetic polarity inversion line (PIL), and this has been regarded as evidence of a typical configuration of magnetic reconnection. However, flares having a closed circular ribbon have rarely been reported, although it is expected in the fan--spine magnetic topology involving reconnection at a three-dimensional (3D) coronal null point. We present five circular ribbon flares with associated surges, using high-resolution and high-cadence \\ha blue wing observations obtained from the recently digitized films of Big Bear Solar Observatory (BBSO). In all the events, a central parasitic magnetic field is encompassed by the opposite magnetic polarity, forming a circular PIL that is also traced by filament material. Consequently, a flare kernel at the center is surrounded by a circular flare ribbon. The four homologous jet-related flares on 1991 March 17 and 18 are of particular interest, as (1) the circular ribbons bright...

  19. Chaotic Motion of Corrugated Circular Plates

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    Large deflection theory of thin anisotropic circular plates was used to analyze the bifurcation behavior and chaotic phenomena of a corrugated thin circular plate with combined transverse periodic excitation and an in-plane static boundary load. The nonlinear dynamic equation for the corrugated plate was derived by employing Galerkin's technique. The critical conditions for occurrence of the homoclinic and subharmonic bifurcations as well as chaos were studied theoretically using the Melnikov function method. The chaotic motion was also simulated numerically using Maple, with the Poincaré map and phase curve used to evaluate when chaotic motion appears. The results indicate some chaotic motion in the corrugated plate. The method is directly applicable to chaotic analysis of an isotropic circular plate.

  20. Charged Particle Optics in Circular Higgs Factory

    Energy Technology Data Exchange (ETDEWEB)

    Cai, Yunhai [SLAC National Accelerator Lab., Menlo Park, CA (United States)

    2015-02-26

    Similar to a super B-factory, a circular Higgs factory will require strong focusing systems near the interaction points and a low-emittance lattice in arcs to achieve a factory luminosity. At electron beam energy of 120 GeV, beamstrahlung effects during the collision pose an additional challenge to the collider design. In particular, a large momentum acceptance at 2 percent level is necessary to retain an adequate beam lifetime. This turns out to be the most challenging aspect in the design of circular Higgs factory. In this paper, an example will be provided to illustrate the beam dynamics in circular Higgs factory, emphasizing on the chromatic optics. Basic optical modules and advanced analysis will be presented. Most important, we will show that 2% momentum aperture is achievable

  1. Response-Adaptive Allocation for Circular Data.

    Science.gov (United States)

    Biswas, Atanu; Dutta, Somak; Laha, Arnab Kumar; Bakshi, Partho K

    2015-01-01

    Response-adaptive designs are used in phase III clinical trials to allocate a larger proportion of patients to the better treatment. Circular data is a natural outcome in many clinical trial setup, e.g., some measurements in opthalmologic studies, degrees of rotation of hand or waist, etc. There is no available work on response-adaptive designs for circular data. With reference to a dataset on cataract surgery we provide some response-adaptive designs where the responses are of circular nature and propose some test statistics for treatment comparison under adaptive data allocation procedure. Detailed simulation study and the analysis of the dataset, including redesigning the cataract surgery data, are carried out.

  2. Circular object recognition based on shape parameters

    Institute of Scientific and Technical Information of China (English)

    Chen Aijun; Li Jinzong; Zhu Bing

    2007-01-01

    To recognize circular objects rapidly in satellite remote sensing imagery, an approach using their geometry properties is presented.The original image is segmented to be a binary one by one dimension maximum entropy threshold algorithm and the binary image is labeled with an algorithm based on recursion technique.Then, shape parameters of all labeled regions are calculated and those regions with shape parameters satisfying certain conditions are recognized as circular objects.The algorithm is described in detail, and comparison experiments with the randomized Hough transformation (RHT) are also provided.The experimental results on synthetic images and real images show that the proposed method has the merits of fast recognition rate, high recognition efficiency and the ability of anti-noise and anti-jamming.In addition, the method performs well when some circular objects are little deformed and partly misshapen.

  3. Analytical Optimization of Piezoelectric Circular Diaphragm Generator

    Directory of Open Access Journals (Sweden)

    S. Mohammadi

    2013-01-01

    Full Text Available This paper presents an analytical study of the piezoelectric circular diaphragm microgenerator using strain energy method. Piezoelectrics are the intelligent materials that can be used as transducer to convert mechanical energy into electrical energy and vice versa. The aim of this paper is to optimize produced electrical energy from mechanical pressure. Therefore, the circular metal plate equipped with piezoelectric circular patch has been considered with simply and clamped supports. A comprehensive modeling, parametrical study and the effect of the boundary conditions on the performance of the microgenerator have been investigated. The system is under variable pressure from an oscillating pressure source. Results are presented for PZT and PMN-PT piezoelectric materials with steel and aluminum substrates. An optimal value for the radius and thickness of the piezoelectric layer with a special support condition has been obtained.

  4. Nanophotonic control of circular dipole emission.

    Science.gov (United States)

    le Feber, B; Rotenberg, N; Kuipers, L

    2015-01-01

    Controlling photon emission by single emitters with nanostructures is crucial for scalable on-chip information processing. Nowadays, nanoresonators can affect the lifetime of linear dipole emitters, while nanoantennas can steer the emission direction. Expanding this control to the emission of orbital angular momentum-changing transitions would enable a future coupling between solid state and photonic qubits. As these transitions are associated with circular dipoles, such control requires knowledge of the interaction of a complex dipole with optical eigenstates containing local helicity. We experimentally map the coupling of classical, circular dipoles to photonic modes in a photonic crystal waveguide. We show that, depending on the combination of the local helicity of the mode and the dipole helicity, circular dipoles can couple to left- or rightwards propagating modes with a near-unity directionality. The experimental maps are in excellent agreement with calculations. Our measurements, therefore, demonstrate the possibility of coupling the spin to photonic pathway. PMID:25833305

  5. Seismic interpretation of circular geological structures

    Energy Technology Data Exchange (ETDEWEB)

    Stewart, S.A. [Amerada Hess Ltd., London (United Kingdom)

    1999-08-01

    3D seismic data provide images of geological features which are approximately circular in plan view but whose shape and origin may be possible to constrain using 2D seismic data. As 3D seismic data become more commonly employed in hydrocarbon exploration, the number of demonstrably 'circular' structures will increase. At least ten different geological processes can result in seismically resolvable 'circular' structures in sedimentary basins. These include salt/shale diapirs, salt withdrawal basins, polygonal fault blocks, dissolution collapse hollows, breccia pipes, calderas, gas pockmarks, bioherms, sand volcanoes, pull-aparts, impact craters and tectonic folds. Geometrical and geological criteria for each are summarized to facilitate identification of such features should they be encountered in the course of a 3D seismic interpretation. Certain types of geological feature have distinctive properties, others are less straightforward to recognize on the basis of individual criteria. (Author)

  6. A physico-chemical study of some areas of fundamental significance to biophysics

    International Nuclear Information System (INIS)

    This report discusses the following topics: Radiation signatures; photoelectron spectroscopy of biologically active molecules; laser optogalvanic effect; magnetic circular dichroism; photochemistry of halogenated molecules; and density effects on high-n rydbergs

  7. The adsorption-desorption cycle. Reversibility of the BSA-silica system

    NARCIS (Netherlands)

    Giacomelli, CE; Norde, W

    2001-01-01

    The reversibility of the adsorption-desorption cycle was established by comparing the thermostability (determined by differential scanning calorimetry) and secondary structure (obtained by circular dichroism spectroscopy) of BSA before adsorption, adsorbed on, and exchanged from silica particles. Ci

  8. BSA structural changes during homomolecular exchange between the adsorbed and dissolved state

    NARCIS (Netherlands)

    Norde, W.; Giacomelli, C.E.

    2000-01-01

    The secondary structure and the thermostability of bovine serum albumin (BSA), before adsorption and after homomolecular displacement from silica and polystyrene particles, are studied by circular dichroism spectroscopy and differential scanning calorimetry. The structural perturbations induced by t

  9. The adsorption-desorption cycle. Reversibility of the BSA-silica system

    NARCIS (Netherlands)

    Giacomelli, C.E.; Norde, W.

    2001-01-01

    The reversibility of the adsorption–desorption cycle was established by comparing the thermostability (determined by differential scanning calorimetry) and secondary structure (obtained by circular dichroism spectroscopy) of BSA before adsorption, adsorbed on, and exchanged from silica particles. Ci

  10. BSA structural changes during homomolecular exchange between the adsorbed and the dissolved states

    NARCIS (Netherlands)

    Norde, W; Giacomelli, CE

    2000-01-01

    The secondary structure and the thermostability of bovine serum albumin (BSA), before adsorption and after homomolecular displacement from silica and polystyrene particles, are studied. by circular dichroism spectroscopy and differential scanning calorimetry. The structural perturbations induced by

  11. Effects of succinylation on the structure and thermostability of lysozyme

    NARCIS (Netherlands)

    Veen, van der M.; Norde, W.; Cohen Stuart, M.A.

    2005-01-01

    The influence of succinylation on lysozyme is studied using circular dichroism, fluorescence spectroscopy, and differential scanning calorimetry. The spectroscopic data reveal that at room temperature the structures of succinylated lysozyme and native lysozyme are similar. However, the calorimetric

  12. Rectangular-to-circular groove waveguide junction

    Institute of Scientific and Technical Information of China (English)

    CUI; Licheng; (崔立成); YANG; Hongsheng; (杨鸿生)

    2003-01-01

    Mode matching method is used to analyze the scattering characteristics of the rectangular-to-circular groove waveguide junction. Firstly, the scattering matrix equation is obtained by matching the electromagnetic fields at the boundary of the junction. The scattering coefficients can be obtained from the equation. Secondly the scattering characteristics of the iris with rectangular window positioned in circular groove waveguide are briefly analyzed. Thirdly, the convergent problem is discussed and the numerical results are given. At last experiment is made and good agreement is found between the calculated results and the measured results.

  13. Circularly polarized U-Slot antenna

    OpenAIRE

    Tong, K. F.; Wong, T P

    2007-01-01

    Circularly polarized single-layer U-slot microstrip patch antenna has been proposed. The suggested asymmetrical U-slot can generate the two orthogonal modes for circular polarization without chamfering any corner of the probe-fed square patch microstrip antenna. A parametric study has been carried out to investigate the effects caused by different arm lengths of the U-slot. The thickness of the foam substrate is about 8.5% of the wavelength at the operating frequency. The 3 dB axial ratio ban...

  14. Broadband Suspended Microstrip Antenna For Circular Polarization

    OpenAIRE

    Kasabegoudar, VG; Vinoy, KJ

    2009-01-01

    In this paper we propose a circularly polarized (CP) microstrip antenna on a suspended substrate with a coplanar capacitive feed and a slot within the rectangular patch. The antenna has an axial ratio bandwidth (< 3 dB) of 7.1%. The proposed antenna exhibits a much higher impedance bandwidth of about 49% (S11 < -10 dB) and also yields return loss better than -15 dB in the useful range of circular polarization. Measured characteristics of the antenna are in good agreement with the simulated re...

  15. Circular economy in China and recommendations

    Institute of Scientific and Technical Information of China (English)

    Zhou Hongchun

    2006-01-01

    @@ It is an overall, urgent and long-term strategic task for China to vigorously develop the circular economy and build a resource-saving and environmental-friendly society. China is now at the accelerating stage of industrialization and urbanization.Lower per-capita resource amount and tendency of environmental deterioration has not been fundamentally averted. Therefore a circular economy development is an inevitable choice to realize the goal of building a well-off society, ensure sustainable development of national economy, and coordinate the relationship between mankind and nature.

  16. Molecular recognition of malachite green by hemoglobin and their specific interactions: insights from in silico docking and molecular spectroscopy.

    Science.gov (United States)

    Peng, Wei; Ding, Fei; Peng, Yu-Kui; Sun, Ying

    2014-01-01

    Malachite green is an organic compound that can be widely used as a dyestuff for various materials; it has also emerged as a controversial agent in aquaculture. Since malachite green is proven to be carcinogenic and mutagenic, it may become a hazard to public health. For this reason, it is urgently required to analyze this controversial dye in more detail. In our current research, the interaction between malachite green and hemoglobin under physiological conditions was investigated by the methods of molecular modeling, fluorescence spectroscopy, circular dichroism (CD) as well as hydrophobic ANS displacement experiments. From the molecular docking, the central cavity of hemoglobin was assigned to possess high-affinity for malachite green, this result was corroborated by time-resolved fluorescence and hydrophobic ANS probe results. The recognition mechanism was found to be of static type, or rather the hemoglobin-malachite green complex formation occurred via noncovalent interactions such as π-π interactions, hydrogen bonds and hydrophobic interactions with an association constant of 10(4) M(-1). Moreover, the results also show that the spatial structure of the biopolymer was changed in the presence of malachite green with a decrease of the α-helix and increase of the β-sheet, turn and random coil suggesting protein damage, as derived from far-UV CD and three-dimensional fluorescence. Results of this work will help to further comprehend the molecular recognition of malachite green by the receptor protein and the possible toxicological profiles of other compounds, which are the metabolites and ramifications of malachite green. PMID:24226412

  17. Structural features of membrane-bound glucocerebrosidase and α-synuclein probed by neutron reflectometry and fluorescence spectroscopy.

    Science.gov (United States)

    Yap, Thai Leong; Jiang, Zhiping; Heinrich, Frank; Gruschus, James M; Pfefferkorn, Candace M; Barros, Marilia; Curtis, Joseph E; Sidransky, Ellen; Lee, Jennifer C

    2015-01-01

    Mutations in glucocerebrosidase (GCase), the enzyme deficient in Gaucher disease, are a common genetic risk factor for the development of Parkinson disease and related disorders, implicating the role of this lysosomal hydrolase in the disease etiology. A specific physical interaction exists between the Parkinson disease-related protein α-synuclein (α-syn) and GCase both in solution and on the lipid membrane, resulting in efficient enzyme inhibition. Here, neutron reflectometry was employed as a first direct structural characterization of GCase and α-syn·GCase complex on a sparsely-tethered lipid bilayer, revealing the orientation of the membrane-bound GCase. GCase binds to and partially inserts into the bilayer with its active site most likely lying just above the membrane-water interface. The interaction was further characterized by intrinsic Trp fluorescence, circular dichroism, and surface plasmon resonance spectroscopy. Both Trp fluorescence and neutron reflectometry results suggest a rearrangement of loops surrounding the catalytic site, where they extend into the hydrocarbon chain region of the outer leaflet. Taking advantage of contrasting neutron scattering length densities, the use of deuterated α-syn versus protiated GCase showed a large change in the membrane-bound structure of α-syn in the complex. We propose a model of α-syn·GCase on the membrane, providing structural insights into inhibition of GCase by α-syn. The interaction displaces GCase away from the membrane, possibly impeding substrate access and perturbing the active site. GCase greatly alters membrane-bound α-syn, moving helical residues away from the bilayer, which could impact the degradation of α-syn in the lysosome where these two proteins interact.

  18. Structural Features of Membrane-bound Glucocerebrosidase and α-Synuclein Probed by Neutron Reflectometry and Fluorescence Spectroscopy*

    Science.gov (United States)

    Yap, Thai Leong; Jiang, Zhiping; Heinrich, Frank; Gruschus, James M.; Pfefferkorn, Candace M.; Barros, Marilia; Curtis, Joseph E.; Sidransky, Ellen; Lee, Jennifer C.

    2015-01-01

    Mutations in glucocerebrosidase (GCase), the enzyme deficient in Gaucher disease, are a common genetic risk factor for the development of Parkinson disease and related disorders, implicating the role of this lysosomal hydrolase in the disease etiology. A specific physical interaction exists between the Parkinson disease-related protein α-synuclein (α-syn) and GCase both in solution and on the lipid membrane, resulting in efficient enzyme inhibition. Here, neutron reflectometry was employed as a first direct structural characterization of GCase and α-syn·GCase complex on a sparsely-tethered lipid bilayer, revealing the orientation of the membrane-bound GCase. GCase binds to and partially inserts into the bilayer with its active site most likely lying just above the membrane-water interface. The interaction was further characterized by intrinsic Trp fluorescence, circular dichroism, and surface plasmon resonance spectroscopy. Both Trp fluorescence and neutron reflectometry results suggest a rearrangement of loops surrounding the catalytic site, where they extend into the hydrocarbon chain region of the outer leaflet. Taking advantage of contrasting neutron scattering length densities, the use of deuterated α-syn versus protiated GCase showed a large change in the membrane-bound structure of α-syn in the complex. We propose a model of α-syn·GCase on the membrane, providing structural insights into inhibition of GCase by α-syn. The interaction displaces GCase away from the membrane, possibly impeding substrate access and perturbing the active site. GCase greatly alters membrane-bound α-syn, moving helical residues away from the bilayer, which could impact the degradation of α-syn in the lysosome where these two proteins interact. PMID:25429104

  19. Lipopolysaccharide-bound structure of the antimicrobial peptide cecropin P1 determined by nuclear magnetic resonance spectroscopy.

    Science.gov (United States)

    Baek, Mi-Hwa; Kamiya, Masakatsu; Kushibiki, Takahiro; Nakazumi, Taichi; Tomisawa, Satoshi; Abe, Chiharu; Kumaki, Yasuhiro; Kikukawa, Takashi; Demura, Makoto; Kawano, Keiichi; Aizawa, Tomoyasu

    2016-04-01

    Antimicrobial peptides (AMPs) are components of the innate immune system and may be potential alternatives to conventional antibiotics because they exhibit broad-spectrum antimicrobial activity. The AMP cecropin P1 (CP1), isolated from nematodes found in the stomachs of pigs, is known to exhibit antimicrobial activity against Gram-negative bacteria. In this study, we investigated the interaction between CP1 and lipopolysaccharide (LPS), which is the main component of the outer membrane of Gram-negative bacteria, using circular dichroism (CD) and nuclear magnetic resonance (NMR). CD results showed that CP1 formed an α-helical structure in a solution containing LPS. For NMR experiments, we expressed (15) N-labeled and (13) C-labeled CP1 in bacterial cells and successfully assigned almost all backbone and side-chain proton resonance peaks of CP1 in water for transferred nuclear Overhauser effect (Tr-NOE) experiments in LPS. We performed (15) N-edited and (13) C-edited Tr-NOE spectroscopy for CP1 bound to LPS. Tr-NOE peaks were observed at the only C-terminal region of CP1 in LPS. The results of structure calculation indicated that the C-terminal region (Lys15-Gly29) formed the well-defined α-helical structure in LPS. Finally, the docking study revealed that Lys15/Lys16 interacted with phosphate at glucosamine I via an electrostatic interaction and that Ile22/Ile26 was in close proximity with the acyl chain of lipid A.

  20. NPCirc: An R Package for Nonparametric Circular Methods

    Directory of Open Access Journals (Sweden)

    María Oliveira

    2014-11-01

    Full Text Available Nonparametric density and regression estimation methods for circular data are included in the R package NPCirc. Specifically, a circular kernel density estimation procedure is provided, jointly with different alternatives for choosing the smoothing parameter. In the regression setting, nonparametric estimation for circular-linear, circular-circular and linear-circular data is also possible via the adaptation of the classical Nadaraya-Watson and local linear estimators. In order to assess the significance of the features observed in the smooth curves, both for density and regression with a circular covariate and a linear response, a SiZer technique is developed for circular data, namely CircSiZer. Some data examples are also included in the package, jointly with a routine that allows generating mixtures of different circular distributions.