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

NASA Astrophysics Data System (ADS)

Koide, T.; Mamiya, K.; Asakura, D.; Osatune, Y.; Fujimori, A.; Suzuki, Y.; Katayama, T.; Yuasa, S.

2014-04-01

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.

Adaptive design of an X-ray magnetic circular dichroism spectroscopy experiment with Gaussian process modelling

NASA Astrophysics Data System (ADS)

Ueno, Tetsuro; Hino, Hideitsu; Hashimoto, Ai; Takeichi, Yasuo; Sawada, Masahiro; Ono, Kanta

2018-01-01

Spectroscopy is a widely used experimental technique, and enhancing its efficiency can have a strong impact on materials research. We propose an adaptive design for spectroscopy experiments that uses a machine learning technique to improve efficiency. We examined X-ray magnetic circular dichroism (XMCD) spectroscopy for the applicability of a machine learning technique to spectroscopy. An XMCD spectrum was predicted by Gaussian process modelling with learning of an experimental spectrum using a limited number of observed data points. Adaptive sampling of data points with maximum variance of the predicted spectrum successfully reduced the total data points for the evaluation of magnetic moments while providing the required accuracy. The present method reduces the time and cost for XMCD spectroscopy and has potential applicability to various spectroscopies.

Anisotropic spin-density distribution and magnetic anisotropy of strained La1-xSrxMnO3 thin films: angle-dependent x-ray magnetic circular dichroism

NASA Astrophysics Data System (ADS)

Shibata, Goro; Kitamura, Miho; Minohara, Makoto; Yoshimatsu, Kohei; Kadono, Toshiharu; Ishigami, Keisuke; Harano, Takayuki; Takahashi, Yukio; Sakamoto, Shoya; Nonaka, Yosuke; Ikeda, Keisuke; Chi, Zhendong; Furuse, Mitsuho; Fuchino, Shuichiro; Okano, Makoto; Fujihira, Jun-ichi; Uchida, Akira; Watanabe, Kazunori; Fujihira, Hideyuki; Fujihira, Seiichi; Tanaka, Arata; Kumigashira, Hiroshi; Koide, Tsuneharu; Fujimori, Atsushi

2018-01-01

Magnetic anisotropies of ferromagnetic thin films are induced by epitaxial strain from the substrate via strain-induced anisotropy in the orbital magnetic moment and that in the spatial distribution of spin-polarized electrons. However, the preferential orbital occupation in ferromagnetic metallic La1-xSrxMnO3 (LSMO) thin films studied by x-ray linear dichroism (XLD) has always been found out-of-plane for both tensile and compressive epitaxial strain and hence irrespective of the magnetic anisotropy. In order to resolve this mystery, we directly probed the preferential orbital occupation of spin-polarized electrons in LSMO thin films under strain by angle-dependent x-ray magnetic circular dichroism (XMCD). Anisotropy of the spin-density distribution was found to be in-plane for the tensile strain and out-of-plane for the compressive strain, consistent with the observed magnetic anisotropy. The ubiquitous out-of-plane preferential orbital occupation seen by XLD is attributed to the occupation of both spin-up and spin-down out-of-plane orbitals in the surface magnetic dead layer.

X-ray magnetic circular dichroism measured at the Fe K-edge with a reduced intrinsic broadening: x-ray absorption spectroscopy versus resonant inelastic x-ray scattering measurements

NASA Astrophysics Data System (ADS)

Juhin, Amélie; Sainctavit, Philippe; Ollefs, Katharina; Sikora, Marcin; Filipponi, Adriano; Glatzel, Pieter; Wilhelm, Fabrice; Rogalev, Andrei

2016-12-01

X-ray magnetic circular dichroism is measured at the Fe K pre-edge in yttrium iron garnet using two different procedures that allow reducing the intrinsic broadening due to the 1s corehole lifetime. First, deconvolution of XMCD data measured in total fluorescence yield (TFY) with an extremely high signal-to-noise ratio enables a factor of 2.4 to be gained in the XMCD intensity. Ligand field multiplet calculations performed with different values of intrinsic broadening show that deconvolving such high quality XMCD data is similar to reducing the lifetime broadening from a 1s corehole to a 2p corehole. Second, MCD is measured by resonant inelastic x-ray scattering spectroscopy as a function of incident energy and emission energy. Selection of a fixed emission energy, instead of using the TFY, allows enhancing the MCD intensity up to a factor of  ˜4.7. However, this significantly changes the spectral shape of the XMCD signal, which cannot be interpreted any more as an absorption spectrum.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ikeno, Hidekazu, E-mail: h-ikeno@21c.osakafu-u.ac.jp

2016-10-14

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

A rapid alternative to X-ray crystallography for chiral determination: case studies of vibrational circular dichroism (VCD) to advance drug discovery projects.

PubMed

Wesolowski, Steven S; Pivonka, Don E

2013-07-15

The absolute stereochemistry of chiral drugs is usually established via X-ray crystallography. However, vibrational circular dichroism (VCD) spectroscopy coupled with quantum mechanics simulations offers a rapid alternative to crystallography and is readily applied to both crystalline and non-crystalline samples. VCD is an effective complement to X-ray analysis of drug candidates, and it can be used as a high-throughput means of assessing absolute stereochemistry at all phases of the discovery process (hundreds of assignments per year). The practical implementation (or fee-for-service outsourcing) of VCD and selected case studies are illustrated with an emphasis on providing utility and impact to pharmaceutical discovery programs. Copyright © 2013 Elsevier Ltd. All rights reserved.

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

DOE PAGES

Janoschek, M.; Haskel, D.; Fernandez-Rodriguez, J.; ...

2015-01-14

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

Quantitative characterization of nanoscale polycrystalline magnets with electron magnetic circular dichroism.

PubMed

Muto, Shunsuke; Rusz, Ján; Tatsumi, Kazuyoshi; Adam, Roman; Arai, Shigeo; Kocevski, Vancho; Oppeneer, Peter M; Bürgler, Daniel E; Schneider, Claus M

2014-01-01

Electron magnetic circular dichroism (EMCD) allows the quantitative, element-selective determination of spin and orbital magnetic moments, similar to its well-established X-ray counterpart, X-ray magnetic circular dichroism (XMCD). As an advantage over XMCD, EMCD measurements are made using transmission electron microscopes, which are routinely operated at sub-nanometre resolution, thereby potentially allowing nanometre magnetic characterization. However, because of the low intensity of the EMCD signal, it has not yet been possible to obtain quantitative information from EMCD signals at the nanoscale. Here we demonstrate a new approach to EMCD measurements that considerably enhances the outreach of the technique. The statistical analysis introduced here yields robust quantitative EMCD signals. Moreover, we demonstrate that quantitative magnetic information can be routinely obtained using electron beams of only a few nanometres in diameter without imposing any restriction regarding the crystalline order of the specimen.

Electronic structure and x-ray magnetic circular dichroism in Mn-doped topological insulators Bi2Se3 and Bi2Te3

NASA Astrophysics Data System (ADS)

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

2017-12-01

We studied the structural, electronic, and magnetic properties of Mn-doped topological insulators Bi2Se3 and Bi2Te3 within the density-functional theory (DFT) using the generalized gradient approximation (GGA) in the framework of the fully relativistic spin-polarized Dirac linear muffin-tin orbital band-structure method. The x-ray absorption spectra (XAS) and x-ray magnetic circular dichroism at the Mn K and L2 ,3 edges were investigated theoretically from first principles. The calculated results are in good agreement with experimental data. The complex fine structure of the Mn L2 ,3 XAS in Mn-doped Bi2Se3 and Bi2Te3 was found to be not compatible with a pure Mn3 + valency state. Its interpretation demands mixed valent states. The theoretically calculated x-ray emission spectra at the Mn K and L2 ,3 edges are also presented and analyzed.

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

NASA Astrophysics Data System (ADS)

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

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

A compact permanent-magnet system for measuring magnetic circular dichroism in resonant inelastic soft X-ray scattering.

PubMed

Miyawaki, Jun; Suga, Shigemasa; Fujiwara, Hidenori; Niwa, Hideharu; Kiuchi, Hisao; Harada, Yoshihisa

2017-03-01

A compact and portable magnet system for measuring magnetic dichroism in resonant inelastic soft X-ray scattering (SX-RIXS) has been developed at the beamline BL07LSU in SPring-8. A magnetic circuit composed of Nd-Fe-B permanent magnets, which realised ∼0.25 T at the center of an 11 mm gap, was rotatable around the axis perpendicular to the X-ray scattering plane. Using the system, a SX-RIXS spectrum was obtained under the application of the magnetic field at an angle parallel, nearly 45° or perpendicular to the incident X-rays. A dedicated sample stage was also designed to be as compact as possible, making it possible to perform SX-RIXS measurements at arbitrary incident angles by rotating the sample stage in the gap between the magnetic poles. This system enables facile studies of magnetic dichroism in SX-RIXS for various experimental geometries of the sample and the magnetic field. A brief demonstration of the application is presented.

Microscopic Magnetic Properties of the Itinerant Metamagnet UCoAl by X-ray Magnetic Circular Dichroism

NASA Astrophysics Data System (ADS)

Combier, Tristan; Palacio-Morales, Alexandra; Sanchez, Jean-Pierre; Wilhelm, Fabrice; Pourret, Alexandre; Brison, Jean-Pascal; Aoki, Dai; Rogalev, Andrei

2017-02-01

The itinerant metamagnet UCoAl has been investigated by high field X-ray magnetic circular dichroism (XMCD) at the U M4,5 and Co K edges. The orbital and spin moments of U at 2.1 K for H || c applied below and above the first order metamagnetic transition field (HM) have been determined. The magnetism of UCoAl is dominated by the U moment. There is no evidence for any change of the orbital to spin moment ratio (˜-2.05) across HM and within the ferromagnetic phase up to 17 T. The possibility of a Fermi surface reconstruction at HM remains an open option. XMCD at the Co K-edge reveals the presence of a small Co 4p-orbital moment parallel to the macroscopic magnetization. In addition, the Co 3d-moment is estimated to be at most 0.1 μB at 17 T. The similar field dependence of the U and Co magnetizations indicates that the Co moment is induced by the U moment.

Multi-frame acquisition scheme for efficient energy-dispersive X-ray magnetic circular dichroism in pulsed high magnetic fields at the Fe K-edge

PubMed Central

Strohm, Cornelius; Perrin, Florian; Dominguez, Marie-Christine; Headspith, Jon; van der Linden, Peter; Mathon, Olivier

2011-01-01

Using a fast silicon strip detector, a multi-frame acquisition scheme was implemented to perform energy-dispersive X-ray magnetic circular dichroism at the iron K-edge in pulsed high magnetic fields. The acquisition scheme makes use of the entire field pulse. The quality of the signal obtained from samples of ferrimagnetic erbium iron garnet allows for quantitative evaluation of the signal amplitude. Below the compensation point, two successive field-induced phase transitions and the reversal of the net magnetization of the iron sublattices in the intermediate phase were observed. PMID:21335909

Uranium 5f shell in UPd2Al3 and URu2Si2 studied by x-ray magnetic circular dichroism

NASA Astrophysics Data System (ADS)

Yaouanc, A.; Dalmas de Réotier, P.; van der Laan, G.; Hiess, A.; Goulon, J.; Neumann, C.; Lejay, P.; Sato, N.

1998-10-01

We report x-ray magnetic circular dichroism (XMCD) measurements performed at the uranium M4,5 edges in the paramagnetic phase of the heavy fermion superconductors UPd2Al3 and URu2Si2. The analysis of the spectra with the first sum rule yields the orbital moment of the 5f shell for both compounds. The shape of the dichroic spectrum at the M5 edge for the two compounds is qualitatively different: a single lobe is observed for URu2Si2 and two lobes are detected for UPd2Al3. This two lobe structure reflects the strong effect of the interaction of the uranium 5f electrons with their environment in the latter compound.

Dzyaloshinskii-Moriya interaction in α -Fe2O3 measured by magnetic circular dichroism in resonant inelastic soft x-ray scattering

NASA Astrophysics Data System (ADS)

Miyawaki, Jun; Suga, Shigemasa; Fujiwara, Hidenori; Urasaki, Masato; Ikeno, Hidekazu; Niwa, Hideharu; Kiuchi, Hisao; Harada, Yoshihisa

2017-12-01

Fe L2 ,3-edge x-ray absorption spectra (XAS) and magnetic circular dichroism (MCD) in resonant inelastic x-ray scattering (RIXS) of α -Fe2O3 were measured to identify the electronic structure responsible for its weak ferromagnetism caused by the Dzyaloshinskii-Moriya interaction (DMI) at room temperature. In contrast to negligible MCD in XAS, MCD in RIXS (RIXS-MCD) was clearly observed in the d d excitation at 1.8 eV via excitation to charge-transfer states. Furthermore, RIXS-MCD showed a crystal orientation dependence, indicating that the observed RIXS-MCD originated from DMI. The observed RIXS-MCD is well described by ab initio charge-transfer multiplet calculations, revealing that the RIXS-MCD derives from spin flip excitations at delocalized eg orbitals. By the combination of the experiments and calculations, RIXS-MCD has unraveled that the origin of DMI in α -Fe2O3 is the eg orbitals, which are strongly hybridized with the 2 p orbitals of oxygen atoms. The results demonstrate the importance of RIXS-MCD for identifying the electronic structure related to DMI.

All-dielectric metasurface circular dichroism waveplate

PubMed Central

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

2017-01-01

We propose and experimentally demonstrate a high efficient circularly polarizing dichroism waveplate (CPDW) using a Si-based all-dielectric 2Dchiral metasurface. We demonstrate that the CPDW exhibits a unique dichroism in that it functions as a transmissive quarter waveplate for one of either left-or right-handed circularly polarized incident lightand a reflective mirror for the opposite polarization. The circular polarization dichroism (CPD = IRCP − ILCP) in transmission at wavelength ~1.5 μm reaches 97% and the extinction ratio (ER = IRCP/ILCP) is as high as 345:1. Experimental fabrications and measurements of the proposed all-dielectric metasurface are implemented and found to be in excellent agreement with the simulations. The proposed all-dielectric chiral metasurface is of advantages of high-dichroism, easy-fabrication and standard semiconductor fabrication techniques compatible, which could lead to enhanced security in fiber and free-space communications, as well as imaging and sensing applications for circularly polarized light with a highly integrated photonic platform. PMID:28139753

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

NASA Astrophysics Data System (ADS)

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

2017-06-01

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

All-dielectric metasurface circular dichroism waveplate.

PubMed

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

2017-01-31

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

Preferred site occupation of 3 d atoms in NixF e4 -xN (x =1 and 3) films revealed by x-ray absorption spectroscopy and magnetic circular dichroism

NASA Astrophysics Data System (ADS)

Takata, Fumiya; Ito, Keita; Takeda, Yukiharu; Saitoh, Yuji; Takanashi, Koki; Kimura, Akio; Suemasu, Takashi

2018-02-01

X-ray absorption spectroscopy (XAS) and x-ray magnetic circular dichroism measurements were performed at the Ni and Fe L2 ,3 absorption edges for N ixF e4 -xN (x =1 and 3) epitaxial films. Spectral line-shape analysis and element-specific magnetic moment evaluations are presented. Shoulders at approximately 2 eV above the Ni L2 ,3 main peaks in the XAS spectrum of N i3FeN were interpreted to originate from hybridization of orbitals between Ni 3 d at face-centered (II) sites and N 2 p at body-centered sites, while such features were missing in NiF e3N film. Similar shoulders were observed at Fe L2 ,3 edges in both films. These results indicate that the orbitals of Ni atoms did not hybridize with those of N atoms in the NiF e3N film. Hence, Ni atoms preferentially occupied corner (I) sites, where the hybridization was weak because of the relatively long distance between Ni at I sites and N atoms. The relatively large magnetic moment deduced from sum-rule analysis of NiF e3N also showed a good agreement with the presence of Ni atoms at I sites.

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

NASA Astrophysics Data System (ADS)

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

2017-10-01

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

Soft x-ray spectromicroscopy using compact scanning transmission x-ray microscope at the photon factory

DOE Office of Scientific and Technical Information (OSTI.GOV)

Takeichi, Yasuo, E-mail: yasuo.takeichi@kek.jp; Inami, Nobuhito; Ono, Kanta

We report the stability and recent performances of a new type of scanning transmission X-ray microscopy. The optics and compact design of the microscope realized mobility and robust performance. Detailed consideration to the vibration control will be described. The insertion device upgraded to elliptical polarization undulator enabled linear dichroism and circular dichroism experiments.

Element-specific observation of the ferromagnetic ordering process in UCoAl via soft x-ray magnetic circular dichroism

NASA Astrophysics Data System (ADS)

Takeda, Yukiharu; Saitoh, Yuji; Okane, Tetsuo; Yamagami, Hiroshi; Matsuda, Tatsuma D.; Yamamoto, Etsuji; Haga, Yoshinori; Ōnuki, Yoshichika

2018-05-01

We have performed soft x-ray magnetic circular dichroism (XMCD) experiments on the itinerant-electron metamagnet UCoAl at the U 4 d -5 f (N4 ,5) and Co 2 p -3 d (L2 ,3) absorption edges in order to investigate the magnetic properties of the U 5 f and Co 3 d electrons separately. From the line shape of the XMCD spectrum, it is deduced that the orbital magnetic moment of the Co 3 d electrons is unusually large. Through the systematic temperature (T )- and magnetic field (H )-dependent XMCD measurements, we have obtained two types of the magnetization curve as a function of H and T (M-H curve and M-T curve, respectively). The metamagnetic transition from a paramagnetic state to a field-induced ferromagnetic state was clearly observed under 15 K at HM. The value of the HM and its T dependence agree well between the U and Co sites, and the bulk magnetization. Whereas, we have discovered the remarkable differences in the M-H and M-T curves between the U and Co sites. The present findings clearly show that the role of the Co 3 d electrons should be considered more carefully in order to understand the origin of the magnetic ordering in UCoAl.

Generation of circularly polarized XUV and soft-x-ray high-order harmonics by homonuclear and heteronuclear diatomic molecules subject to bichromatic counter-rotating circularly polarized intense laser fields

NASA Astrophysics Data System (ADS)

Heslar, John; Telnov, Dmitry A.; Chu, Shih-I.

2017-12-01

Recently, studies of bright circularly polarized high-harmonic beams from atoms in the soft-x-ray region as a source for x-ray magnetic circular dichroism measurement in a tabletop-scale setup have received considerable attention. In this paper, we address the problem with molecular targets and perform a detailed quantum study of H2 +, CO, and N2 molecules in bichromatic counter-rotating circularly polarized laser fields where we adopt wavelengths (1300 and 790 nm) and intensities (2 ×1014W /cm2 ) reported in a recent experiment [Proc. Natl. Acad. Sci. USA 112, 14206 (2015), 10.1073/pnas.1519666112]. Our treatment of multiphoton processes in homonuclear and heteronuclear diatomic molecules is nonperturbative and based on the time-dependent density-functional theory for multielectron systems. The calculated radiation spectrum contains doublets of left and right circularly polarized harmonics with high-energy photons in the XUV and soft-x-ray ranges. Our results reveal intriguing and substantially different nonlinear optical responses for homonuclear and heteronuclear diatomic molecules subject to circularly polarized intense laser fields. We study in detail the below- and above-threshold harmonic regions and analyze the ellipticity and phase of the generated harmonic peaks.

X-ray magnetic circular dichroism in d and f ferromagnetic materials: recent theoretical progress. Part II (Review Article)

NASA Astrophysics Data System (ADS)

Antonov, V. N.; Shpak, A. P.; Yaresko, A. N.

2008-02-01

The present state of theoretical understanding of the x-ray magnetic circular dichroism (XMCD) of 4f and 5f compounds is reviewed. Energy band theory based upon the local spin-density approximation (LSDA) describes the XMCD spectra of transition metal compounds with high accuracy. However, the LSDA does not suffice for lanthanide compounds which have a correlated 4f shell. A satisfactory description of the XMCD spectra could be obtained by using a generalization of the LSDA, in which explicitly f electron Coulomb correlations are taken into account (LSDA +U approach). As examples of this group we consider the compound GdN. We also consider uranium 5f compounds. In those compounds where the 5f electrons are rather delocalized, the LSDA describes the XMCD spectra reasonably well. As an example of this group we consider UFe2. Particular differences occur for uranium compounds in which the 5f electrons are neither delocalized nor localized, but more or less semilocalized. Typical examples are UXAl (X =Co, Rh, and Pt), and UX (X =S, Se, Te). However, the semilocalized 5f's are not inert, but their interaction with conduction electrons plays an important role. We also consider the electronic structure and XMCD spectra of the heavy-fermion compounds UPt3, URu2Si2, UPd2Al3, UNi2Al3, and UBe13, where the degree of the 5f localization is increased in comparison with other uranium compounds. The electronic structure and XMCD spectra of UGe2 which possesses simultaneously ferromagnetism and superconductivity also presented. Recently achieved improvements for describing 5f compounds are discussed.

Photoexcitation circular dichroism in chiral molecules

NASA Astrophysics Data System (ADS)

Beaulieu, S.; Comby, A.; Descamps, D.; Fabre, B.; Garcia, G. A.; Géneaux, R.; Harvey, A. G.; Légaré, F.; Mašín, Z.; Nahon, L.; Ordonez, A. F.; Petit, S.; Pons, B.; Mairesse, Y.; Smirnova, O.; Blanchet, V.

2018-05-01

Chiral effects appear in a wide variety of natural phenomena and are of fundamental importance in science, from particle physics to metamaterials. The standard technique of chiral discrimination—photoabsorption circular dichroism—relies on the magnetic properties of a chiral medium and yields an extremely weak chiral response. Here, we propose and demonstrate an orders of magnitude more sensitive type of circular dichroism in neutral molecules: photoexcitation circular dichroism. This technique does not rely on weak magnetic effects, but takes advantage of the coherent helical motion of bound electrons excited by ultrashort circularly polarized light. It results in an ultrafast chiral response and the efficient excitation of a macroscopic chiral density in an initially isotropic ensemble of randomly oriented chiral molecules. We probe this excitation using linearly polarized laser pulses, without the aid of further chiral interactions. Our time-resolved study of vibronic chiral dynamics opens a way to the efficient initiation, control and monitoring of chiral chemical change in neutral molecules at the level of electrons.

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

NASA Astrophysics Data System (ADS)

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.

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

PubMed

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

2014-03-01

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

Terahertz circular dichroism spectroscopy of biomolecules

NASA Astrophysics Data System (ADS)

Xu, Jing; Galan, Jhenny; Ramian, Gerald; Savvidis, Pavlos; Scopatz, Anthony; Birge, Robert R.; Allen, S. James; Plaxco, Kevin

2004-02-01

Biopolymers such as proteins, DNA and RNA fold into large, macromolecular chiral structures. As charged macromolecules, they absorb strongly in the terahertz due to large-scale collective vibrational modes; as chiral objects, this absorption should be coupled with significant circular dichroism. Terahertz circular dichroism (TCD) is potentially important as a biospecific sensor, unobscured by spectral features related to abiological material. We have constructed atomistic simulations and elastic continuum models of TCD. These models estimate the magnitude of the TCD and the relation between TCD spectroscopic signatures (zero crossings) and the structure, charge distribution and mechanical properties of biomaterials. A broad band TCD spectrometer based on a polarizing interferometer is developed to explore TCD in biomolecules in aqueous solution. Preliminary results on TCD in lysozyme in water at several terahertz frequencies is presented.

Circular dichroism in photoelectron images from aligned nitric oxide molecules

DOE PAGES

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

2017-05-03

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

Circular dichroism in photoelectron images from aligned nitric oxide molecules

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

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

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

PubMed Central

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

2016-01-01

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 Fe2+ ions by Co2+ 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

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

PubMed

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

2016-08-01

The biomineralization of magnetite nanocrystals (called magnetosomes) by magnetotactic bacteria (MTB) has attracted intense interest in biology, geology and materials science due to the precise morphology of the particles, the chain-like assembly and their unique magnetic properties. Great efforts have been recently made in producing transition metal-doped magnetosomes with modified magnetic properties for a range of applications. Despite some successful outcomes, the coordination chemistry and magnetism of such metal-doped magnetosomes still remain largely unknown. Here, we present new evidences from X-ray magnetic circular dichroism (XMCD) for element- and site-specific magnetic analyses that cobalt is incorporated in the spinel structure of the magnetosomes within Magnetospirillum magneticum AMB-1 through the replacement of Fe(2+) ions by Co(2+) ions in octahedral (Oh) sites of magnetite. Both XMCD at Fe and Co L2,3 edges, and energy-dispersive X-ray spectroscopy on transmission electron microscopy analyses reveal a heterogeneous distribution of cobalt occurring either in different particles or inside individual particles. Compared with non-doped one, cobalt-doped magnetosome sample has lower Verwey transition temperature and larger magnetic coercivity, related to the amount of doped cobalt. This study also demonstrates that the addition of trace cobalt in the growth medium can significantly improve both the cell growth and the magnetosome formation within M. magneticum AMB-1. Together with the cobalt occupancy within the spinel structure of magnetosomes, this study indicates that MTB may provide a promising biomimetic system for producing chains of metal-doped single-domain magnetite with an appropriate tuning of the magnetic properties for technological and biomedical applications. © 2016 The Author(s).

Photoinduced molecular chirality probed by ultrafast resonant X-ray spectroscopy

DOE PAGES

Rouxel, Jérémy R.; Kowalewski, Markus; Mukamel, Shaul

2017-07-01

Recently developed circularly polarized X-ray light sources can probe the ultrafast chiral electronic and nuclear dynamics through spatially localized resonant core transitions. Here, we present simulations of time-resolved circular dichroism signals given by the difference of left and right circularly polarized X-ray probe transmission following an excitation by a circularly polarized optical pump with the variable time delay. Application is made to formamide which is achiral in the ground state and assumes two chiral geometries upon optical excitation to the first valence excited state. Probes resonant with various K-edges (C, N, and O) provide different local windows onto the paritymore » breaking geometry change thus revealing the enantiomer asymmetry.« less

Photoinduced molecular chirality probed by ultrafast resonant X-ray spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rouxel, Jérémy R.; Kowalewski, Markus; Mukamel, Shaul

Recently developed circularly polarized X-ray light sources can probe the ultrafast chiral electronic and nuclear dynamics through spatially localized resonant core transitions. Here, we present simulations of time-resolved circular dichroism signals given by the difference of left and right circularly polarized X-ray probe transmission following an excitation by a circularly polarized optical pump with the variable time delay. Application is made to formamide which is achiral in the ground state and assumes two chiral geometries upon optical excitation to the first valence excited state. Probes resonant with various K-edges (C, N, and O) provide different local windows onto the paritymore » breaking geometry change thus revealing the enantiomer asymmetry.« less

Terahertz Absorption and Circular Dichroism Spectroscopy of Solvated Biopolymers

NASA Astrophysics Data System (ADS)

Xu, Jing; Plaxco, Kevin; Allen, S. James

2006-03-01

Biopolymers are expected to exhibit broad spectral features in the terahertz frequency range, corresponding to their functionally relevant, global and sub-global collective vibrational modes with ˜ picosecond timescale. Recent advances in terahertz technology have stimulated researchers to employ terahertz absorption spectroscopy to directly probe these postulated collective modes. However, these pioneering studies have been limited to dry and, at best, moist samples. Successful isolation of low frequency vibrational activities of solvated biopolymers in their natural water environment has remained elusive, due to the overwhelming attenuation of the terahertz radiation by water. Here we have developed a terahertz absorption and circular dichroism spectrometer suitable for studying biopolymers in biologically relevant water solutions. We have precisely isolated, for the first time, the terahertz absorption of solvated prototypical proteins, Bovine Serum Albumin and Lysozyme, and made important direct comparison to the existing molecular dynamic simulations and normal mode calculations. We have also successfully demonstrated the magnetic circular dichroism in semiconductors, and placed upper bounds on the terahertz circular dichroism signatures of prototypical proteins in water solution.

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

PubMed

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

2013-12-21

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

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lehmann, C. Stefan; Ram, N. Bhargava; Janssen, Maurice H. M., E-mail: m.h.m.janssen@vu.nl

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-flightmore » 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

Near shot-noise limited time-resolved circular dichroism pump-probe spectrometer

NASA Astrophysics Data System (ADS)

Stadnytskyi, Valentyn; Orf, Gregory S.; Blankenship, Robert E.; Savikhin, Sergei

2018-03-01

We describe an optical near shot-noise limited time-resolved circular dichroism (TRCD) pump-probe spectrometer capable of reliably measuring circular dichroism signals in the order of μdeg with nanosecond time resolution. Such sensitivity is achieved through a modification of existing TRCD designs and introduction of a new data processing protocol that eliminates approximations that have caused substantial nonlinearities in past measurements and allows the measurement of absorption and circular dichroism transients simultaneously with a single pump pulse. The exceptional signal-to-noise ratio of the described setup makes the TRCD technique applicable to a large range of non-biological and biological systems. The spectrometer was used to record, for the first time, weak TRCD kinetics associated with the triplet state energy transfer in the photosynthetic Fenna-Matthews-Olson antenna pigment-protein complex.

A novel x-ray circularly polarized ranging method

NASA Astrophysics Data System (ADS)

Song, Shi-Bin; Xu, Lu-Ping; Zhang, Hua; Gao, Na; Shen, Yang-He

2015-05-01

Range measurement has found multiple applications in deep space missions. With more and further deep space exploration activities happening now and in the future, the requirement for range measurement has risen. In view of the future ranging requirement, a novel x-ray polarized ranging method based on the circular polarization modulation is proposed, termed as x-ray circularly polarized ranging (XCPolR). XCPolR utilizes the circular polarization modulation to process x-ray signals and the ranging information is conveyed by the circular polarization states. As the circular polarization states present good stability in space propagation and x-ray detectors have light weight and low power consumption, XCPolR shows great potential in the long-distance range measurement and provides an option for future deep space ranging. In this paper, we present a detailed illustration of XCPolR. Firstly, the structure of the polarized ranging system is described and the signal models in the ranging process are established mathematically. Then, the main factors that affect the ranging accuracy, including the Doppler effect, the differential demodulation, and the correlation error, are analyzed theoretically. Finally, numerical simulation is carried out to evaluate the performance of XCPolR. Projects supported by the National Natural Science Foundation of China (Grant Nos. 61172138 and 61401340), the Natural Science Basic Research Plan in Shaanxi Province of China (Grant No. 2013JQ8040), the Research Fund for the Doctoral Program of Higher Education of China (Grant No. 20130203120004), the Open Research Fund of the Academy of Satellite Application, China (Grant No. 2014 CXJJ-DH 12), the Xi’an Science and Technology Plan, China (Grant No. CXY1350(4)), the Fundamental Research Funds for the Central Universities, China (Grant Nos. 201413B, 201412B, and JB141303), and the Open Fund of Key Laboratory of Precision Navigation and Timing Technology, National Time Service Center, Chinese

Investigation of a Spin Transition in a LaCoO3 Single Crystal by the Method of X-Ray Magnetic Circular Dichroism at the Cobalt K- and L 2,3-Edges

NASA Astrophysics Data System (ADS)

Sikolenko, V. V.; Troyanchuk, I. O.; Karpinsky, D. V.; Rogalev, A.; Wilhelm, F.; Rosenberg, R.; Prabhakaran, D.; Efimova, E. A.; Efimov, V. V.; Tiutiunnikov, S. I.; Bobrikov, I. A.

2018-02-01

Spin transitions of cobalt ions in LaCoO3 single crystals have been studied by the method of X-ray magnetic circular dichroism (XMCD) at the K- and L 2,3-edges of Co3+ ions. The orbital momentum of cobalt ions obtained for the K-edge at the 3 d level in the region of the spin transition in the temperature range from 25 to 120 K increases by a factor of approximately 1.6, whereas the slope of the magnetization curve value in the same temperature range and magnetic field increases by a factor of more than 10. XMCD experiments at the cobalt L 2,3-edges demonstrate gradual growth of the ratio of the orbital momentum to the spin one L/ S from 0.48 to 0.53 in the temperature range from 60 K to 120 K.

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

PubMed Central

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

2016-01-01

Optical activity and circular dichroism are fascinating physical phenomena originating from the interaction of light with chiral molecules or other nano objects lacking mirror symmetries in three-dimensional (3D) space. While chiral optical properties are weak in most of naturally occurring materials, they can be engineered and significantly enhanced in synthetic optical media known as chiral metamaterials, where the spatial symmetry of their building blocks is broken on a nanoscale. Although originally discovered in 3D structures, circular dichroism can also emerge in a two-dimensional (2D) metasurface. The origin of the resulting circular dichroism is rather subtle, and is related to non-radiative (Ohmic) dissipation of the constituent metamolecules. Because such dissipation occurs on a nanoscale, this effect has never been experimentally probed and visualized. Using a suite of recently developed nanoscale-measurement tools, we establish that the circular dichroism in a nanostructured metasurface occurs due to handedness-dependent Ohmic heating. PMID:27329108

Determination of protein-dye association by near infrared fluorescence-detected circular dichroism.

PubMed

Meadows, F; Narayanan, N; Patonay, G

2000-01-10

Near-infrared (NIR) squarylium dye spectral properties were evaluated by absorption, fluorescence, circular dichroism (CD), and fluorescence-detected circular dichroism (FDCD). Substituents of the two NN dyes differed at R(1) and R(2), located symmetrically on the chromophore. The side chains of NN525 are R(1)=hexanoic acid, R(2)=butyl sulfonate and R(1)=R(2)=ethyl for NN127. FDCD signals were first confirmed by denaturing BSA with 2-8 M urea showing a diminution of dye FDCD peaks, but no change occurred in spectral properties of the dyes in urea. This indicated that the observed cotton effects occurred by noncovalent interactions with the secondary structure of the protein. The average BSA-dye association constants found by fluorescence, absorbance, and FDCD were 1.27 x 10(6) (n=1) and 3.3 x 10(6) M(-1) (n=1) for NN127 and NN525 respectively. These values were in good agreement when calculated by the three spectroscopic methods validating the use of NIRFDCD for optical parameter calculations. These results are useful to describe NIR squarylium dye labeling of BSA.

Probing ultrafast spin dynamics with high-harmonic magnetic circular dichroism spectroscopy

NASA Astrophysics Data System (ADS)

Willems, F.; Smeenk, C. T. L.; Zhavoronkov, N.; Kornilov, O.; Radu, I.; Schmidbauer, M.; Hanke, M.; von Korff Schmising, C.; Vrakking, M. J. J.; Eisebitt, S.

2015-12-01

Magnetic circular dichroism in the extreme ultraviolet (XUV) spectral range is a powerful technique for element-specific probing of magnetization in multicomponent magnetic alloys and multilayers. We combine a high-harmonic generation source with a λ /4 phase shifter to obtain circularly polarized XUV femtosecond pulses for ultrafast magnetization studies. We report on simultaneously measured resonant magnetic circular dichroism (MCD) of Co and Ni at their respective M2 ,3 edges and of Pt at its O edge, originating from interface magnetism. We present a time-resolved MCD absorption measurement of a thin magnetic Pt/Co/Pt film, showing simultaneous demagnetization of Co and Pt on a femtosecond time scale.

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

PubMed

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

2018-01-01

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

Amide I vibrational circular dichroism of dipeptide: Conformation dependence and fragment analysis

NASA Astrophysics Data System (ADS)

Choi, Jun-Ho; Cho, Minhaeng

2004-03-01

The amide I vibrational circular dichroic response of alanine dipeptide analog (ADA) was theoretically investigated and the density functional theory calculation and fragment analysis results are presented. A variety of vibrational spectroscopic properties, local and normal mode frequencies, coupling constant, dipole, and rotational strengths, are calculated by varying two dihedral angles determining the three-dimensional ADA conformation. Considering two monopeptide fragments separately, we show that the amide I vibrational circular dichroism of the ADA can be quantitatively predicted. For several representative conformations of the model ADA, vibrational circular dichroism spectra are calculated by using both the density functional theory calculation and fragment analysis methods.

Quantized Rabi oscillations and circular dichroism in quantum Hall systems

NASA Astrophysics Data System (ADS)

Tran, D. T.; Cooper, N. R.; Goldman, N.

2018-06-01

The dissipative response of a quantum system upon periodic driving can be exploited as a probe of its topological properties. Here we explore the implications of such phenomena in two-dimensional gases subjected to a uniform magnetic field. It is shown that a filled Landau level exhibits a quantized circular dichroism, which can be traced back to its underlying nontrivial topology. Based on selection rules, we find that this quantized effect can be suitably described in terms of Rabi oscillations, whose frequencies satisfy simple quantization laws. We discuss how quantized dissipative responses can be probed locally, both in the bulk and at the boundaries of the system. This work suggests alternative forms of topological probes based on circular dichroism.

Electronic structure and x-ray spectroscopy of Cu2MnAl1-xGax

NASA Astrophysics Data System (ADS)

Rai, D. P.; Ekuma, C. E.; Boochani, A.; Solaymani, S.; Thapa, R. K.

2018-04-01

We explore the electronic and related properties of Cu2MnAl1-xGax with a first-principles, relativistic multiscattering Green function approach. We discuss our results in relation to existing experimental data and show that the electron-core hole interaction is essential for the description of the optical spectra especially in describing the X-ray absorption and magnetic circular dichroism spectra at the L2,3 edges of Cu and Mn.

Iron L2,3-Edge X-ray Absorption and X-ray Magnetic Circular Dichroism Studies of Molecular Iron Complexes with Relevance to the FeMoco and FeVco Active Sites of Nitrogenase

PubMed Central

2017-01-01

Herein, a systematic study of a series of molecular iron model complexes has been carried out using Fe L2,3-edge X-ray absorption (XAS) and X-ray magnetic circular dichroism (XMCD) spectroscopies. This series spans iron complexes of increasing complexity, starting from ferric and ferrous tetrachlorides ([FeCl4]−/2–), to ferric and ferrous tetrathiolates ([Fe(SR)4]−/2–), to diferric and mixed-valent iron–sulfur complexes [Fe2S2R4]2–/3–. This test set of compounds is used to evaluate the sensitivity of both Fe L2,3-edge XAS and XMCD spectroscopy to oxidation state and ligation changes. It is demonstrated that the energy shift and intensity of the L2,3-edge XAS spectra depends on both the oxidation state and covalency of the system; however, the quantitative information that can be extracted from these data is limited. On the other hand, analysis of the Fe XMCD shows distinct changes in the intensity at both L3 and L2 edges, depending on the oxidation state of the system. It is also demonstrated that the XMCD intensity is modulated by the covalency of the system. For mononuclear systems, the experimental data are correlated with atomic multiplet calculations in order to provide insights into the experimental observations. Finally, XMCD is applied to the tetranuclear heterometal–iron–sulfur clusters [MFe3S4]3+/2+ (M = Mo, V), which serve as structural analogues of the FeMoco and FeVco active sites of nitrogenase. It is demonstrated that the XMCD data can be utilized to obtain information on the oxidation state distribution in complex clusters that is not readily accessible for the Fe L2,3-edge XAS data alone. The advantages of XMCD relative to standard K-edge and L2,3-edge XAS are highlighted. This study provides an important foundation for future XMCD studies on complex (bio)inorganic systems. PMID:28653855

A magnetic and electronic circular dichroism study of azurin, plastocyanin, cucumber basic protein, and nitrite reductase based on time-dependent density functional theory calculations.

PubMed

Zhekova, Hristina R; Seth, Michael; Ziegler, Tom

2010-06-03

The excitation, circular dichroism, magnetic circular dichroism (MCD) and electron paramagnetic resonance (EPR) spectra of small models of four blue copper proteins are simulated on the TDDFT/BP86 level. X-Ray diffraction geometries are used for the modeling of the blue copper sites in azurin, plastocyanin, cucumber basic protein, and nitrite reductase. Comparison with experimental data reveals that the calculations reproduce most of the qualitative trends of the observed experimental spectra with some discrepancies in the orbital decompositions and the values of the excitation energies, the g( parallel) components of the g tensor, and the components of the A tensor. These discrepancies are discussed relative to deficiencies in the time-dependent density functional theory (TDDFT) methodology, as opposed to previous studies which address them as a result of insufficient model size or poor performance of the BP86 functional. In addition, attempts are made to elucidate the correlation between the MCD and EPR signals.

Tuning the hybridization and magnetic ground state of electron and hole doped CeOs2Al10 : An x-ray spectroscopy study

NASA Astrophysics Data System (ADS)

Chen, Kai; Sundermann, Martin; Strigari, Fabio; Kawabata, Jo; Takabatake, Toshiro; Tanaka, Arata; Bencok, Peter; Choueikani, Fadi; Severing, Andrea

2018-04-01

Here we present linear and circular polarized soft x-ray absorption spectroscopy (XAS) data at the Ce M4 ,5 edges of the electron (Ir) and hole-doped (Re) Kondo semiconductor CeOs2Al10 . Both substitutions have a strong impact on the unusual high Néel temperature TN=28.5 K, and also the direction of the ordered moment in case of Ir. The substitution dependence of the linear dichroism is weak thus validating the crystal-field description of CeOs2Al10 being representative for the Re and Ir substituted compounds. The impact of electron and hole doping on the hybridization between conduction and 4 f electrons is related to the amount of f0 in the ground state and reduction of x-ray magnetic circular dichroism. A relationship of c f -hybridization strength and enhanced TN is discussed. The direction and doping dependence of the circular dichroism strongly supports the idea of strong Kondo screening along the crystallographic a direction.

Spin and orbital magnetic moments of Fe and Co in Co/Fe and Fe/Co multilayers on Si from L2,3 edge X-ray Magnetic Circular Dichroism Spectroscopy

NASA Astrophysics Data System (ADS)

Vemuru, Krishnamurthy; Rosenberg, Richard; Mankey, Gary

Nanostructured FeCo thin films are interesting for magnetic recording applications due to their high saturation magnetization, high Curie temperature and low magnetocrystalline anisotropy. It is desirable to know how the magnetism is modified by the nanostructrure. We report Fe L 2 , 3 edge and Co L2 , 3 edge x-ray magnetic circular dichroism (XMCD) investigations of element specific spin and orbital magnetism of Fe and Co in two multilayer samples: (S1) Si/SiO2/[Co 0.8 nm/Fe 1.6 nm]x32/W (2nm) and (S2) Si/SiO2/[Co 1.6 nm/Fe 0.8 nm]x32/W (2nm) thin films at room temperature. Sum rule analysis of XMCD at Fe L2 , 3 edge in sample S1 shows that the orbital moment of Fe is strongly enhanced and the spin moment is strongly reduced as compared to the values found in bulk Fe. Details of sum rule analysis will be presented to compare and contrast spin magnetic moments and orbital magnetic moments of Fe and Co in the two multilayer samples. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357.

Salts employed in hydrophobic interaction chromatography can change protein structure - insights from protein-ligand interaction thermodynamics, circular dichroism spectroscopy and small angle X-ray scattering.

PubMed

Komaromy, Andras Z; Kulsing, Chadin; Boysen, Reinhard I; Hearn, Milton T W

2015-03-01

Key requirements of protein purification by hydrophobic interaction chromatography (HIC) are preservation of the tertiary/quaternary structure, maintenance of biological function, and separation of the correctly folded protein from its unfolded forms or aggregates. This study examines the relationship between the HIC retention behavior of hen egg white lysozyme (HEWL) in high concentrations of several kosmotropic salts and its conformation, assessed by circular dichroism (CD) spectroscopy. Further, the physicochemical properties of HEWL in the presence of high concentrations of ammonium sulfate, sodium chloride and magnesium chloride were investigated by small angle X-ray scattering (SAXS) at different temperatures. Radii of gyration were extrapolated from Guinier approximations and the indirect transform program GNOM with protein-protein interaction and contrast variation taken into account. A bead model simulation provided information on protein structural changes using ab initio reconstruction with GASBOR. These results correlated to the secondary structure content obtained from CD spectroscopy of HEWL. These changes in SAXS and CD data were consistent with heat capacity ΔCp -values obtained from van't Hoff plot analyses of the retention data. Collectively, these insights enable informed decisions to be made on the choice of chromatographic conditions, leading to improved separation selectivity and opportunities for innovative column-assisted protein refolding methods. Copyright © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enantiomeric resolution and X-ray optical activity of a tricobalt extended metal atom chain.

PubMed

Srinivasan, Anandi; Cortijo, Miguel; Bulicanu, Vladimir; Naim, Ahmad; Clérac, Rodolphe; Sainctavit, Philippe; Rogalev, Andrei; Wilhelm, Fabrice; Rosa, Patrick; Hillard, Elizabeth A

2018-02-07

A simple procedure based on anion exchange was employed for the enantiomeric resolution of the extended metal atom chain (EMAC) [Co 3 (dpa) 4 (MeCN) 2 ] 2+ . Use of the chiral salt (NBu 4 ) 2 [As 2 (tartrate) 2 ], (Λ- 1 or Δ- 1 ), resulted in the selective crystallization of the EMAC enantiomers as [Δ-Co 3 (dpa) 4 (MeCN) 2 ](NBu 4 ) 2 [Λ-As 2 (tartarte) 2 ] 2 , (Δ- 2 ) and [Λ-Co 3 (dpa) 4 (MeCN) 2 ](NBu 4 ) 2 [Δ-As 2 (tartrate) 2 ] 2 (Λ- 2 ), respectively, in the P 42 1 2 space group, whereas a racemic mixture of 1 yielded [Co 3 (dpa) 4 (MeCN) 2 ][As 2 (tartrate) 2 ]·2MeCN ( rac - 3 ), which crystallized in the C 2/ c space group. The local electronic and magnetic structure of the EMAC enantiomers was studied, exploiting a variety of dichroisms in single crystals. A strong linear dichroism at the Co K-edge was observed in the orthoaxial configuration, whereas it vanished in the axial orientation, thus spectroscopically confirming the D 4 crystal symmetry. Compounds Δ- 2 and Λ- 2 are shown to be enantiopure materials as evidenced by mirror-image natural circular dichroism spectra in the UV/vis in solution and in the X-ray range at the Co K-edge in single crystals. The surprising absence of detectable X-ray magnetic circular dichroism or X-ray magnetochiral dichroism signals at the Co K-edge, even at low temperature (3 K) and a high magnetic field (17 T), is ascribed to a strongly delocalized spin density on the tricobalt core.

Conformational effects in photoelectron circular dichroism

NASA Astrophysics Data System (ADS)

Turchini, S.

2017-12-01

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

Characterization of CaMn2O4 By X-Ray Magnetic Linear Dichroism

NASA Astrophysics Data System (ADS)

Holroyd, Johnathon; Bhatkar, Harshawardhan; Arenholz, Elke; White, Ben; Neumeier, John; Idzerda, Yves

2008-05-01

Perovskite manganite such as LaxCa(1-x)MnO3 (LCMO) have recently drawn attention for their useful electronic and magnetic properties such as Colossal Magnetoresistance. It has been shown that under stress, LCMO thin films show changes in La and Ca concentrations near the interface. One potential impurity under La depleted conditions is antiferromagnetic CaMn2O4. In order to better understand the range of properties available within LCMO systems, it is important to be able to identify and characterize CaMn2O4 within LCMO thin films. X-ray absorption spectroscopy (XAS) and X-ray magnetic linear dichroism (XMLD) are well suited to this task due to their element specificity, sensitivity, and ability to characterize the measure the magnetic properties of antiferromagnetic systems. XAS and XMLD were measured on high quality single crystals of CaMn2O4. These spectra are distinguished from CaMnO3 and demonstrate antiferromagnetic structure.

Measurement of the Circular Dichroism of Electronic Transitions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sutherland, J.C.

2010-08-11

This chapter describes the measurement of circular dichroism (CD) for absorption due to transitions between two distinct electronic states. This is distinguished from absorption of lower energy photons, which are associated with changes of only the vibrational modes of the absorber and from the absorption of higher energy photons, which may result in ionizations. From the instrumental viewpoint, the chapter describes the measurement of CD that can be recorded using a photomultiplier or avalanche photodiode to quantify the intensity of a light beam, a photoelastic modulator to periodically alter the beam's polarization, and a monochromator located between the light sourcemore » and the modulator. Using either criterion, the focus is on the spectral domain spanning about a decade in wavelength (photon energy) from roughly 1.2 {micro}m (1 eV {approx} 160 zJ) in the near infrared to 120 nm (10 eV {approx} 1.6 aJ) in the vacuum ultraviolet (VUV). In the near infrared, there is overlap between the domain of electronic and purely vibrational transitions, the use of photomultipliers or avalanche photodiodes versus solid state detectors and dispersive versus Fourier-transform spectrometers. There is also some overlap in the VUV with synchrotron beamlines that use arrays of magnets called 'insertion devices' to cause the emitted synchrotron radiation to be elliptically polarized. To my knowledge, no single spectrometer spans this entire spectral domain discussed here, and the vast majority of laboratory instruments come nowhere close to either the upper or lower limit. However, similar analytical approaches and types of instrumentation are employed throughout this spectral domain and thus are logically treated together. The focus in this chapter is on the measurement of CD resulting from the inherent chirality of the absorbing system. Several spectroscopic methods that are closely related in terms of science or instrumentation are treated in other chapters. These include

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

1997-04-01

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

Circular dichroism in photo-single-ionization of unoriented atoms.

PubMed

Feagin, James M

2002-01-28

We predict circular dichroism in photo-single-ionization angular distributions from spherically symmetric atomic states if the ionized electron is detected using two-slit interferometry. We demonstrate that the resulting electron interference pattern captures phase information on quadrupole corrections to the photoionization amplitude lost in conventional angular distributions.

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

NASA Astrophysics Data System (ADS)

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

2013-04-01

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

UV-CD12: synchrotron radiation circular dichroism beamline at ANKA

PubMed Central

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

2015-01-01

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

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

ERIC Educational Resources Information Center

Abriata, Luciano A.

2011-01-01

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

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

NASA Astrophysics Data System (ADS)

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

1991-06-01

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

Determination of the ground state of an Au-supported FePc film based on the interpretation of Fe K - and L -edge x-ray magnetic circular dichroism measurements

NASA Astrophysics Data System (ADS)

Natoli, Calogero R.; Krüger, Peter; Bartolomé, Juan; Bartolomé, Fernando

2018-04-01

We determine the magnetic ground state of the FePc molecule on Au-supported thin films based on the observed values of orbital anisotropy and spectroscopic x-ray magnetic circular dichroism (XMCD) measurements at the Fe K and L edges. Starting from ab initio molecular orbital multiplet calculations for the isolated molecule, we diagonalize the spin-orbit interaction in the subspace spanned by the three lowest spin triplet states of 3A2 g and 3Eg symmetry in the presence of a saturating magnetic field at a polar angle θ with respect to the normal to the plane of the film, plus an external perturbation representing the effect of the molecules in the stack on the FePc molecule under consideration. We find that the orbital moment of the ground state strongly depends on the magnetic field direction in agreement with the sum rule analysis of the L23-edge XMCD data. We calculate integrals over the XMCD spectra at the Fe K and L23 edges as used in the sum rules and explicitly show that they agree with the expectation values of the orbital moment and effective spin moment of the ground state. On the basis of this analysis, we can rule out alternative candidates proposed in the literature.

Analysis of protein circular dichroism spectra for secondary structure using a simple matrix multiplication.

PubMed

Compton, L A; Johnson, W C

1986-05-15

Inverse circular dichroism (CD) spectra are presented for each of the five major secondary structures of proteins: alpha-helix, antiparallel and parallel beta-sheet, beta-turn, and other (random) structures. The fraction of the each secondary structure in a protein is predicted by forming the dot product of the corresponding inverse CD spectrum, expressed as a vector, with the CD spectrum of the protein digitized in the same way. We show how this method is based on the construction of the generalized inverse from the singular value decomposition of a set of CD spectra corresponding to proteins whose secondary structures are known from X-ray crystallography. These inverse spectra compute secondary structure directly from protein CD spectra without resorting to least-squares fitting and standard matrix inversion techniques. In addition, spectra corresponding to the individual secondary structures, analogous to the CD spectra of synthetic polypeptides, are generated from the five most significant CD eigenvectors.

Bright Linearly and Circularly Polarized Extreme Ultraviolet and Soft X-ray High Harmonics for Absorption Spectroscopy

NASA Astrophysics Data System (ADS)

Fan, Tingting

High harmonic generation (HHG) is an extreme nonlinear optical process. When implemented in a phase-matched geometry, HHG coherent upconverts femtosecond laser light into coherent "X-ray laser" beams, while retaining excellent spatial and temporal coherence, as well as the polarization state of the driving laser. HHG has a tabletop footprint, with femtosecond to attosecond time resolution, combined with nanometer spatial resolution. As a consequence of these unique capabilities, HHG is now being widely adopted for use in molecular spectroscopy and imaging, materials science, as well as nanoimaging in general. In the first half of this thesis, I demonstrate high flux linearly polarized soft X-ray HHG, driven by a single-stage 10-mJ Ti:sapphire regenerative amplifier at a repetition rate of 1 kHz. I first down-converted the laser to 1.3 mum using an optical parametric amplifier, before up-converting it into the soft X-ray region using HHG in a high-pressure, phase-matched, hollow waveguide geometry. The resulting optimally phase-matched broadband spectrum extends to 200 eV, with a soft X-ray photon flux of > 106 photons/pulse/1% bandwidth at 1 kHz, corresponding to > 109 photons/s/1% bandwidth, or approximately a three orders-of-magnitude increase compared with past work. Using this broad bandwidth X-ray source, I demonstrated X-ray absorption spectroscopy of multiple elements and transitions in molecules in a single spectrum, with a spectral resolution of 0.25 eV, and with the ability to resolve the near edge fine structure. In the second half of this thesis, I discuss how to generate the first bright circularly polarized (CP) soft X-ray HHG and also use them to implement the first tabletop X-ray magnetic circular dichroism (XMCD) measurements. Using counter-rotating CP lasers at 1.3 mum and 0.79 mum, I generated CPHHG with photon energies exceeding 160 eV. The harmonic spectra emerge as a sequence of closely spaced pairs of left and right CP peaks, with energies

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

PubMed

Kamiński, Maciej; Cukras, Janusz; Pecul, Magdalena; Rizzo, Antonio; Coriani, Sonia

2015-07-15

We present a computational methodology to calculate the intensity of circular dichroism (CD) in spin-forbidden absorption and of circularly polarized phosphorescence (CPP) signals, a manifestation of the optical activity of the triplet-singlet transitions in chiral compounds. The protocol is based on the response function formalism and is implemented at the level of time-dependent density functional theory. It has been employed to calculate the spin-forbidden circular dichroism and circularly polarized phosphorescence signals of valence n → π* and n ← π* transitions, respectively, in several chiral enones and diketones. Basis set effects in the length and velocity gauge formulations have been explored, and the accuracy achieved when employing approximate (mean-field and effective nuclear charge) spin-orbit operators has been investigated. CPP is shown to be a sensitive probe of the triplet excited state structure. In many cases the sign of the spin-forbidden CD and CPP signals are opposite. For the β,γ-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.

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

PubMed

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

2017-01-04

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

Note: Soft X-ray transmission polarizer based on ferromagnetic thin films

NASA Astrophysics Data System (ADS)

Müller, L.; Hartmann, G.; Schleitzer, S.; Berntsen, M. H.; Walther, M.; Rysov, R.; Roseker, W.; Scholz, F.; Seltmann, J.; Glaser, L.; Viefhaus, J.; Mertens, K.; Bagschik, K.; Frömter, R.; De Fanis, A.; Shevchuk, I.; Medjanik, K.; Öhrwall, G.; Oepen, H. P.; Martins, M.; Meyer, M.; Grübel, G.

2018-03-01

A transmission polarizer for producing elliptically polarized soft X-ray radiation from linearly polarized light is presented. The setup is intended for use at synchrotron and free-electron laser beamlines that do not directly offer circularly polarized light for, e.g., X-ray magnetic circular dichroism (XMCD) measurements or holographic imaging. Here, we investigate the degree of ellipticity upon transmission of linearly polarized radiation through a cobalt thin film. The experiment was performed at a photon energy resonant to the Co L3-edge, i.e., 778 eV, and the polarization of the transmitted radiation was determined using a polarization analyzer that measures the directional dependence of photo electrons emitted from a gas target. Elliptically polarized radiation can be created at any absorption edge showing the XMCD effect by using the respective magnetic element.

Perfect Circular Dichroism in the Haldane Model

NASA Astrophysics Data System (ADS)

Ghalamkari, Kazu; Tatsumi, Yuki; Saito, Riichiro

2018-06-01

We theoretically show that perfect circular dichroism (CD) occurs in the Haldane model in which the two-dimensional (2D) material absorbs only either left-handed or right-handed circularly polarized light. Perfect CD occurs in the phase diagram of the Haldane model when the zero-field quantum Hall conductivity has a nonzero value. The coincidence of the occurrence of perfect CD and zero-field quantum Hall effect is attributed to the fact that the effect of broken time-reversal symmetry is larger than the effect of broken inversion symmetry. On the other hand, valley polarization and perfect CD occur exclusively in the phase diagram. Further, for the four regions of the phase diagram, pseudospin polarization occurs at the K and K' points in the hexagonal Brillouin zone with either the same sign or opposite sign for the K and K' points and for the valence and conduction bands. This theoretical prediction may have an impact on search for a new optical device that selects circularly polarized light controlled by the electric field.

Photoelectron circular dichroism in different ionization regimes

NASA Astrophysics Data System (ADS)

Wollenhaupt, Matthias

2016-12-01

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

Chiral surface waves for enhanced circular dichroism

NASA Astrophysics Data System (ADS)

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

2017-06-01

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

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

PubMed Central

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

2015-01-01

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

Magnetic circular dichroism of CdTe nanoparticles

NASA Astrophysics Data System (ADS)

Malakhovskii, A. V.; Sokolov, A. E.; Tsipotan, A. S.; Zharkov, S. M.; Zabluda, V. N.

2018-04-01

Magnetic circular dichroism (MCD) of water-soluble CdTe nanoparticles was observed in the visible spectral range for the first time. Diameter of nanoparticles varied from 2.3 to 4.5 nm. Absorption and photoluminescence spectra were also recorded. Absorption line at 19400 cm-1 and luminescent line at 18200 cm-1 were observed. Splitting of value 960 cm-1 was revealed in the MCD spectrum. Approximately the same splitting was extracted from the absorption spectrum. The MCD was identified as the temperature independent paramagnetic mixing effect. Nature of the absorption line and of its splitting are discussed.

Nuclear spin circular dichroism.

PubMed

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

2014-04-07

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

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

PubMed

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

2016-05-25

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

Theoretical Calculation of Electronic Circular Dichroism of a Hexahydroxydiphenoyl-Containing Flavanone Glycoside

USDA-ARS?s Scientific Manuscript database

Time-dependent density functional theory (TDDFT) was employed for theoretical calculation of electronic circular dichroism (ECD) of a hexahydroxydiphenoyl (HHDP)-containing flavanone glycoside, mattucinol-7-O-[4'',6''-O-(aS)-hexahydroxydiphenoyl]-ß-d-glucopyranoside (2). It identified the roles of t...

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

ERIC Educational Resources Information Center

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

2017-01-01

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

Chiral detection in high-performance liquid chromatography by vibrational circular dichroism.

PubMed

Tran, C D; Grishko, V I; Huang, G

1994-09-01

A novel chiral detector for high-performance liquid chromatography has been developed. This detector is based on the measurement of circular dichroism of chiral effluents in the infrared region, i.e., vibrational circular dichroism (VCD). In this instrument, a solid-state spectral tunable (from 2.4 to 3.5 microns) F-center laser was used as the light source. The linearly polarized laser beam was converted into left circularly polarized light (LCPL) and right circularly polarized light (RCPL) at 42 kHz by means of a photoelastic modulator. The intensity of the LCPL and RCPL transmitted through the sample was measured by a liquid nitrogen cooled indium antimonide detector. Double modulation was employed to reduce the noise associated with the laser beam. Specifically, the linearly polarized laser beam, prior to being converted to CPL, was modulated at 85 Hz by a mechanical chopper. Demodulation and amplification were accomplished with the use of two lock-in amplifiers. In its present configuration, the instrument can be used to measure the VCD of O-H groups. Its sensitivity is so high that it was able, for the first time, to detect chirally (with limits of detection of micrograms) (R)- and (S)-2,2,2-trifluoro-1-(9- anthryl)ethanol and (R)- and (S)-benzoin when these compounds were chromatographically separated from the corresponding racemic mixtures by a Chiralcel-OD column. The main advantage of this chiral detector is, however, its universality; i.e., it can be used to virtually detect any chiral compounds which has O-H group (e.g, aliphatic alcohols such as 2-octanol).

Dynamic perturbation effects upon the circular dichroism intensity induced in an aggregate of dye chromophores bound to biopolymers

NASA Astrophysics Data System (ADS)

Kamiya, Mamoru

1980-11-01

The dynamic perturbation effects of polarizable monomer perturbers upon the circular dichroism intensity arising from absorption transitions of an arbitrary aggregate of dye chromophores bound to a large host polymer are formulated using the linear response theory in the decorrelation approximation, where the interchromophoric retardation phase factors are eliminated by a first-order Taylor expansion which is compatible with the use of the retarded helix selection rules in the long-wavelength approximation. A space-averaged and closed-form formulation of the non-conservative circular dichroism intensity which is perturbed by intensity with the outside perturber transitions is derived in the limit of the weak dynamic perturbation where perturber—perturber interactions are negligible. The relevant formulation is applied in order to investigate the intercalation model dependence of the non-conservative circular dichroism intensity induced at the visible absorption band of proflavine molecules intercalated in either poly(A—T) or poly(G—C).

A reaction cell for ambient pressure soft x-ray absorption spectroscopy

NASA Astrophysics Data System (ADS)

Castán-Guerrero, C.; Krizmancic, D.; Bonanni, V.; Edla, R.; Deluisa, A.; Salvador, F.; Rossi, G.; Panaccione, G.; Torelli, P.

2018-05-01

We present a new experimental setup for performing X-ray Absorption Spectroscopy (XAS) in the soft X-ray range at ambient pressure. The ambient pressure XAS setup is fully compatible with the ultra high vacuum environment of a synchrotron radiation spectroscopy beamline end station by means of ultrathin Si3N4 membranes acting as windows for the X-ray beam and seal of the atmospheric sample environment. The XAS detection is performed in total electron yield (TEY) mode by probing the drain current from the sample with a picoammeter. The high signal/noise ratio achievable in the TEY mode, combined with a continuous scanning of the X-ray energies, makes it possible recording XAS spectra in a few seconds. The first results show the performance of this setup to record fast XAS spectra from sample surfaces exposed at atmospheric pressure, even in the case of highly insulating samples. The use of a permanent magnet inside the reaction cell enables the measurement of X-ray magnetic circular dichroism at ambient pressure.

X-ray Characterization of Oxide-based Magnetic Semiconductors

NASA Astrophysics Data System (ADS)

Idzerda, Yves

2008-05-01

Although the evidence for magnetic semiconductors (not simply semiconductors which are ferromagnetic) is compelling, there is much uncertainty in the mechanism for the polarization of the carriers, suggesting that it must be quite novel. Recent experimental evidence suggests that this mechanism is similar to the polaron percolation theory proposed by Kaminski and Das Sarma,ootnotetextKaminski and S. Das Sarma, Physical Review Letters 88, 247202 (2002). which was recently applied specifically to doped oxides by Coey et al.ootnotetextJ. M. D. Coey, M. Venkatesan, and C. B. Fitzgerald, Nature Materials 4, 173 (2005). where the ferromagnetism is driven by the percolation of polarons generated by defects or dopants. We have used X-ray absorption spectroscopy at the L-edges and K-edges for low concentrations transition metal (TM) doped magnetic oxides (including TiO2, La1-xSrxO3, HfO2, and In2O3). We have found that in most cases, the transition metal assumes a valence consistent with being at a substitutional, and not interstitial site. We have also measured the X-ray Magnetic Circular Dichroism spectra. Although these materials show strong bulk magnetization, we are unable to detect a robust dichroism feature associated with magnetic elements in the host semiconductor. In the cases where a dichroism signal was observed, it was very weak and could be ascribed to a distinct ferromagnetic phase (TM metal cluster, TM oxide particulate, etc.) separate from the host material. This fascinating absence of a dichroic signal and its significant substantiation of important features of the polaron percolation model may help to finally resolve the issue of ferromagnetism in magnetically doped oxides.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Goings, Joshua J.; Li, Xiaosong, E-mail: xsli@uw.edu

2016-06-21

One of the challenges of interpreting electronic circular dichroism (ECD) band spectra is that different states may have different rotatory strength signs, determined by their absolute configuration. If the states are closely spaced and opposite in sign, observed transitions may be washed out by nearby states, unlike absorption spectra where transitions are always positive additive. To accurately compute ECD bands, it is necessary to compute a large number of excited states, which may be prohibitively costly if one uses the linear-response time-dependent density functional theory (TDDFT) framework. Here we implement a real-time, atomic-orbital based TDDFT method for computing the entiremore » 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.« less

Twisting dirac fermions: circular dichroism in bilayer graphene

NASA Astrophysics Data System (ADS)

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

2017-09-01

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

Soft-x-ray magneto-optical Kerr effect and element-specific hysteresis measurement

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kortright, J.B.; Rice, M.

1997-04-01

Interest in the utilization of x-ray magneto-optical properties to provide element-specific magnetic information, combined with recent development of tunable linear polarizers for spectroscopic polarization measurement, have led the authors to the study of magneto-optical rotation (MOR) near core levels of magnetic atoms in magnetic multilayer and alloy films. Their initial observation of Faraday rotation (in transmission) demonstrated that for Fe MOR is easily measured and is larger at its L{sub 3} resonance than in the near-visible spectral regions. This work also demonstrated that the spectroscopic behavior of the MOR signal in transmission, resulting from the differential reaction of left- andmore » right-circular components of a linearly polarized beam, is related to the magnetic circular dichroism (MCD), or differential absorption, as expected by a Kramers-Kronig transformation. Thus MCD measurements using circular polarization and MOR measurements using linear polarization can provide complementary, and in some cases equivalent, information. On beamline 6.3.2 the authors have begun to investigate soft x-ray MOR in the reflection geometry, the x-ray magneto-optic Kerr effect (XMOKE). Early measurements have demonstrated the ability to measure element-specific hysteresis loops and large rotations compared to analogous near-visible measurements. The authors are investigating the spectral dependence of the XMOKE signal, and have initiated systematic materials studies of sputter-deposited films of Fe, Fe{sub x}Cr{sub 1{minus}x} alloys, and Fe/Cr multilayers.« less

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

NASA Astrophysics Data System (ADS)

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.

DichroCalc: Improvements in Computing Protein Circular Dichroism Spectroscopy in the Near-Ultraviolet.

PubMed

Jasim, Sarah B; Li, Zhuo; Guest, Ellen E; Hirst, Jonathan D

2017-12-16

A fully quantitative theory connecting protein conformation and optical spectroscopy would facilitate deeper insights into biophysical and simulation studies of protein dynamics and folding. The web server DichroCalc (http://comp.chem.nottingham.ac.uk/dichrocalc) allows one to compute from first principles the electronic circular dichroism spectrum of a (modeled or experimental) protein structure or ensemble of structures. The regular, repeating, chiral nature of secondary structure elements leads to intense bands in the far-ultraviolet (UV). The near-UV bands are much weaker and have been challenging to compute theoretically. We report some advances in the accuracy of calculations in the near-UV, realized through the consideration of the vibrational structure of the electronic transitions of aromatic side chains. The improvements have been assessed over a set of diverse proteins. We illustrate them using bovine pancreatic trypsin inhibitor and present a new, detailed analysis of the interactions which are most important in determining the near-UV circular dichroism spectrum. Copyright © 2018. Published by Elsevier Ltd.

Hard X-ray polarizer to enable simultaneous three-dimensional nanoscale imaging of magnetic structure and lattice strain

DOE PAGES

Logan, Jonathan; Harder, Ross; Li, Luxi; ...

2016-01-01

Recent progress in the development of dichroic Bragg coherent diffractive imaging, a new technique for simultaneous three-dimensional imaging of strain and magnetization at the nanoscale, is reported. This progress includes the installation of a diamond X-ray phase retarder at beamline 34-ID-C of the Advanced Photon Source. Here, the performance of the phase retarder for tuning X-ray polarization is demonstrated with temperature-dependent X-ray magnetic circular dichroism measurements on a gadolinium foil in transmission and on a Gd 5Si 2Ge 2crystal in diffraction geometry with a partially coherent, focused X-ray beam. Feasibility tests for dichroic Bragg coherent diffractive imaging are presented. Thesemore » tests include (1) using conventional Bragg coherent diffractive imaging to determine whether the phase retarder introduces aberrations using a nonmagnetic gold nanocrystal as a control sample, and (2) collecting coherent diffraction patterns of a magnetic Gd 5Si 2Ge 2nanocrystal with left- and right-circularly polarized X-rays. Future applications of dichroic Bragg coherent diffractive imaging for the correlation of strain and lattice defects with magnetic ordering and inhomogeneities are considered.« less

A Circular Dichroism Reference Database for Membrane Proteins

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wallace,B.; Wien, F.; Stone, T.

2006-01-01

Membrane proteins are a major product of most genomes and the target of a large number of current pharmaceuticals, yet little information exists on their structures because of the difficulty of crystallising them; hence for the most part they have been excluded from structural genomics programme targets. Furthermore, even methods such as circular dichroism (CD) spectroscopy which seek to define secondary structure have not been fully exploited because of technical limitations to their interpretation for membrane embedded proteins. Empirical analyses of circular dichroism (CD) spectra are valuable for providing information on secondary structures of proteins. However, the accuracy of themore » results depends on the appropriateness of the reference databases used in the analyses. Membrane proteins have different spectral characteristics than do soluble proteins as a result of the low dielectric constants of membrane bilayers relative to those of aqueous solutions (Chen & Wallace (1997) Biophys. Chem. 65:65-74). To date, no CD reference database exists exclusively for the analysis of membrane proteins, and hence empirical analyses based on current reference databases derived from soluble proteins are not adequate for accurate analyses of membrane protein secondary structures (Wallace et al (2003) Prot. Sci. 12:875-884). We have therefore created a new reference database of CD spectra of integral membrane proteins whose crystal structures have been determined. To date it contains more than 20 proteins, and spans the range of secondary structures from mostly helical to mostly sheet proteins. This reference database should enable more accurate secondary structure determinations of membrane embedded proteins and will become one of the reference database options in the CD calculation server DICHROWEB (Whitmore & Wallace (2004) NAR 32:W668-673).« less

X-Ray Polarization from High Mass X-Ray Binaries

NASA Technical Reports Server (NTRS)

Kallman, T.; Dorodnitsyn, A.; Blondin, J.

2015-01-01

X-ray astronomy allows study of objects which may be associated with compact objects, i.e. neutron stars or black holes, and also may contain strong magnetic fields. Such objects are categorically non-spherical, and likely non-circular when projected on the sky. Polarization allows study of such geometric effects, and X-ray polarimetry is likely to become feasible for a significant number of sources in the future. A class of potential targets for future X-ray polarization observations is the high mass X-ray binaries (HMXBs), which consist of a compact object in orbit with an early type star. In this paper we show that X-ray polarization from HMXBs has a distinct signature which depends on the source inclination and orbital phase. The presence of the X-ray source displaced from the star creates linear polarization even if the primary wind is spherically symmetric whenever the system is viewed away from conjunction. Direct X-rays dilute this polarization whenever the X-ray source is not eclipsed; at mid-eclipse the net polarization is expected to be small or zero if the wind is circularly symmetric around the line of centers. Resonance line scattering increases the scattering fraction, often by large factors, over the energy band spanned by resonance lines. Real winds are not expected to be spherically symmetric, or circularly symmetric around the line of centers, owing to the combined effects of the compact object gravity and ionization on the wind hydrodynamics. A sample calculation shows that this creates polarization fractions ranging up to tens of percent at mid-eclipse.

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

ERIC Educational Resources Information Center

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

2005-01-01

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

Fourier transform vibrational circular dichroism of small pharmaceutical molecules

NASA Astrophysics Data System (ADS)

Long, Fujin; Freedman, Teresa B.; Nafie, Laurence A.

1998-06-01

Fourier transform vibrational circular dichroism (FT-VCD) spectra of the small pharmaceutical molecules propanolol, ibuprofen and naproxen have been measured in the hydrogen stretching and mid-infrared regions to obtain information on solution conformation and to identify markers for absolute configuration determination. Ab initio molecular orbital calculations of low energy conformations, vibrational frequencies and VCD intensities for fragments of the drugs were utilized in interpreting the spectra. Features characteristic of five conformers of propranolol were identified. The weak positive CH stretching VCD signal in ibuprofen and naproxen is characteristic of the S-configuration of the chiral center common to these two analgesics.

Room temperature high circular dichroism ultraviolet lasing from planar spiral metal-GaN nanowire cavity (Conference Presentation)

NASA Astrophysics Data System (ADS)

Shih, Min-Hsiung

2016-09-01

Circularly polarized light and chiroptical effect have received considerable attention in advanced photonic and electronic technologies including optical spintronics, quantum-based optical information processing and communication, and high-efficiency liquid crystal display backlights. Moreover, the development of circularly polarized photon sources has played a major role in circular dichroism (CD) spectroscopy, which is important for analyses of optically active molecules, chiral synthesis in biology and chemistry, and ultrafast magnetization control. However, the conventional collocation of light-emitting devices and additional circular-polarization converters that produce circularly polarized beams makes the setup bulky and hardly compatible with nanophotonic devices in ultrasmall scales. In fact, the direct generation of circularly polarized photons may simplify the system integration, compact the setup, lower the cost of external components, and perhaps enhance the power efficiency. In this work, with the spiral-type metal-gallium nitride (GaN) nanowire cavity, 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 decently high degrees of circular polarizations.

Protein fiber linear dichroism for structure determination and kinetics in a low-volume, low-wavelength couette flow cell.

PubMed

Dafforn, Timothy R; Rajendra, Jacindra; Halsall, David J; Serpell, Louise C; Rodger, Alison

2004-01-01

High-resolution structure determination of soluble globular proteins relies heavily on x-ray crystallography techniques. Such an approach is often ineffective for investigations into the structure of fibrous proteins as these proteins generally do not crystallize. Thus investigations into fibrous protein structure have relied on less direct methods such as x-ray fiber diffraction and circular dichroism. Ultraviolet linear dichroism has the potential to provide additional information on the structure of such biomolecular systems. However, existing systems are not optimized for the requirements of fibrous proteins. We have designed and built a low-volume (200 microL), low-wavelength (down to 180 nm), low-pathlength (100 microm), high-alignment flow-alignment system (couette) to perform ultraviolet linear dichroism studies on the fibers formed by a range of biomolecules. The apparatus has been tested using a number of proteins for which longer wavelength linear dichroism spectra had already been measured. The new couette cell has also been used to obtain data on two medically important protein fibers, the all-beta-sheet amyloid fibers of the Alzheimer's derived protein Abeta and the long-chain assemblies of alpha1-antitrypsin polymers.

Circular dichroism of magnetically induced transitions for D2 lines of alkali atoms

NASA Astrophysics Data System (ADS)

Tonoyan, A.; Sargsyan, A.; Klinger, E.; Hakhumyan, G.; Leroy, C.; Auzinsh, M.; Papoyan, A.; Sarkisyan, D.

2018-03-01

In this letter we study magnetic circular dichroism in alkali atoms exhibiting asymmetric behaviour of magnetically induced transitions. The magnetic field \\textbf{B}\\parallel\\textbf{k} induces transitions between Δ F = +/-2 hyperfine levels of alkali atoms and in the range of ∼0.1{\\text{--}}3 \\text{kG} magnetic field, the intensities of these transitions experience significant enhancement. We have inferred a general rule applicable for the D 2 lines of all alkali atoms, that is the transition intensity enhancement is around four times larger for the case of σ+ than for σ- excitation for Δ F = +2 , whereas it is several hundreds of thousand times larger in the case of σ- than that for σ+ polarization for Δ F = -2 . This asymmetric behaviour results in circular dichroism. For experimental verification we employed half-wavelength-thick atomic vapor nanocells using a derivative of the selective reflection technique, which provides a sub-Doppler spectroscopic linewidth (∼50 \\text{MHz} ). The presented theoretical curves well describe the experimental results. This effect can find applications particularly in parity violation experiments.

Frenkel-exciton decomposition analysis of circular dichroism and circularly polarized luminescence for multichromophoric systems.

PubMed

Shiraogawa, Takafumi; Ehara, Masahiro; Jurinovich, Sandro; Cupellini, Lorenzo; Mennucci, Benedetta

2018-06-15

Recently, a method to calculate the absorption and circular dichroism (CD) spectra based on the exciton coupling has been developed. In this work, the method was utilized for the decomposition of the CD and circularly polarized luminescence (CPL) spectra of a multichromophoric system into chromophore contributions for recently developed through-space conjugated oligomers. The method which has been implemented using rotatory strength in the velocity form and therefore it is gauge-invariant, enables us to evaluate the contribution from each chromophoric unit and locally excited state to the CD and CPL spectra of the total system. The excitonic calculations suitably reproduce the full calculations of the system, as well as the experimental results. We demonstrate that the interactions between electric transition dipole moments of adjacent chromophoric units are crucial in the CD and CPL spectra of the multichromophoric systems, while the interactions between electric and magnetic transition dipole moments are not negligible. © 2018 Wiley Periodicals, Inc. © 2018 Wiley Periodicals, Inc.

Understanding electron magnetic circular dichroism in a transition potential approach

NASA Astrophysics Data System (ADS)

Barthel, J.; Mayer, J.; Rusz, J.; Ho, P.-L.; Zhong, X. Y.; Lentzen, M.; Dunin-Borkowski, R. E.; Urban, K. W.; Brown, H. G.; Findlay, S. D.; Allen, L. J.

2018-04-01

This paper introduces an approach based on transition potentials for inelastic scattering to understand the underlying physics of electron magnetic circular dichroism (EMCD). The transition potentials are sufficiently localized to permit atomic-scale EMCD. Two-beam and three-beam systematic row cases are discussed in detail in terms of transition potentials for conventional transmission electron microscopy, and the basic symmetries which arise in the three-beam case are confirmed experimentally. Atomic-scale EMCD in scanning transmission electron microscopy (STEM), using both a standard STEM probe and vortex beams, is discussed.

Rapid magnetosome formation shown by real-time x-ray magnetic circular dichroism.

PubMed

Staniland, Sarah; Ward, Bruce; Harrison, Andrew; van der Laan, Gerrit; Telling, Neil

2007-12-04

Magnetosomes are magnetite nanoparticles formed by biomineralization within magnetotactic bacteria. Although there have been numerous genetic and proteomic studies of the magnetosome-formation process, there have been only limited and inconclusive studies of mineral-phase evolution during the formation process, and no real-time studies of such processes have yet been performed. Thus, suggested formation mechanisms still need substantiating with data. Here we report the examination of the magnetosome material throughout the formation process in a real-time in vivo study of Magnetospirillum gryphiswaldense, strain MSR-1. Transmission EM and x-ray absorption spectroscopy studies reveal that full-sized magnetosomes are seen 15 min after formation is initiated. These immature magnetosomes contain a surface layer of the nonmagnetic iron oxide-phase hematite. Mature magnetite is found after another 15 min, concurrent with a dramatic increase in magnetization. This rapid formation result is contrary to previously reported studies and discounts the previously proposed slow, multistep formation mechanisms. Thus, we conclude that the biomineralization of magnetite occurs rapidly in magnetotactic bacteria on a similar time scale to high-temperature chemical precipitation reactions, and we suggest that this finding is caused by a biological catalysis of the process.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

B Wallace; R Janes

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,more » 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.« less

Circular dichroism spectra of uridine derivatives: ChiraSac study.

PubMed

Miyahara, Tomoo; Nakatsuji, Hiroshi; Wada, Takehiko

2014-04-24

The experimental circular dichroism (CD) spectra of uridine and NH2-uridine that were different in the intensity and shape were studied in the light of the ChiraSac method. The theoretical CD spectra at several different conformations using the symmetry-adapted-cluster configuration-interaction (SAC-CI) theory largely depended on the conformational angle, but those of the anti-conformers and the Boltzmann average reproduced the experimentally obtained CD spectra of both uridine and NH2-uridine. The differences in the CD spectra between the two uridine derivatives were analyzed by using the angle θ between the electric transition dipole moment (ETDM) and the magnetic transition dipole moment (MTDM).

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

PubMed

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

2017-10-01

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

Electronic structure and magnetic properties of the half-metallic ferrimagnet Mn2VAl probed by soft x-ray spectroscopies

NASA Astrophysics Data System (ADS)

Nagai, K.; Fujiwara, H.; Aratani, H.; Fujioka, S.; Yomosa, H.; Nakatani, Y.; Kiss, T.; Sekiyama, A.; Kuroda, F.; Fujii, H.; Oguchi, T.; Tanaka, A.; Miyawaki, J.; Harada, Y.; Takeda, Y.; Saitoh, Y.; Suga, S.; Umetsu, R. Y.

2018-01-01

We have studied the electronic structure of ferrimagnetic Mn2VAl single crystals by means of soft x-ray absorption spectroscopy (XAS), x-ray absorption magnetic circular dichroism (XMCD), and resonant soft x-ray inelastic scattering (RIXS). We have successfully observed the XMCD signals for all the constituent elements. The Mn L2 ,3 XAS and XMCD spectra are reproduced by spectral simulations based on density-functional theory, indicating the itinerant character of the Mn 3 d states. On the other hand, the V 3 d electrons are rather localized since the ionic model can qualitatively explain the V L2 ,3 XAS and XMCD spectra. This picture is consistent with local d d excitations revealed by the V L3 RIXS.

Magnetic circular dichroism of chlorofullerenes: Experimental and computational study

NASA Astrophysics Data System (ADS)

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

2016-03-01

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

Accurate secondary structure prediction and fold recognition for circular dichroism spectroscopy

PubMed Central

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

2015-01-01

Circular dichroism (CD) spectroscopy is a widely used technique for the study of protein structure. Numerous algorithms have been developed for the estimation of the secondary structure composition from the CD spectra. These methods often fail to provide acceptable results on α/β-mixed or β-structure–rich proteins. The problem arises from the spectral diversity of β-structures, which has hitherto been considered as an intrinsic limitation of the technique. The predictions are less reliable for proteins of unusual β-structures such as membrane proteins, protein aggregates, and amyloid fibrils. Here, we show that the parallel/antiparallel orientation and the twisting of the β-sheets account for the observed spectral diversity. We have developed a method called β-structure selection (BeStSel) for the secondary structure estimation that takes into account the twist of β-structures. This method can reliably distinguish parallel and antiparallel β-sheets and accurately estimates the secondary structure for a broad range of proteins. Moreover, the secondary structure components applied by the method are characteristic to the protein fold, and thus the fold can be predicted to the level of topology in the CATH classification from a single CD spectrum. By constructing a web server, we offer a general tool for a quick and reliable structure analysis using conventional CD or synchrotron radiation CD (SRCD) spectroscopy for the protein science research community. The method is especially useful when X-ray or NMR techniques fail. Using BeStSel on data collected by SRCD spectroscopy, we investigated the structure of amyloid fibrils of various disease-related proteins and peptides. PMID:26038575

Toward broad-band x-ray detected ferromagnetic resonance in longitudinal geometry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ollefs, K.; European Synchrotron Radiation Facility; Meckenstock, R.

2015-06-14

An ultrahigh-vacuum-compatible setup for broad-band X-ray detected ferromagnetic resonance (XFMR) in longitudinal geometry is introduced which relies on a low-power, continuous-wave excitation of the ferromagnetic sample. A simultaneous detection of the conventional ferromagnetic resonance via measuring the reflected microwave power and the XFMR signal of the X-ray absorption is possible. First experiments on the Fe and Co L{sub 3}-edges of a permalloy film covered with Co nanostripes as well as the Fe and Ni K-edges of a permalloy film are presented and discussed. Two different XFMR signals are found, one of which is independent of the photon energy and thereforemore » does not provide element-selective information. The other much weaker signal is element-selective, and the dynamic magnetic properties could be detected for Fe and Co separately. The dependence of the latter XFMR signal on the photon helicity of the synchrotron light is found to be distinct from the usual x-ray magnetic circular dichroism effect.« less

Time-resolved circular dichroism: Application to the study of conformal changes in biomolecules

NASA Astrophysics Data System (ADS)

Hache, F.

2010-06-01

Circular dichroism (CD) is known to be a very sensitive probe of the conformation of molecules and biomolecules. It is therefore tempting to implement CD in a pump-probe experiment in order to measure ultrarapid conformational changes which occur in photochemical processes. We present two technical developments of such time-resolved CD experiments. The first one relies on the modulation of the probe polarization from left to right circular whereas the second one measures the pump-induced ellipticity of the probe with a Babinet-Soleil compensator. Some applications are described and extension of these techniques towards the study of elementary protein folding processes is discussed.

[Study of "bound insulin" of the blood sera of blood/donors and patients with diabetes mellitus by circular dichroism].

PubMed

Gracheva, N K; Kharitonenkov, I G

1978-01-01

Circular dichroism was applied to the study of the structure of the insulin-transferrin complexes ("bound insulin") isolated from the blood sera of donors and patients suffering from diabetes mellitus of moderate severity. There proved to be a considerable (in comparison with the normal) reduction of the alpha-helix areas in the "bound insulin"molecule of the patients. A comparative study of the circular dichroism spectra in the area of absorption of aromatic amino acids permitted to suppose that the structural changes of the molecule of a complex isolated from the blood sera of patients could not be explained by alterations in the area of the aromatic amino acids.

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

PubMed

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

2017-08-09

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

Dielectric tuned circular dichroism of L-shaped plasmonic metasurface

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

Corrigendum to "Co-occurrence of linear and circular dichroism in chiral sculptured ZrO2 thin films" [Opt. Mater. 75 (January 2018) 319-324

NASA Astrophysics Data System (ADS)

Muhammad, Zahir; Wali, Faiz; Song, Li

2018-05-01

The authors regret circular dichroism and linear dichroism [1]>.

On vibrational circular dichroism chirality transfer in electron donor-acceptor complexes: a prediction for the quinine···BF3 system.

PubMed

Rode, Joanna E; Jamróz, Michał H; Dobrowolski, Jan Cz; Sadlej, Joanna

2012-08-02

Vibrational circular dichroism (VCD) chirality transfer occurs when an achiral molecule interacts with a chiral one and becomes VCD-active. Unlike for H-bonds, for organic electron donor-acceptor (EDA) complexes this phenomenon remains almost unknown. Here, the VCD chirality transfer from chiral quinine to achiral BF3 is studied at the B3LYP/aug-cc-pVDZ level. Accessibility of four quinine electron donor sites changes with conformation. Therefore, the quinine conformational landscape was explored and a considerable agreement between X-ray and the most stable conformer geometries was achieved. The BF3 complex through the aliphatic quinuclidine N atom is definitely dominating and is predicted to be easily recognizable in the VCD spectrum. Out of several VCD chirality transfer modes, the ν(s)(BF3) mode, the most intense in the entire VCD spectrum, satisfies the VCD mode robustness criterion and can be used for monitoring the chirality transfer phenomenon in quinine···BF3 system.

Atomic scale imaging of magnetic circular dichroism by achromatic electron microscopy.

PubMed

Wang, Zechao; Tavabi, Amir H; Jin, Lei; Rusz, Ján; Tyutyunnikov, Dmitry; Jiang, Hanbo; Moritomo, Yutaka; Mayer, Joachim; Dunin-Borkowski, Rafal E; Yu, Rong; Zhu, Jing; Zhong, Xiaoyan

2018-03-01

In order to obtain a fundamental understanding of the interplay between charge, spin, orbital and lattice degrees of freedom in magnetic materials and to predict and control their physical properties 1-3 , experimental techniques are required that are capable of accessing local magnetic information with atomic-scale spatial resolution. Here, we show that a combination of electron energy-loss magnetic chiral dichroism 4 and chromatic-aberration-corrected transmission electron microscopy, which reduces the focal spread of inelastically scattered electrons by orders of magnitude when compared with the use of spherical aberration correction alone, can achieve atomic-scale imaging of magnetic circular dichroism and provide element-selective orbital and spin magnetic moments atomic plane by atomic plane. This unique capability, which we demonstrate for Sr 2 FeMoO 6 , opens the door to local atomic-level studies of spin configurations in a multitude of materials that exhibit different types of magnetic coupling, thereby contributing to a detailed understanding of the physical origins of magnetic properties of materials at the highest spatial resolution.

Element specific determination of the magnetic properties of two macrocyclic tetranuclear 3d-4f complexes with a Cu3Tb core by means of X-ray magnetic circular dichroism (XMCD).

PubMed

Balinski, K; Schneider, L; Wöllermann, J; Buling, A; Joly, L; Piamonteze, C; Feltham, H L C; Brooker, S; Powell, A K; Delley, B; Kuepper, K

2018-06-20

We apply X-ray magnetic circular dichroism to study the internal magnetic structure of two very promising star shaped macrocyclic complexes with a CuII3TbIII core. These complexes are rare examples prepared with a macrocyclic ligand that show indications of SMM (Single Molecule Magnet) behavior, and they differ only in ring size: one has a propylene linked macrocycle, [CuII3TbIII(LPr)(NO3)2(MeOH)(H2O)2](NO3)·3H2O (nickname: Cu3Tb(LPr)), and the other has the butylene linked analogue, [CuII3TbIII(LBu)(NO3)2(MeOH)(H2O)](NO3)·3H2O (nickname: Cu3Tb(LBu)). We analyze the orbital and spin contributions to the Cu and Tb ions quantitatively by applying the spin and orbital sum rules concerning the L2 (M4)/L3 (M5) edges. In combination with appropriate ligand field simulations, we demonstrate that the Tb(iii) ions contribute with high orbital magnetic moments to the magnetic anisotropy, whereas the ligand field determines the easy axis of magnetization. Furthermore, we confirm that the Cu(ii) ions in both molecules are in a divalent valence state, the magnetic moments of the three Cu ions appear to be canted due to 3d-3d intramolecular magnetic interactions. For Cu3Tb(LPr), the corresponding element specific magnetization loops reflect that the Cu(ii) contribution to the overall magnetic picture becomes more important as the temperature is lowered. This implies a low value for the 3d-4f coupling.

A circular dichroism and structural study of the inclusion complex artemisinin-β-cyclodextrin

NASA Astrophysics Data System (ADS)

Marconi, Giancarlo; Monti, Sandra; Manoli, Francesco; Degli Esposti, Alessandra; Mayer, Bernd

2004-01-01

The inclusion complex between the powerful antimalarial agent Artemisinin and β-cyclodextrin has been studied by means of Circular Dichroism and elucidated by Density Functional Theory calculations on the isolated molecule combined to a statistical Monte Carlo search of the most stable geometry of the complex. The results evidence a host-guest structure in full agreement with the almost unaffected functionality of the drug, which is found to experience a significant hydrophilic environment when complexed.

Measuring spectroscopy and magnetism of extracted and intracellular magnetosomes using soft X-ray ptychography

PubMed Central

Zhu, Xiaohui; Hitchcock, Adam P.; Bazylinski, Dennis A.; Denes, Peter; Joseph, John; Lins, Ulysses; Marchesini, Stefano; Shiu, Hung-Wei; Tyliszczak, Tolek; Shapiro, David A.

2016-01-01

Characterizing the chemistry and magnetism of magnetotactic bacteria (MTB) is an important aspect of understanding the biomineralization mechanism and function of the chains of magnetosomes (Fe3O4 nanoparticles) found in such species. Images and X-ray absorption spectra (XAS) of magnetosomes extracted from, and magnetosomes in, whole Magnetovibrio blakemorei strain MV-1 cells have been recorded using soft X-ray ptychography at the Fe 2p edge. A spatial resolution of 7 nm is demonstrated. Precursor-like and immature magnetosome phases in a whole MV-1 cell were visualized, and their Fe 2p spectra were measured. Based on these results, a model for the pathway of magnetosome biomineralization for MV-1 is proposed. Fe 2p X-ray magnetic circular dichroism (XMCD) spectra have been derived from ptychography image sequences recorded using left and right circular polarization. The shape of the XAS and XMCD signals in the ptychographic absorption spectra of both sample types is identical to the shape and signals measured with conventional bright-field scanning transmission X-ray microscope. A weaker and inverted XMCD signal was observed in the ptychographic phase spectra of the extracted magnetosomes. The XMCD ptychographic phase spectrum of the intracellular magnetosomes differed from the ptychographic phase spectrum of the extracted magnetosomes. These results demonstrate that spectro-ptychography offers a superior means of characterizing the chemical and magnetic properties of MTB at the individual magnetosome level. PMID:27930297

Measuring spectroscopy and magnetism of extracted and intracellular magnetosomes using soft X-ray ptychography.

PubMed

Zhu, Xiaohui; Hitchcock, Adam P; Bazylinski, Dennis A; Denes, Peter; Joseph, John; Lins, Ulysses; Marchesini, Stefano; Shiu, Hung-Wei; Tyliszczak, Tolek; Shapiro, David A

2016-12-20

Characterizing the chemistry and magnetism of magnetotactic bacteria (MTB) is an important aspect of understanding the biomineralization mechanism and function of the chains of magnetosomes (Fe 3 O 4 nanoparticles) found in such species. Images and X-ray absorption spectra (XAS) of magnetosomes extracted from, and magnetosomes in, whole Magnetovibrio blakemorei strain MV-1 cells have been recorded using soft X-ray ptychography at the Fe 2p edge. A spatial resolution of 7 nm is demonstrated. Precursor-like and immature magnetosome phases in a whole MV-1 cell were visualized, and their Fe 2p spectra were measured. Based on these results, a model for the pathway of magnetosome biomineralization for MV-1 is proposed. Fe 2p X-ray magnetic circular dichroism (XMCD) spectra have been derived from ptychography image sequences recorded using left and right circular polarization. The shape of the XAS and XMCD signals in the ptychographic absorption spectra of both sample types is identical to the shape and signals measured with conventional bright-field scanning transmission X-ray microscope. A weaker and inverted XMCD signal was observed in the ptychographic phase spectra of the extracted magnetosomes. The XMCD ptychographic phase spectrum of the intracellular magnetosomes differed from the ptychographic phase spectrum of the extracted magnetosomes. These results demonstrate that spectro-ptychography offers a superior means of characterizing the chemical and magnetic properties of MTB at the individual magnetosome level.

Measuring spectroscopy and magnetism of extracted and intracellular magnetosomes using soft X-ray ptychography

DOE PAGES

Zhu, Xiaohui; Hitchcock, Adam P.; Bazylinski, Dennis A.; ...

2016-12-07

Characterizing the chemistry and magnetism of magnetotactic bacteria (MTB) is an important aspect of understanding the biomineralization mechanism and function of the chains of magnetosomes (Fe 3O 4 nanoparticles) found in such species. Images and X-ray absorption spectra (XAS) of magnetosomes extracted from, and magnetosomes in, whole Magnetovibrio blakemorei strain MV-1 cells have been recorded using soft X-ray ptychography at the Fe 2p edge. A spatial resolution of 7 nm is demonstrated. Precursor-like and immature magnetosome phases in a whole MV-1 cell were visualized, and their Fe 2p spectra were measured. Based on these results, a model for the pathwaymore » of magnetosome biomineralization for MV-1 is proposed. Fe 2p X-ray magnetic circular dichroism (XMCD) spectra have been derived from ptychography image sequences recorded using left and right circular polarization. The shape of the XAS and XMCD signals in the ptychographic absorption spectra of both sample types is identical to the shape and signals measured with conventional bright-field scanning transmission X-ray microscope. A weaker and inverted XMCD signal was observed in the ptychographic phase spectra of the extracted magnetosomes. The XMCD ptychographic phase spectrum of the intracellular magnetosomes differed from the ptychographic phase spectrum of the extracted magnetosomes. Lastly, these results demonstrate that spectro-ptychography offers a superior means of characterizing the chemical and magnetic properties of MTB at the individual magnetosome level.« less

Design and performance of BOREAS, the beamline for resonant X-ray absorption and scattering experiments at the ALBA synchrotron light source

DOE PAGES

Barla, Alessandro; Nicolas, Josep; Cocco, Daniele; ...

2016-10-07

The optical design of the BOREAS beamline operating at the ALBA synchrotron radiation facility is described. BOREAS is dedicated to resonant X-ray absorption and scattering experiments using soft X-rays, in an unusually extended photon energy range from 80 to above 4000 eV, and with full polarization control. Its optical scheme includes a fixed-included-angle, variable-line-spacing grating monochromator and a pair of refocusing mirrors, equipped with benders, in a Kirkpatrick–Baez arrangement. It is equipped with two end-stations, one for X-ray magnetic circular dichroism and the other for resonant magnetic scattering. In conclusion, the commissioning results show that the expected beamline performance ismore » achieved both in terms of energy resolution and of photon flux at the sample position.« less

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

1997-04-01

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

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

USDA-ARS?s Scientific Manuscript database

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...

Stereospecific analysis of loxoprofen in plasma by chiral column liquid chromatography with a circular dichroism-based detector.

PubMed

Kanazawa, Hideko; Tsubayashi, Akane; Nagata, Yoshiko; Matsushima, Yoshikazu; Mori, Chiharu; Kizu, Junko; Higaki, Megumu

2002-03-01

The chiral separation of loxoprofen was achieved on a chiral column with UV and circular dichroism (CD) detection. The good resolution of four loxoprofen stereoisomers was obtained. The column used for the chiral separation was Chiralcel OJ column (250 x 4.6 mm) using hexane-2-propanol-trifluoroacetic acid (95:5:0.1), as an eluent. The flow-rate was 1.0 ml/min and the detection was at 225 nm. In addition, CD and UV spectra were obtained by stopped flow scanning. The method allows the determination of the stereoisomers of loxoprofen in human plasma after the administration of therapeutic dose of the racemic drug, thus HPLC with CD detector is useful for the stereospecific determination of loxoprofen products in biological samples.

Electrically controlled magnetic circular dichroism and Faraday rotation in graphene

NASA Astrophysics Data System (ADS)

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

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

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

ERIC Educational Resources Information Center

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

2017-01-01

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

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

PubMed

Keiderling, Timothy A

2017-12-01

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

Enhanced Circular Dichroism via Symmetry Breaking in a Chiral Plasmonic Nanoparticle Oligomer

NASA Astrophysics Data System (ADS)

Le, Khai Q.

2018-02-01

A chiral plasmonic nanoparticle oligomer, consisting of four symmetrically arranged nanodisks of different heights and having different optical absorption responses to left and right-handed circularly polarized light illumination, has been experimentally reported in the literature. The resulting circular dichroism (CD) signal was detectable with state of the art CD spectrometers but was much weaker than those of existing chiral nanostructures, i.e., three-dimensional (3-D) chiral metamaterials. In this letter, via symmetry breaking in such an oligomer, the author demonstrates that the CD can be enhanced up to six times compared to that of a symmetric oligomer, and is in the range of a relevant 3-D chiral metamolecule. Through investigation of geometrical parameters including particle size, asymmetric and symmetric gaps, the CD evolution was reported, which provides a useful guideline for design of two-dimensional chiral oligomers adopted as efficient probes for CD spectroscopic applications.

Assessment of amsacrine binding with DNA using UV-visible, circular dichroism and Raman spectroscopic techniques.

PubMed

Jangir, Deepak Kumar; Dey, Sanjay Kumar; Kundu, Suman; Mehrotra, Ranjana

2012-09-03

Proper understanding of the mechanism of binding of drugs to their targets in cell is a fundamental requirement to develop new drug therapy regimen. Amsacrine is a rationally designed anticancer drug, used to treat leukemia and lymphoma. Binding with cellular DNA is a crucial step in its mechanism of cytotoxicity. Despite numerous studies, DNA binding properties of amsacrine are poorly understood. Its reversible binding with DNA does not permit X-ray crystallography or NMR spectroscopic evaluation of amsacrine-DNA complexes. In the present work, interaction of amsacrine with calf thymus DNA is investigated at physiological conditions. UV-visible, FT-Raman and circular dichroism spectroscopic techniques were employed to determine the binding mode, binding constant, sequence specificity and conformational effects of amsacrine binding to native calf thymus DNA. Our results illustrate that amsacrine interacts with DNA by and large through intercalation between base pairs. Binding constant of the amsacrine-DNA complex was found to be K=1.2±0.1×10(4) M(-1) which is indicative of moderate type of binding of amsacrine to DNA. Raman spectroscopic results suggest that amsacrine has a binding preference of intercalation between AT base pairs of DNA. Minor groove binding is also observed in amsacrine-DNA complexes. These results are in good agreement with in silico investigation of amsacrine binding to DNA and thus provide detailed insight into DNA binding properties of amsacrine, which could ultimately, renders its cytotoxic efficacy. Copyright © 2012 Elsevier B.V. All rights reserved.

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

PubMed

Longo, Edoardo; Hussain, Rohanah; Siligardi, Giuliano

2015-03-01

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

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

NASA Astrophysics Data System (ADS)

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

2014-03-01

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

Probing topology by "heating": Quantized circular dichroism in ultracold atoms.

PubMed

Tran, Duc Thanh; Dauphin, Alexandre; Grushin, Adolfo G; Zoller, Peter; Goldman, Nathan

2017-08-01

We reveal an intriguing manifestation of topology, which appears in the depletion rate of topological states of matter in response to an external drive. This phenomenon is presented by analyzing the response of a generic two-dimensional (2D) Chern insulator subjected to a circular time-periodic perturbation. Because of the system's chiral nature, the depletion rate is shown to depend on the orientation of the circular shake; taking the difference between the rates obtained from two opposite orientations of the drive, and integrating over a proper drive-frequency range, provides a direct measure of the topological Chern number (ν) of the populated band: This "differential integrated rate" is directly related to the strength of the driving field through the quantized coefficient η 0 = ν/ ℏ 2 , where h = 2π ℏ is Planck's constant. Contrary to the integer quantum Hall effect, this quantized response is found to be nonlinear with respect to the strength of the driving field, and it explicitly involves interband transitions. We investigate the possibility of probing this phenomenon in ultracold gases and highlight the crucial role played by edge states in this effect. We extend our results to 3D lattices, establishing a link between depletion rates and the nonlinear photogalvanic effect predicted for Weyl semimetals. The quantized circular dichroism revealed in this work designates depletion rate measurements as a universal probe for topological order in quantum matter.

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

PubMed

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

2014-01-01

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

Circular Dichroism Control of Tungsten Diselenide (WSe2) Atomic Layers with Plasmonic Metamolecules.

PubMed

Lin, Hsiang-Ting; Chang, Chiao-Yun; Cheng, Pi-Ju; Li, Ming-Yang; Cheng, Chia-Chin; Chang, Shu-Wei; Li, Lance L J; Chu, Chih-Wei; Wei, Pei-Kuen; Shih, Min-Hsiung

2018-05-09

Controlling circularly polarized (CP) states of light is critical to the development of functional devices for key and emerging applications such as display technology and quantum communication, and the compact circular polarization-tunable photon source is one critical element to realize the applications in the chip-scale integrated system. The atomic layers of transition metal dichalcogenides (TMDCs) exhibit intrinsic CP emissions and are potential chiroptical materials for ultrathin CP photon sources. In this work, we demonstrated CP photon sources of TMDCs with device thicknesses approximately 50 nm. CP photoluminescence from the atomic layers of tungsten diselenide (WSe 2 ) was precisely controlled with chiral metamolecules (MMs), and the optical chirality of WSe 2 was enhanced more than 4 times by integrating with the MMs. Both the enhanced and reversed circular dichroisms had been achieved. Through integrations of the novel gain material and plasmonic structure which are both low-dimensional, a compact device capable of efficiently manipulating emissions of CP photon was realized. These ultrathin devices are suitable for important applications such as the optical information technology and chip-scale biosensing.

Emitter-site-selective photoelectron circular dichroism of trifluoromethyloxirane

DOE PAGES

Ilchen, M.; Hartmann, G.; Rupprecht, P.; ...

2017-05-30

The angle-resolved inner-shell photoionization of R-trifluoromethyloxirane, C 3H 3F 3O, is studied experimentally and theoretically. Thereby, we investigate the photoelectron circular dichroism (PECD) for nearly symmetric O 1s and F 1s electronic orbitals, which are localized on different molecular sites. The respective dichroic β 1 and angular distribution β 2 parameters are measured at the photoelectron kinetic energies from 1 to 16 eV by using variably polarized synchrotron radiation and velocity map imaging spectroscopy. The present experimental results are in good agreement with the outcome of ab initio electronic structure calculations. We report a sizable chiral asymmetry β 1 ofmore » up to about 9% for the K -shell photoionization of oxygen atom. For the individual fluorine atoms, the present calculations predict asymmetries of similar size. However, being averaged over all fluorine atoms, it drops down to about 2%, as also observed in the present experiment. Our study demonstrates a strong emitter and site sensitivity of PECD in the one-photon inner-shell ionization of this chiral molecule.« less

Circular dichroism study of the carbohydrate-modified opioid peptides

NASA Astrophysics Data System (ADS)

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

1999-09-01

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

Enhanced Circular Dichroism of Gold Bilayered Slit Arrays Embedded with Rectangular Holes.

PubMed

Zhang, Hao; Wang, Yongkai; Luo, Lina; Wang, Haiqing; Zhang, Zhongyue

2017-01-01

Gold bilayered slit arrays with rectangular holes embedded into the metal surface are designed to enhance the circular dichroism (CD) effect of gold bilayered slit arrays. The rectangular holes in these arrays block electric currents and generate localized surface plasmons around these holes, thereby strengthening the CD effect. The CD enhancement factor depends strongly on the rotational angle and the structural parameters of the rectangular holes; this factor can be enhanced further by drilling two additional rectangular holes into the metal surfaces of the arrays. These results help facilitate the design of chiral structures to produce a strong CD effect and large electric fields.

Computer programs to assist in high resolution thermal denaturation and circular dichroism studies on nucleic acids

PubMed Central

Goodman, Thomas C.; Hardies, Stephen C.; Cortez, Carlos; Hillen, Wolfgang

1981-01-01

Computer programs are described that direct the collection, processing, and graphical display of numerical data obtained from high resolution thermal denaturation (1-3) and circular dichroism (4) studies. Besides these specific applications, the programs may also be useful, either directly or as programming models, in other types of spectrophotometric studies employing computers, programming languages, or instruments similar to those described here (see Materials and Methods). PMID:7335498

Soft X-ray Spectromicroscopy of Polymers

NASA Astrophysics Data System (ADS)

Ade, Harald

1997-03-01

The development of Near Edge X-ray Absorption Fine Structure (NEXAFS) microscopy^1 and linear dichroism microscopy^2 over the last few years utilizing the X1-Scanning Transmission X-ray Microscope (X1-STXM) at the National Synchrotron Light Source provides excellent specificity to various functional groups and moieties in organic molecules and polymeric materials at a spatial resolution of 50 nm. This chemical specificity can be utilized to map the distribution of various compounds in a material, or to micro-chemically analyze small sample areas. Examples of applications include the study of various phase-separated polymers (polyurethanes, liquid crystalline polyesters), multicomponent polymer blends, polymer laminates, and other organic materials such as coal^3. Linear dichroism microscopy furthermore explores the polarization dependence of NEXAFS in (partially) oriented materials, and can determine the orientation of specific functional groups. Applications of linear dichroism microscopy have focused so far on determining the relative degree of radial orientation in Kevlar fibers^3. ^1 H. Ade, X. Zhang, S. Cameron, C. Costello, J. Kirz, and S. Williams, Science 258, 972 (1992). ^2 H. Ade and B. Hsiao, Science 262, 1427 (1993). ^3 Acknowledgement: My callaborators are B. Hsiao, S. Subramoney, B. Wood, I. Plotzker, E. Rightor, G. Mitchell, C. Sloop, D.-J. Liu, S.-C. Liu, J. Marti, C. Zimba, A. P. Smith, R. Spontak, R. Fornes, R. Gilbert, C. Cody, A. Hitchcock and S. Urquhart. The X1-STXM is built and maintained by J. Kirz and C. Jacobsen and their groups. Work supported by: NSF Young Investigator Award (DMR-9458060), DuPont Young Professor Grant, and Dow Chemical.

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

PubMed

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

2016-01-01

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

Determination of the absolute chirality of tellurium using resonant diffraction with circularly polarized x-rays.

PubMed

Tanaka, Y; Collins, S P; Lovesey, S W; Matsumami, M; Moriwaki, T; Shin, S

2010-03-31

Many proteins, sugars and pharmaceuticals crystallize into two forms that are mirror images of each other (enantiomers) like our right and left hands. Tellurium is one enantiomer having a space group pair, P3(1)21 (right-handed screw) and P3(2)21 (left-handed screw). X-ray diffraction with dispersion correction terms has been playing an important role in determining the handedness of enantiomers for a long time. However, this approach is not applicable for an elemental crystal such as tellurium or selenium. We have demonstrated that positive and negative circularly polarized x-rays at the resonant energy of tellurium can be used to absolutely distinguish right from left tellurium. This method is applicable to chiral motifs that occur in biomolecules, liquid crystals, ferroelectrics and antiferroelectrics, multiferroics, etc.

Probing topology by “heating”: Quantized circular dichroism in ultracold atoms

PubMed Central

Tran, Duc Thanh; Dauphin, Alexandre; Grushin, Adolfo G.; Zoller, Peter; Goldman, Nathan

2017-01-01

We reveal an intriguing manifestation of topology, which appears in the depletion rate of topological states of matter in response to an external drive. This phenomenon is presented by analyzing the response of a generic two-dimensional (2D) Chern insulator subjected to a circular time-periodic perturbation. Because of the system’s chiral nature, the depletion rate is shown to depend on the orientation of the circular shake; taking the difference between the rates obtained from two opposite orientations of the drive, and integrating over a proper drive-frequency range, provides a direct measure of the topological Chern number (ν) of the populated band: This “differential integrated rate” is directly related to the strength of the driving field through the quantized coefficient η0 = ν/ℏ2, where h = 2π ℏ is Planck’s constant. Contrary to the integer quantum Hall effect, this quantized response is found to be nonlinear with respect to the strength of the driving field, and it explicitly involves interband transitions. We investigate the possibility of probing this phenomenon in ultracold gases and highlight the crucial role played by edge states in this effect. We extend our results to 3D lattices, establishing a link between depletion rates and the nonlinear photogalvanic effect predicted for Weyl semimetals. The quantized circular dichroism revealed in this work designates depletion rate measurements as a universal probe for topological order in quantum matter. PMID:28835930

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

NASA Astrophysics Data System (ADS)

Kuzmenko, Alexey B.

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

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

NASA Astrophysics Data System (ADS)

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

2017-05-01

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

Holographic Reconstruction of Photoelectron Diffraction and Its Circular Dichroism for Local Structure Probing

NASA Astrophysics Data System (ADS)

Matsui, Fumihiko; Matsushita, Tomohiro; Daimon, Hiroshi

2018-06-01

The local atomic structure around a specific element atom can be recorded as a photoelectron diffraction pattern. Forward focusing peaks and diffraction rings around them indicate the directions and distances from the photoelectron emitting atom to the surrounding atoms. The state-of-the-art holography reconstruction algorithm enables us to image the local atomic arrangement around the excited atom in a real space. By using circularly polarized light as an excitation source, the angular momentum transfer from the light to the photoelectron induces parallax shifts in these diffraction patterns. As a result, stereographic images of atomic arrangements are obtained. These diffraction patterns can be used as atomic-site-resolved probes for local electronic structure investigation in combination with spectroscopy techniques. Direct three-dimensional atomic structure visualization and site-specific electronic property analysis methods are reviewed. Furthermore, circular dichroism was also found in valence photoelectron and Auger electron diffraction patterns. The investigation of these new phenomena provides hints for the development of new techniques for local structure probing.

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

PubMed

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

2008-09-22

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. 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 degrees C showed that Tat Eli is not a random coil at 20 degrees 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. We show that active Tat variants share a similar folding pattern whatever their size, but mutations induce local structural changes.

Intrinsic transmission magnetic circular dichroism spectra of GaMnAs

NASA Astrophysics Data System (ADS)

Terada, Hiroshi; Ohya, Shinobu; Tanaka, Masaaki

2018-03-01

Transmission magnetic circular dichroism (MCD) spectroscopy has been widely used to reveal the spin-dependent band structure of ferromagnetic semiconductors. In these previous studies, some band pictures have been proposed from the spectral shapes observed in transmission MCD; however, extrinsic signals originating from optical interference have not been appropriately considered. In this study, we calculate the MCD spectra taking into account the optical interference of the layered structure of samples and show that the spectral shape of MCD is strongly influenced by optical interference. To correctly understand the transmission MCD, we also calculate the intrinsic MCD spectra of GaMnAs that are not influenced by the optical interference. The spectral shape of the intrinsic MCD can be explained by the characteristic band structure of GaMnAs, that is, the spin-polarized valence band and the impurity band existing above the valence band top.

Determination of the absolute configurations of natural products via density functional theory calculations of optical rotation, electronic circular dichroism, and vibrational circular dichroism: the cytotoxic sesquiterpene natural products quadrone, suberosenone, suberosanone, and suberosenol A acetate.

PubMed

Stephens, P J; McCann, D M; Devlin, F J; Smith, A B

2006-07-01

The determination of the absolute configurations (ACs) of chiral molecules using the chiroptical techniques of optical rotation (OR), electronic circular dichroism (ECD), and vibrational circular dichroism (VCD) has been revolutionized by the development of density functional theory (DFT) methods for the prediction of these properties. Here, we demonstrate the significance of these advances for the stereochemical characterization of natural products. Time-dependent DFT (TDDFT) calculations of the specific rotations, [alpha](D), of four cytotoxic natural products, quadrone (1), suberosenone (2), suberosanone (3), and suberosenol A acetate (4), are used to assign their ACs. TDDFT calculations of the ECD of 1 are used to assign its AC. The VCD spectrum of 1 is reported and also used, together with DFT calculations, to assign its AC. The ACs of 1 derived from its [alpha](D), ECD, and VCD are identical and in agreement with the AC previously determined via total synthesis. The previously undetermined ACs of 2-4, derived from their [alpha](D) values, have absolute configurations of their tricyclic cores identical to that of 1. Further studies of the ACs of these molecules using ECD and, especially, VCD are recommended to establish more definitively this finding. Our studies of the OR, ECD, and VCD of quadrone are the first to utilize DFT calculations of all three properties for the determination of the AC of a chiral natural product molecule.

X-ray imaging of spin currents and magnetisation dynamics at the nanoscale

NASA Astrophysics Data System (ADS)

Bonetti, Stefano

2017-04-01

Understanding how spins move in time and space is the aim of both fundamental and applied research in modern magnetism. Over the past three decades, research in this field has led to technological advances that have had a major impact on our society, while improving the understanding of the fundamentals of spin physics. However, important questions still remain unanswered, because it is experimentally challenging to directly observe spins and their motion with a combined high spatial and temporal resolution. In this article, we present an overview of the recent advances in x-ray microscopy that allow researchers to directly watch spins move in time and space at the microscopically relevant scales. We discuss scanning x-ray transmission microscopy (STXM) at resonant soft x-ray edges, which is available at most modern synchrotron light sources. This technique measures magnetic contrast through the x-ray magnetic circular dichroism (XMCD) effect at the resonant absorption edges, while focusing the x-ray radiation at the nanometre scale, and using the intrinsic pulsed structure of synchrotron-generated x-rays to create time-resolved images of magnetism at the nanoscale. In particular, we discuss how the presence of spin currents can be detected by imaging spin accumulation, and how the magnetisation dynamics in thin ferromagnetic films can be directly imaged. We discuss how a direct look at the phenomena allows for a deeper understanding of the the physics at play, that is not accessible to other, more indirect techniques. Finally, we present an overview of the exciting opportunities that lie ahead to further understand the fundamentals of novel spin physics, opportunities offered by the appearance of diffraction limited storage rings and free electron lasers.

X-ray imaging of spin currents and magnetisation dynamics at the nanoscale.

PubMed

Bonetti, Stefano

2017-04-05

Understanding how spins move in time and space is the aim of both fundamental and applied research in modern magnetism. Over the past three decades, research in this field has led to technological advances that have had a major impact on our society, while improving the understanding of the fundamentals of spin physics. However, important questions still remain unanswered, because it is experimentally challenging to directly observe spins and their motion with a combined high spatial and temporal resolution. In this article, we present an overview of the recent advances in x-ray microscopy that allow researchers to directly watch spins move in time and space at the microscopically relevant scales. We discuss scanning x-ray transmission microscopy (STXM) at resonant soft x-ray edges, which is available at most modern synchrotron light sources. This technique measures magnetic contrast through the x-ray magnetic circular dichroism (XMCD) effect at the resonant absorption edges, while focusing the x-ray radiation at the nanometre scale, and using the intrinsic pulsed structure of synchrotron-generated x-rays to create time-resolved images of magnetism at the nanoscale. In particular, we discuss how the presence of spin currents can be detected by imaging spin accumulation, and how the magnetisation dynamics in thin ferromagnetic films can be directly imaged. We discuss how a direct look at the phenomena allows for a deeper understanding of the the physics at play, that is not accessible to other, more indirect techniques. Finally, we present an overview of the exciting opportunities that lie ahead to further understand the fundamentals of novel spin physics, opportunities offered by the appearance of diffraction limited storage rings and free electron lasers.

Digital tomosynthesis (DTS) with a Circular X-ray tube: Its image reconstruction based on total-variation minimization and the image characteristics

NASA Astrophysics Data System (ADS)

Park, Y. O.; Hong, D. K.; Cho, H. S.; Je, U. K.; Oh, J. E.; Lee, M. S.; Kim, H. J.; Lee, S. H.; Jang, W. S.; Cho, H. M.; Choi, S. I.; Koo, Y. S.

2013-09-01

In this paper, we introduce an effective imaging system for digital tomosynthesis (DTS) with a circular X-ray tube, the so-called circular-DTS (CDTS) system, and its image reconstruction algorithm based on the total-variation (TV) minimization method for low-dose, high-accuracy X-ray imaging. Here, the X-ray tube is equipped with a series of cathodes distributed around a rotating anode, and the detector remains stationary throughout the image acquisition. We considered a TV-based reconstruction algorithm that exploited the sparsity of the image with substantially high image accuracy. We implemented the algorithm for the CDTS geometry and successfully reconstructed images of high accuracy. The image characteristics were investigated quantitatively by using some figures of merit, including the universal-quality index (UQI) and the depth resolution. For selected tomographic angles of 20, 40, and 60°, the corresponding UQI values in the tomographic view were estimated to be about 0.94, 0.97, and 0.98, and the depth resolutions were about 4.6, 3.1, and 1.2 voxels in full width at half maximum (FWHM), respectively. We expect the proposed method to be applicable to developing a next-generation dental or breast X-ray imaging system.

Relativistic effects on magnetic circular dichroism studied by GUHF/SECI method

NASA Astrophysics Data System (ADS)

Honda, Y.; Hada, M.; Ehara, M.; Nakatsuji, H.; Downing, J.; Michl, J.

2002-04-01

Quasi-relativistic formulation of the Magnetic circular dichroism (MCD) Faraday terms are presented using the generalized unrestricted Hartree-Fock (GUHF)/single excitation configuration interaction (SECI) method combined with the finite perturbation method and applied to the MCD of the three n-σ ∗ states ( 3Q1, 3Q0, 1Q1) of CH 3I. The Faraday B term for the 1Q1 state was 0.1976( Debye) 2( Bohr magneton )/(10 3 cm-1) in the non-relativistic theory, but was dramatically improved by the relativistic effect and became 0.0184 in agreement with the experimental values, 0.014 and 0.0257. This change was mainly due to the one-electron spin-orbit (SO1) term rather than the spin-free relativistic (SFR) and the two-electron spin-orbit (SO2) terms.

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

PubMed Central

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

2008-01-01

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

Fast helicity switching of x-ray circular polarization at beamline P09 at PETRA III

DOE Office of Scientific and Technical Information (OSTI.GOV)

Strempfer, J., E-mail: Joerg.Strempfer@desy.de; Mardegan, J. R. L.; Francoual, S.

At the resonant scattering and diffraction beamline P09 at PETRA III/DESY, polarization manipulation in the X-ray energy range 3-13 keV is possible using wave-plates. Recently, fast flipping of circular polarization helicity using the Raspberry Pi controlled FPGA (PiLC) device developed at DESY and dedicated piezo-electric flippers has been commissioned. Functionality of the PiLC for XMCD and first XMCD measurements at the Fe K-and Dy-L{sub 3} absorption edges are presented.

Electronic structure and soft-X-ray-induced photoreduction studies of iron-based magnetic polyoxometalates of type {(M)M5}12Fe(III)30 (M = Mo(VI), W(VI)).

PubMed

Kuepper, Karsten; Derks, Christine; Taubitz, Christian; Prinz, Manuel; Joly, Loïc; Kappler, Jean-Paul; Postnikov, Andrei; Yang, Wanli; Kuznetsova, Tatyana V; Wiedwald, Ulf; Ziemann, Paul; Neumann, Manfred

2013-06-14

Giant Keplerate-type molecules with a {Mo72Fe30} core show a number of very interesting properties, making them particularly promising for various applications. So far, only limited data on the electronic structure of these molecules from X-ray spectra and electronic structure calculations have been available. Here we present a combined electronic and magnetic structure study of three Keplerate-type nanospheres--two with a {Mo72Fe30} core and one with a {W72Fe30} core by means of X-ray absorption spectroscopy, X-ray magnetic circular dichroism (XMCD), SQUID magnetometry, and complementary theoretical approaches. Furthermore, we present detailed studies of the Fe(3+)-to-Fe(2+) photoreduction process, which is induced under soft X-ray radiation in these molecules. We observe that the photoreduction rate greatly depends on the ligand structure surrounding the Fe ions, with negatively charged ligands leading to a dramatically reduced photoreduction rate. This opens the possibility of tailoring such polyoxometalates by X-ray spectroscopic studies and also for potential applications in the field of X-ray induced photochemistry.

Circular birefringence/dichroism measurement of optical scattering samples using amplitude-modulation polarimetry

NASA Astrophysics Data System (ADS)

Liu, Wei-Chun; Lo, Yu-Lung; Phan, Quoc-Hung

2018-03-01

A method is proposed for extracting the circular birefringence (CB), circular dichroism (CD) and depolarization (Dep) properties of optical scattering samples using an amplitude-modulation polarimetry technique. The validity of the proposed method is demonstrated by extracting the CB property of pure glucose aqueous samples, the CB/Dep properties of glucose solutions containing 0.02% lipofundin particles, and the CD/Dep properties of chlorophyllin solutions containing suspended polystyrene microspheres. The results show that the proposed technique has the ability to detect pure glucose with a resolution of 66 mg/dL over a concentration range of 0-500 mg/dL. Moreover, the glucose concentration of the CB/Dep samples can be detected over the same range with a resolution of 168 mg/dL. Finally, the chlorophyllin concentration of the CD/Dep sample can be detected over the range of 0-200 μg/dL with a resolution of 6.5 × 10-5. In general, the results show that the proposed technique provides a reliable and accurate means of measuring the CB/CD properties of optical samples with scattering effects, and thus has significant potential for biological sensing applications.

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

NASA Astrophysics Data System (ADS)

Baǧda, Efkan; Baǧda, Esra; Yabaş, Ebru

2017-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2016-08-01

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

Theoretical Investigation of Single-Molecule Sensing Using Nanotube-Enhanced Circular Dichroism.

PubMed

Silva, Jaime; Milne, Bruce F; Nogueira, Fernando

2018-06-19

First-principles calculations have been used to investigate the potential use of circular dichroism (CD) spectroscopy in single-molecule sensing. Using a real-space implementation of time-dependent density functional theory (TDDFT), several systems involving single-walled carbon nanotubes (SWCNT) and small molecules have been studied to evaluate their CD response. Large induced CD (ICD) effects, differing for each test molecule, were observed in all SWCNT-molecule complexes. As the SWCNT used in this study shows no intrinsic CD response, the ICD spectra are the result of interaction with the small molecules. This finding is general and independent of the (a)chiral nature of the adsorbed molecule. Our results indicate that it is possible to design a system that uses SWCNT for detection of molecules using the change in CD spectrum of the system induced by adsorption of the molecule onto the SWCNT surface.

Combination of acoustic levitation with small angle scattering techniques and synchrotron radiation circular dichroism. Application to the study of protein solutions.

PubMed

Cristiglio, Viviana; Grillo, Isabelle; Fomina, Margarita; Wien, Frank; Shalaev, Evgenyi; Novikov, Alexey; Brassamin, Séverine; Réfrégiers, Matthieu; Pérez, Javier; Hennet, Louis

2017-01-01

The acoustic levitation technique is a useful sample handling method for small solid and liquids samples, suspended in air by means of an ultrasonic field. This method was previously used at synchrotron sources for studying pharmaceutical liquids and protein solutions using x-ray diffraction and small angle x-ray scattering (SAXS). In this work we combined for the first time this containerless method with small angle neutron scattering (SANS) and synchrotron radiation circular dichroism (SRCD) to study the structural behavior of proteins in solutions during the water evaporation. SANS results are also compared with SAXS experiments. The aggregation behavior of 45μl droplets of lysozyme protein diluted in water was followed during the continuous increase of the sample concentration by evaporating the solvent. The evaporation kinetics was followed at different drying stage by SANS and SAXS with a good data quality. In a prospective work using SRCD, we also studied the evolution of the secondary structure of the myoglobin protein in water solution in the same evaporation conditions. Acoustic levitation was applied for the first time with SANS and the high performances of the used neutron instruments made it possible to monitor fast container-less reactions in situ. A preliminary work using SRCD shows the potentiality of its combination with acoustic levitation for studying the evolution of the protein structure with time. This multi-techniques approach could give novel insights into crystallization and self-assembly phenomena of biological compound with promising potential applications in pharmaceutical, food and cosmetics industry. This article is part of a Special Issue entitled "Science for Life" Guest Editor: Dr. Austen Angell, Dr. Salvatore Magazù and Dr. Federica Migliardo. Copyright © 2016 Elsevier B.V. All rights reserved.

Two-photon x-ray diffraction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stohr, J.

The interference pattern of a circular photon source has long been used to define the optical diffraction limit. Here we show the breakdown of conventional x-ray diffraction theory for the fundamental case of a “source”, consisting of a back-illuminated thin film in a circular aperture. When the conventional spontaneous x-ray scattering by atoms in the film is replaced at high incident intensity by stimulated resonant scattering, the film becomes the source of cloned photon twins and the diffraction pattern becomes self-focused beyond the diffraction limit. Furthermore, the case of cloned photon pairs is compared to and distinguished from entangled photonmore » pairs or biphotons.« less

Two-photon x-ray diffraction

DOE PAGES

Stohr, J.

2017-01-11

The interference pattern of a circular photon source has long been used to define the optical diffraction limit. Here we show the breakdown of conventional x-ray diffraction theory for the fundamental case of a “source”, consisting of a back-illuminated thin film in a circular aperture. When the conventional spontaneous x-ray scattering by atoms in the film is replaced at high incident intensity by stimulated resonant scattering, the film becomes the source of cloned photon twins and the diffraction pattern becomes self-focused beyond the diffraction limit. Furthermore, the case of cloned photon pairs is compared to and distinguished from entangled photonmore » pairs or biphotons.« less

Quantitatively analyzing the mechanism of giant circular dichroism in extrinsic plasmonic chiral nanostructures by tracking the interplay of electric and magnetic dipoles.

PubMed

Hu, Li; Tian, Xiaorui; Huang, Yingzhou; Fang, Liang; Fang, Yurui

2016-02-14

Plasmonic chirality has drawn much attention because of tunable circular dichroism (CD) and the enhancement for chiral molecule signals. Although various mechanisms have been proposed to explain the plasmonic CD, a quantitative explanation like the ab initio mechanism for chiral molecules, is still unavailable. In this study, a mechanism similar to the mechanisms associated with chiral molecules was analyzed. The giant extrinsic circular dichroism of a plasmonic splitting rectangle ring was quantitatively investigated from a theoretical standpoint. The interplay of the electric and magnetic modes of the meta-structure is proposed to explain the giant CD. We analyzed the interplay using both an analytical coupled electric-magnetic dipole model and a finite element method model. The surface charge distributions showed that the circular current yielded by the splitting rectangle ring causes the ring to behave like a magneton at some resonant modes, which then interact with the electric modes, resulting in a mixing of the two types of modes. The strong interplay of the two mode types is primarily responsible for the giant CD. The analysis of the chiral near-field of the structure shows potential applications for chiral molecule sensing.

Magnetic properties of strained multiferroic CoC r2O4 : A soft x-ray study

NASA Astrophysics Data System (ADS)

Windsor, Y. W.; Piamonteze, C.; Ramakrishnan, M.; Scaramucci, A.; Rettig, L.; Huever, J. A.; Bothschafter, E. M.; Bingham, N. S.; Alberca, A.; Avula, S. R. V.; Noheda, B.; Staub, U.

2017-06-01

Using resonant soft x-ray techniques we follow the magnetic behavior of a strained epitaxial film of CoC r2O4 , a type-II multiferroic. The film is [110] oriented, such that both the ferroelectric and ferromagnetic moments can coexist in-plane. X-ray magnetic circular dichroism (XMCD) is used in scattering and in transmission modes to probe the magnetization of Co and Cr separately. The transmission measurements utilized x-ray excited optical luminescence from the substrate. Resonant soft x-ray diffraction (RXD) was used to study the magnetic order of the low temperature phase. The XMCD signals of Co and Cr appear at the same ordering temperature TC≈90 K , and are always opposite in sign. The coercive field of the Co and of Cr moments is the same, and is approximately two orders of magnitude higher than in bulk. Through sum rules analysis an enlarged C o2 + orbital moment (mL) is found, which can explain this hardening. The RXD signal of the (q q 0) reflection appears below TS, the same ordering temperature as the conical magnetic structure in bulk, indicating that this phase remains multiferroic under strain. To describe the azimuthal dependence of this reflection, a slight modification is required to the spin model proposed by the conventional Lyons-Kaplan-Dwight-Menyuk theory for magnetic spinels.

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

NASA Astrophysics Data System (ADS)

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

2015-11-01

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.

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

PubMed

Górecki, Marcin; Groszek, Grażyna; Frelek, Jadwiga

2017-10-01

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

Magnetic properties of Gd T2Zn20 (T =Fe , Co) investigated by x-ray diffraction and spectroscopy

NASA Astrophysics Data System (ADS)

Mardegan, J. R. L.; Francoual, S.; Fabbris, G.; Veiga, L. S. I.; Strempfer, J.; Haskel, D.; Ribeiro, R. A.; Avila, M. A.; Giles, C.

2016-01-01

We investigate the magnetic and electronic properties of the Gd T2Zn20 (T =Fe and Co) compounds using x-ray resonant magnetic scattering (XRMS), x-ray absorption near-edge structure (XANES), and x-ray magnetic circular dichroism (XMCD). The XRMS measurements reveal that GdCo2Zn20 has a commensurate antiferromagnetic spin structure with a magnetic propagation vector τ ⃗=(1/2 ,1/2 ,1/2 ) below the Néel temperature (TN˜ 5.7 K). Only the Gd ions carry a magnetic moment forming an antiferromagnetic structure with magnetic representation Γ6. For the ferromagnetic GdFe2Zn20 compound, an extensive investigation was performed at low temperature and under magnetic field using XANES and XMCD. A strong XMCD signal of about 12.5 % and 9.7 % is observed below the Curie temperature (TC˜85 K ) at the Gd L2 and L3 edges, respectively. In addition, a small magnetic signal of about 0.06 % of the jump is recorded at the Zn K edge, suggesting that the Zn 4 p states are spin polarized by the Gd 5 d extended orbitals.

Magnetic properties of GdT 2Zn 20 (T = Fe, Co) investigated by x-ray diffraction and spectroscopy

DOE PAGES

J. R. L. Mardegan; Fabbris, G.; Francoual, S.; ...

2016-01-26

In this study, we investigate the magnetic and electronic properties of the GdT 2Zn 20 (T=Fe and Co) compounds using x-ray resonant magnetic scattering (XRMS), x-ray absorption near-edge structure (XANES), and x-ray magnetic circular dichroism (XMCD). The XRMS measurements reveal that GdCo 2Zn 20 has a commensurate antiferromagnetic spin structure with a magnetic propagation vector →/ τ = (12,12,12) below the Néel temperature (T N ~ 5.7 K). Only the Gd ions carry a magnetic moment forming an antiferromagnetic structure with magnetic representation Γ 6. For the ferromagnetic GdFe 2Zn 20 compound, an extensive investigation was performed at low temperaturemore » and under magnetic field using XANES and XMCD. A strong XMCD signal of about 12.5% and 9.7% is observed below the Curie temperature (T C ~ 85K) at the Gd L 2 and L 3 edges, respectively. In addition, a small magnetic signal of about 0.06% of the jump is recorded at the Zn K edge, suggesting that the Zn 4p states are spin polarized by the Gd 5d extended orbitals.« less

Enantiomeric resolution and X-ray optical activity of a tricobalt extended metal atom chain† †Electronic supplementary information (ESI) available: Bond distances and angles for 2 and 3, thermal ellipsoid plots, packing diagrams, PXRD data, magnetization curves, thermogravimetric analysis, and additional XNCD and XMCD plots and CD spectra. CCDC 1574514–1574516 and 1588703. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc04131d

PubMed Central

Srinivasan, Anandi; Cortijo, Miguel; Bulicanu, Vladimir; Naim, Ahmad; Clérac, Rodolphe; Rogalev, Andrei; Wilhelm, Fabrice; Rosa, Patrick

2017-01-01

A simple procedure based on anion exchange was employed for the enantiomeric resolution of the extended metal atom chain (EMAC) [Co3(dpa)4(MeCN)2]2+. Use of the chiral salt (NBu4)2[As2(tartrate)2], (Λ-1 or Δ-1), resulted in the selective crystallization of the EMAC enantiomers as [Δ-Co3(dpa)4(MeCN)2](NBu4)2[Λ-As2(tartarte)2]2, (Δ-2) and [Λ-Co3(dpa)4(MeCN)2](NBu4)2[Δ-As2(tartrate)2]2 (Λ-2), respectively, in the P4212 space group, whereas a racemic mixture of 1 yielded [Co3(dpa)4(MeCN)2][As2(tartrate)2]·2MeCN (rac-3), which crystallized in the C2/c space group. The local electronic and magnetic structure of the EMAC enantiomers was studied, exploiting a variety of dichroisms in single crystals. A strong linear dichroism at the Co K-edge was observed in the orthoaxial configuration, whereas it vanished in the axial orientation, thus spectroscopically confirming the D4 crystal symmetry. Compounds Δ-2 and Λ-2 are shown to be enantiopure materials as evidenced by mirror-image natural circular dichroism spectra in the UV/vis in solution and in the X-ray range at the Co K-edge in single crystals. The surprising absence of detectable X-ray magnetic circular dichroism or X-ray magnetochiral dichroism signals at the Co K-edge, even at low temperature (3 K) and a high magnetic field (17 T), is ascribed to a strongly delocalized spin density on the tricobalt core. PMID:29675158

Enantiomeric characterization and structure elucidation of LH601A using vibrational circular dichroism spectroscopy

NASA Astrophysics Data System (ADS)

Shen, Jian; Magesh, Sadagopan; Chen, Lin; Hu, Longqin; He, Yanan

2018-03-01

LH601A is a novel non-reactive chiral molecule inhibiting Keap1-Nrf2 protein-protein interaction. The absolute configuration (AC) was independently determined in this study using vibrational circular dichroism (VCD) spectroscopy. Because of band overlapping and broadening in the IR spectrum, a direct VCD spectrum comparison method is devised without the conventional IR band alignment. Being an unbiased AC inquiry, all possible chiralities are evaluated based on the statistical analysis of VCD similarity, Sv. The AC of three-center stereoisomer LH601A is unambiguously assigned to (S,R,S). A comparative study was also carried out to investigate the structural and energy differences of calculated conformers using the polarized continuum model of dimethyl sulfoxide.

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

PubMed

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

2014-01-01

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

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

ERIC Educational Resources Information Center

Yakubu, Abdallah; Suzuki, Takayoshi; Kita, Masakazu

2017-01-01

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

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

PubMed

Cukras, Janusz; Kauczor, Joanna; Norman, Patrick; Rizzo, Antonio; Rikken, Geert L J A; Coriani, Sonia

2016-05-21

A computational protocol for magneto-chiral dichroism and magneto-chiral birefringence dispersion is presented within the framework of damped response theory, also known as complex polarization propagator theory, at the level of time-dependent Hartree-Fock and time-dependent density functional theory. Magneto-chiral dichroism and magneto-chiral birefringence spectra in the (resonant) frequency region below the first ionization threshold of R-methyloxirane and l-alanine are presented and compared with the corresponding results obtained for both the electronic circular dichroism and the magnetic circular dichroism. The additional information content yielded by the magneto-chiral phenomena, as well as their potential experimental detectability for the selected species, is discussed.

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

PubMed

Phan, Quoc-Hung; Lo, Yu-Lung

2017-04-01

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

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

NASA Astrophysics Data System (ADS)

Kaminský, Jakub; Kříž, Jan; Bouř, Petr

2017-04-01

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

Construction and performance of BL28 of the Photon Factory for circularly polarized synchrotron radiation

NASA Astrophysics Data System (ADS)

Kagoshima, Yasushi; Muto, Sadatsugu; Miyahara, Tsuneaki; Koide, Tsuneharu; Yamamoto, Shigeru; Kitamura, Hideo

1992-01-01

A branch beamline, BL28A, has been constructed for the application of circularly polarized vacuum ultraviolet radiation. The radiation can be obtained in the helical undulator operation mode of an insertion device, EMPW♯28, which is also cut for elliptically polarized hard x-ray radiation. T first harmonic of the helical undulator radiation can be tuned from 40 to 350 eV with its corresponding K value from 3 to 0.2. A monochromator working basically with constant deviation optics was installed, and has started its operation. A circularly polarized flux of ˜1010 photons/s has been achieved with energy resolution of around 500-1000 at the first harmonic peak. The circular polarization after the monochromator was estimated to be higher than 70% by comparing theory and experiment on the magnetic circular dichroism of nickel films in the 3p-3d excitation region. The design philosophy of the beamline and recent results on the performance tests are presented.

Irreversible Denaturation of Maltodextrin Glucosidase Studied by Differential Scanning Calorimetry, Circular Dichroism, and Turbidity Measurements

PubMed Central

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

2014-01-01

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

Unusual Circularly Polarized and Aggregation-Induced Near-Infrared Phosphorescence of Helical Platinum(II) Complexes with Tetradentate Salen Ligands.

PubMed

Song, Jintong; Wang, Man; Zhou, Xiangge; Xiang, Haifeng

2018-05-17

A series of chiral and helical Pt II -Salen complexes with 1,1'-binaphthyl linkers were synthesized and characterized. Owing to the restriction of intramolecular motions of central 1,1'-binaphthyls, the complexes exhibit unusual near-infrared aggregation-induced phosphorescence (AIP). The (R)/(S) enantiopure complexes were characterized by X-ray diffraction, circular dichroism spectra, time-dependent density functional theory calculations, and circularly polarized luminescence (CPL). The present work explores the use of tetradentate ligands that can be easily prepared from commercially available enantiopure compounds, and the subsequent preparation of stable CPL-active square planar Pt II complexes with AIP effect that may have interest in many applications. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Characterization of Glutaredoxin Fe-S Cluster-Binding Interactions Using Circular Dichroism Spectroscopy.

PubMed

Albetel, Angela-Nadia; Outten, Caryn E

2018-01-01

Monothiol glutaredoxins (Grxs) with a conserved Cys-Gly-Phe-Ser (CGFS) active site are iron-sulfur (Fe-S) cluster-binding proteins that interact with a variety of partner proteins and perform crucial roles in iron metabolism including Fe-S cluster transfer, Fe-S cluster repair, and iron signaling. Various analytical and spectroscopic methods are currently being used to monitor and characterize glutaredoxin Fe-S cluster-dependent interactions at the molecular level. The electronic, magnetic, and vibrational properties of the protein-bound Fe-S cluster provide a convenient handle to probe the structure, function, and coordination chemistry of Grx complexes. However, some limitations arise from sample preparation requirements, complexity of individual techniques, or the necessity for combining multiple methods in order to achieve a complete investigation. In this chapter, we focus on the use of UV-visible circular dichroism spectroscopy as a fast and simple initial approach for investigating glutaredoxin Fe-S cluster-dependent interactions. © 2018 Elsevier Inc. All rights reserved.

Laser mass spectrometry with circularly polarized light: circular dichroism of cold molecules in a supersonic gas beam.

PubMed

Titze, Katharina; Zollitsch, Tilo; Heiz, Ulrich; Boesl, Ulrich

2014-09-15

An experiment on chiral molecules that combines circular dichroism (CD) spectroscopy, mass-selective detection by laser mass spectrometry (MS), and cooling of molecules by using a supersonic beam is presented. The combination of the former two techniques (CD-laser-MS) is a new method to investigate chiral molecules and is now used by several research groups. Cooling in a supersonic beam supplies a substantial increase in spectroscopic resolution, a feature that has not yet been used in CD spectroscopy. In the experiments reported herein, a large variation in the electronic CD of carbonyl 3-methylcyclopentanone was observed depending on the excited vibrational modes in the n → π* transition. This finding should be of interest for the detection of chiral molecules and for the theoretical understanding of the CD of vibronic bands. It is expected that this effect will show up in other chiral carbonyls because the n → π* transition is typical for the carbonyl group. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Evidence that a formyl-substituted iron porphyrin is the prosthetic group of myeloperoxidase: magnetic circular dichroism similarity of the peroxidase to Spirographis heme-reconstituted myoglobin.

PubMed Central

Sono, M; Bracete, A M; Huff, A M; Ikeda-Saito, M; Dawson, J H

1991-01-01

To probe the identity of the active site heme-type prosthetic group of myeloperoxidase, whose structure has not been established unambiguously [proposed structures are (i) a chlorin (dihydroporphyrin) or (ii) a formyl-substituted porphyrin such as present in heme a], Spirographis heme (2-formyl-4-vinyldeuteroheme IX) has been incorporated into apo-myoglobin as a possible iron porphyrin model. Comparison of parallel derivatives of these two green proteins with magnetic circular dichroism spectroscopy reveals considerable similarities between several derivatives of these proteins, including the pyridine hemochromogen, the native ferric, ferrous-oxy, and ferrous-CO forms. In contrast, the magnetic circular dichroism spectra of available iron chlorin (octaethylchlorin) model complexes in analogous ligation and oxidation states do not show any significant spectral similarities to myeloperoxidase. This finding provides important evidence in favor of a formyl-substituted porphyrin as the structure of the prosthetic group macrocycle of myeloperoxidase. PMID:1662385

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

NASA Astrophysics Data System (ADS)

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

2008-02-01

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

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

PubMed

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

2015-07-01

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

Polarization control in an X-ray free-electron laser

DOE PAGES

Lutman, Alberto A.; MacArthur, James P.; Ilchen, Markus; ...

2016-05-09

X-ray free-electron lasers are unique sources of high-brightness coherent radiation. However, existing devices supply only linearly polarized light, precluding studies of chiral dynamics. A device called the Delta undulator has been installed at the Linac Coherent Light Source (LCLS) to provide tunable polarization. With a reverse tapered planar undulator line to pre-microbunch the beam and the novel technique of beam diverting, hundreds of microjoules of circularly polarized X-ray pulses are produced at 500–1,200 eV. These X-ray pulses are tens of femtoseconds long, have a degree of circular polarization of 0.98 –0.04 +0.02 at 707 eV and may be scanned inmore » energy. We also present a new two-colour X-ray pump–X-ray probe operating mode for the LCLS. As a result, energy differences of ΔE/E = 2.4% are supported, and the second pulse can be adjusted to any elliptical polarization. In this mode, the pointing, timing, intensity and wavelength of the two pulses can be modified.« less

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

PubMed

Gorinstein, S; Zemser, M; Vargas-Albores, F; Ochoa, J L; Paredes-Lopez, O; Scheler, C; Aksu, S; Salnikow, J

1999-02-01

Characterization of three cactus proteins (native and denatured) from Machaerocereus gummosus (Pitahaya agria), Lophocereu schottii (Garambullo), and Cholla opuntia (Cholla), was based on electrophoretic, fluorescence, CD (circular dichroism), DSC (differential scanning calorimetry), and FT-IR (Fourier transform infrared) measurements. The obtained results of intrinsic fluorescence, DSC, and CD were dissimilar for the three species of cactus, providing evidence of differences in secondary and tertiary structures. Cactus proteins may be situated in the following order corresponding to their relative stability: Machaerocereus gummosus (Pitahaya agria) > Cholla opuntia (Cholla) > Lophocereu schottii (Garambullo). Thermodynamic properties of proteins and their changes upon denaturation (temperature of denaturation, enthalphy, and the number of ruptured hydrogen bonds) were correlated with the secondary structure of proteins and disappearance of alpha-helix.

X-Ray Diffractive Optics

NASA Technical Reports Server (NTRS)

Dennis, Brian; Li, Mary; Skinner, Gerald

2013-01-01

X-ray optics were fabricated with the capability of imaging solar x-ray sources with better than 0.1 arcsecond angular resolution, over an order of magnitude finer than is currently possible. Such images would provide a new window into the little-understood energy release and particle acceleration regions in solar flares. They constitute one of the most promising ways to probe these regions in the solar atmosphere with the sensitivity and angular resolution needed to better understand the physical processes involved. A circular slit structure with widths as fine as 0.85 micron etched in a silicon wafer 8 microns thick forms a phase zone plate version of a Fresnel lens capable of focusing approx. =.6 keV x-rays. The focal length of the 3-cm diameter lenses is 100 microns, and the angular resolution capability is better than 0.1 arcsecond. Such phase zone plates were fabricated in Goddard fs Detector Development Lab. (DDL) and tested at the Goddard 600-microns x-ray test facility. The test data verified that the desired angular resolution and throughput efficiency were achieved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ovchinnikova, E. N.; Rogalev, A.; Wilhelm, F.

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

How and How Much Molecular Conformation Affects Electronic Circular Dichroism: The Case of 1,1-Diarylcarbinols.

PubMed

Padula, Daniele; Pescitelli, Gennaro

2018-01-09

Chiroptical spectra such as electronic circular dichroism (ECD) are said to be much more sensitive to conformation than their non-chiroptical counterparts, however, it is difficult to demonstrate such a common notion in a clear-cut way. We run DFT and TDDFT calculations on two closely related 1,1-diarylmethanols which show mirror-image ECD spectra for the same absolute configuration. We demonstrate that the main reason for the different chiroptical response of the two compounds lies in different conformational ensembles, caused by a single hydrogen-to-methyl substitution. We conclude that two compounds, having the same configuration but different conformation, may exhibit mirror-image ECD signals, stressing the importance and impact of conformational factors on ECD spectra.

Elemental moment variation of bcc FexMn1-x on MgO(001)

NASA Astrophysics Data System (ADS)

Bhatkar, H.; Snow, R. J.; Arenholz, E.; Idzerda, Y. U.

2017-02-01

We report the growth, structural characterization, and electronic structure evolution of epitaxially grown bcc FexMn1-x on MgO(001). It is observed that the 20 nm thick FexMn1-x alloy films remained bcc from 0.65≤x≤1, much beyond the bulk stability range of 0.88≤x≤1. X-ray absorption spectroscopy and X-ray magnetic circular dichroism show that both the Fe and Mn L3 binding energies slightly increase with Mn incorporation and that the elemental moment of Fe in the 20 nm crystalline bcc alloy film remain nearly constant, then shows a dramatic collapse near x 0.84. The Mn MCD intensity is found to be small at all compositions that exhibit ferromagnetism

Use of magnetic circular dichroism to study dinuclear metallohydrolases and the corresponding biomimetics.

PubMed

Larrabee, James A; Schenk, Gerhard; Mitić, Nataša; Riley, Mark J

2015-09-01

Magnetic circular dichroism (MCD) is a convenient technique for providing structural and mechanistic insight into enzymatic systems in solution. The focus of this review is on aspects of geometric and electronic structure that can be determined by MCD, and how this method can further our understanding of enzymatic mechanisms. Dinuclear Co(II) systems that catalyse hydrolytic reactions were selected to illustrate the approach. These systems all contain active sites with similar structures consisting of two Co(II) ions bridged by one or two carboxylates and a water or hydroxide. In most of these active sites one Co(II) is five-coordinate and one is six-coordinate, with differing binding affinities. It is shown how MCD can be used to determine which binding site--five or six-coordinate--has the greater affinity. Importantly, zero-field-splitting data and magnetic exchange coupling constants may be determined from the temperature and field dependence of MCD data. The relevance of these data to the function of the enzymatic systems is discussed.

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

PubMed

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. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

X-ray magnetic spectroscopy of MBE-grown Mn-doped Bi{sub 2}Se{sub 3} thin films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Collins-McIntyre, L. J.; Watson, M. D.; Zhang, S. L.

2014-12-15

We report the growth of Mn-doped Bi{sub 2}Se{sub 3} thin films by molecular beam epitaxy (MBE), investigated by x-ray diffraction (XRD), atomic force microscopy (AFM), SQUID magnetometry and x-ray magnetic circular dichroism (XMCD). Epitaxial films were deposited on c-plane sapphire substrates by co-evaporation. The films exhibit a spiral growth mechanism typical of this material class, as revealed by AFM. The XRD measurements demonstrate a good crystalline structure which is retained upon doping up to ∼7.5 atomic-% Mn, determined by Rutherford backscattering spectrometry (RBS), and show no evidence of the formation of parasitic phases. However an increasing interstitial incorporation of Mnmore » is observed with increasing doping concentration. A magnetic moment of 5.1 μ{sub B}/Mn is obtained from bulk-sensitive SQUID measurements, and a much lower moment of 1.6 μ{sub B}/Mn from surface-sensitive XMCD. At ∼2.5 K, XMCD at the Mn L{sub 2,3} edge, reveals short-range magnetic order in the films and indicates ferromagnetic order below 1.5 K.« less

Swift-X-Ray Telescope Monitoring of the Candidate Supergiant Fast X-ray Transient IGR J16418-4532

NASA Technical Reports Server (NTRS)

Romano, P.; Mangano, V.; Ducci, L.; Esposito, P.; Evans, P. A.; Vercellone, S.; Kennea, J. A.; Burrows, D. N.; Gehrels, N.

2012-01-01

We report on the Swift monitoring of the candidate supergiant fast X-ray transient (SFXT) IGR J16418-4532, for which both orbital and spin periods are known (approx. 3.7 d and approx.1250 s, respectively). Our observations, for a total of approx. 43 ks, span over three orbital periods and represent the most intense and complete sampling of the light curve of this source with a sensitive X-ray instrument. With this unique set of observations, we can address the nature of this transient. By applying the clumpy wind model for blue supergiants to the observed X-ray light curve, and assuming a circular orbit, the X-ray emission from this source can be explained in terms of the accretion from a spherically symmetric clumpy wind, composed of clumps with different masses, ranging from approx. 5 × 10(exp 16) to 10(exp 21) g. Our data suggest, based on the X-ray behaviour, that this is an intermediate SFXT.

Magnetization reversal of the domain structure in the anti-perovskite nitride Co{sub 3}FeN investigated by high-resolution X-ray microscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hajiri, T., E-mail: t.hajiri@numse.nagoya-u.ac.jp; Kuroki, Y.; Ando, H.

2016-05-14

We performed X-ray magnetic circular dichroism (XMCD) photoemission electron microscopy imaging to reveal the magnetic domain structure of anti-perovskite nitride Co{sub 3}FeN exhibiting a negative spin polarization. In square and disc patterns, we systematically and quantitatively determined the statistics of the stable states as a function of geometry. By direct imaging during the application of a magnetic field, we revealed the magnetic reversal process in a spatially resolved manner. We compared the hysteresis on the continuous area and the square patterns from the magnetic field-dependent XMCD ratio, which can be explained as resulting from the effect of the shape anisotropy,more » present in nanostructured thin films.« less

Theory of magnetic cataclysmic binary X-ray sources

NASA Technical Reports Server (NTRS)

Lamb, Don Q.

1988-01-01

The theory of magnetic cataclysmic binary X-ray sources is reviewed. The physics of the accretion torque for disk and for stream accretion is described, and the magnetic field strengths of DQ Her stars inferred from their spin behavior and of AM Her stars from direct measurement are discussed. The implications of disk and stream accretion for the geometry of the emission region and for the X-ray pulse profiles are considered. The physicl properties of the X-ray emission region and the expected infrared, optical, soft X-ray, and hard X-ray spectra are described. The orientations of the magnetic moment in AM Her stars inferred from the circular and linear polarization of the optical light and the optical light curve are commented on.

Circular dichroism spectroscopy: Enhancing a traditional undergraduate biochemistry laboratory experience.

PubMed

Lewis, Russell L; Seal, Erin L; Lorts, Aimee R; Stewart, Amanda L

2017-11-01

The undergraduate biochemistry laboratory curriculum is designed to provide students with experience in protein isolation and purification protocols as well as various data analysis techniques, which enhance the biochemistry lecture course and give students a broad range of tools upon which to build in graduate level laboratories or once they begin their careers. One of the most common biochemistry protein purification experiments is the isolation and characterization of cytochrome c. Students across the country purify cytochrome c, lysozyme, or some other well-known protein to learn these common purification techniques. What this series of experiments lacks is the use of sophisticated instrumentation that is rarely available to undergraduate students. To give students a broader background in biochemical spectroscopy techniques, a new circular dichroism (CD) laboratory experiment was introduced into the biochemistry laboratory curriculum. This CD experiment provides students with a means of conceptualizing the secondary structure of their purified protein, and assessments indicate that students' understanding of the technique increased significantly. Students conducted this experiment with ease and in a short time frame, so this laboratory is conducive to merging with other data analysis techniques within a single laboratory period. © 2017 by The International Union of Biochemistry and Molecular Biology, 45(6):515-520, 2017. © 2017 The International Union of Biochemistry and Molecular Biology.

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

NASA Astrophysics Data System (ADS)

Valencia, Israel; Ávila-Torres, Yenny; Barba-Behrens, Norah; Garzón, Ignacio L.

2015-04-01

Studies on the physicochemical properties of biomimetic compounds of multicopper oxidases are fundamental to understand their reaction mechanisms and catalytic behavior. In this work, electronic, optical, and chiroptical properties of copper(II) complexes with amino-alcohol chiral ligands are theoretically studied by means of time-dependent density functional theory. The calculated absorption and circular dichroism spectra are compared with experimental measurements of these spectra for an uncoordinated pseudoephedrine derivative, as well as for the corresponding mononuclear and trinuclear copper(II)-coordinated complexes. This comparison is useful to gain insights into their electronic structure, optical absorption and optical activity. The optical absorption and circular dichroism bands of the pseudoephedrine derivative are located in the UV-region. They are mainly due to transitions originated from n to π anti-bonding orbitals of the alcohol and amino groups, as well as from π bonding to π anti-bonding orbitals of carboxyl and phenyl groups. In the case of the mononuclear and trinuclear compounds, additional signals in the visible spectral region are present. In both systems, the origin of these bands is due to charge transfer from ligand to metal and d-d transitions.

Wavelength dependent photoelectron circular dichroism of limonene studied by femtosecond multiphoton laser ionization and electron-ion coincidence imaging

NASA Astrophysics Data System (ADS)

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

2016-09-01

Enantiomers of the monoterpene limonene have been investigated by (2 + 1) resonance enhanced multiphoton ionization and photoelectron circular dichroism employing tuneable, circularly polarized femtosecond laser pulses. Electron imaging detection provides 3D momentum measurement while electron-ion coincidence detection can be used to mass-tag individual electrons. Additional filtering, by accepting only parent ion tagged electrons, can be then used to provide discrimination against higher energy dissociative ionization mechanisms where more than three photons are absorbed to better delineate the two photon resonant, one photon ionization pathway. The promotion of different vibrational levels and, tentatively, different electronic ion core configurations in the intermediate Rydberg states can be achieved with different laser excitation wavelengths (420 nm, 412 nm, and 392 nm), in turn producing different state distributions in the resulting cations. Strong chiral asymmetries in the lab frame photoelectron angular distributions are quantified, and a comparison made with a single photon (synchrotron radiation) measurement at an equivalent photon energy.

Strong circular dichroism in a non-chiral metasurface based on an array of metallic V-shaped nanostructures

NASA Astrophysics Data System (ADS)

Ardakani, Abbas Ghasempour; Moradi, Khatereh

2018-02-01

In this paper, an extrinsic chiral metasurface based on a silver thin film containing a periodic array of V-shaped nanostructures is proposed. The proposed structure is normally and obliquely illuminated by right- and left-handed circularly polarized plane waves and the transmission through the structure is calculated using the frequency domain finite-integration technique. Our simulation results show that the designed metasurface exhibits strong circular dichroism (CD) in the transmission Δ = T_{RCP}- T_{LCP}=0.98 in the near-infrared region under oblique incidence. To our knowledge, this is one of highest CD effects that have been achieved so far in the single-layer metasurface based on metallic nanostructures. The physical mechanism for this strong CD effect is explained in terms of the current density distribution. Furthermore, the effects of change of the incident angle, the refractive index of surrounding medium and structure parameters, such as film thickness and lattice constants on CD spectrum, are investigated. In addition, the CD phenomenon in the structure is analyzed in other frequency regions.

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

NASA Astrophysics Data System (ADS)

Orlov, Sergey; Goncharova, Iryna; Urbanová, Marie

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

PDB2CD: a web-based application for the generation of circular dichroism spectra from protein atomic coordinates.

PubMed

Mavridis, Lazaros; Janes, Robert W

2017-01-01

Circular dichroism (CD) spectroscopy is extensively utilized for determining the percentages of secondary structure content present in proteins. However, although a large contributor, secondary structure is not the only factor that influences the shape and magnitude of the CD spectrum produced. Other structural features can make contributions so an entire protein structural conformation can give rise to a CD spectrum. There is a need for an application capable of generating protein CD spectra from atomic coordinates. However, no empirically derived method to do this currently exists. PDB2CD has been created as an empirical-based approach to the generation of protein CD spectra from atomic coordinates. The method utilizes a combination of structural features within the conformation of a protein; not only its percentage secondary structure content, but also the juxtaposition of these structural components relative to one another, and the overall structure similarity of the query protein to proteins in our dataset, the SP175 dataset, the 'gold standard' set obtained from the Protein Circular Dichroism Data Bank (PCDDB). A significant number of the CD spectra associated with the 71 proteins in this dataset have been produced with excellent accuracy using a leave-one-out cross-validation process. The method also creates spectra in good agreement with those of a test set of 14 proteins from the PCDDB. The PDB2CD package provides a web-based, user friendly approach to enable researchers to produce CD spectra from protein atomic coordinates. http://pdb2cd.cryst.bbk.ac.uk CONTACT: r.w.janes@qmul.ac.ukSupplementary information: Supplementary data are available at Bioinformatics online. © The Author 2016. Published by Oxford University Press.

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

PubMed Central

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

1994-01-01

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

Freeze-Quench Magnetic Circular Dichroism Spectroscopic Study of the "Very Rapid" Intermediate in Xanthine Oxidase.

PubMed

Jones, Robert M.; Inscore, Frank E.; Hille, Russ; Kirk, Martin L.

1999-11-01

Freeze-quench magnetic circular dichroism spectroscopy (MCD) has been used to trap and study the excited-state electronic structure of the Mo(V) active site in a xanthine oxidase intermediate generated with substoichiometric concentrations of the slow substrate 2-hydroxy-6-methylpurine. EPR spectroscopy has shown that the intermediate observed in the MCD experiment is the "very rapid" intermediate, which lies on the main catalytic pathway. The low-energy (< approximately 30 000 cm(-1)) C-term MCD of this intermediate is remarkably similar to that of the model compound LMoO(bdt) (L = hydrotris(3,5-dimethyl-1-pyrazolyl)borate; bdt = 1,2-benzenedithiolate), and the MCD bands have been assigned as dithiolate S(ip) --> Mo d(xy) and S(op) --> Mo d(xz,yz) LMCT transitions. These transitions result from a coordination geometry of the intermediate where the Mo=O bond is oriented cis to the ene-1,2-dithiolate of the pyranopterin. Since X-ray crystallography has indicated that a terminal sulfido ligand is oriented cis to the ene-1,2-dithiolate in oxidized xanthine oxidase related Desulfovibrio gigas aldehyde oxidoreductase, we have suggested that a conformational change occurs upon substrate binding. The substrate-mediated conformational change is extremely significant with respect to electron-transfer regeneration of the active site, as covalent interactions between the redox-active Mo d(xy) orbital and the S(ip) orbitals of the ene-1,2-dithiolate are maximized when the oxo ligand is oriented cis to the dithiolate plane. This underlies the importance of the ene-1,2-dithiolate portion of the pyranopterin in providing an efficient superexchange pathway for electron transfer. The results of this study indicate that electron-transfer regeneration of the active site may be gated by the orientation of the Mo=O bond relative to the ene-1,2-dithiolate chelate. Poor overlap between the Mo d(xy) orbital and the S(ip) orbitals of the dithiolate in the oxidized enzyme geometry may

Computational circular dichroism estimation for point-of-care diagnostics via vortex half-wave retarders

NASA Astrophysics Data System (ADS)

Haider, Shahid A.; Tran, Megan Y.; Wong, Alexander

2018-02-01

Observing the circular dichroism (CD) caused by organic molecules in biological fluids can provide powerful indicators of patient health and provide diagnostic clues for treatment. Methods for this kind of analysis involve tabletop devices that weigh tens of kilograms with costs on the order of tens of thousands of dollars, making them prohibitive in point-of-care diagnostic applications. In an e ort to reduce the size, cost, and complexity of CD estimation systems for point-of-care diagnostics, we propose a novel method for CD estimation that leverages a vortex half-wave retarder in between two linear polarizers and a two-dimensional photodetector array to provide an overall complexity reduction in the system. This enables the measurement of polarization variations across multiple polarizations after they interact with a biological sample, simultaneously, without the need for mechanical actuation. We further discuss design considerations of this methodology in the context of practical applications to point-of-care diagnostics.

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

PubMed

Harada, Takunori; Hayakawa, Hiroshi; Kuroda, Reiko

2008-07-01

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

Specific features of the circular dichroism of a chiral photonic crystal with a defect layer inside in the presence of a gain

NASA Astrophysics Data System (ADS)

Gevorgyan, A. H.

2017-01-01

The specific features of the circular dichroism (CD) spectra of a cholesteric liquid crystal (CLC) layer with a defect layer inside in the presence of gain have been investigated. The features of the dependence of CD on the parameter characterizing the gain on the defect mode are analyzed for two cases: (i) gain is present in the defect layer and is absent in the CLC sublayers and (ii) gain is absent in the defect layer but is present in the CLC sublayers. It is shown that these dependences significantly differ in the two aforementioned cases. The dependences of the reflection, transmission, and absorption on the defect mode on the gain parameter have been investigated for incident light with both circular polarizations.

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

NASA Astrophysics Data System (ADS)

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

2007-06-01

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

Visualizing chemical states and defects induced magnetism of graphene oxide by spatially-resolved-X-ray microscopy and spectroscopy.

PubMed

Wang, Y F; Singh, Shashi B; Limaye, Mukta V; Shao, Y C; Hsieh, S H; Chen, L Y; Hsueh, H C; Wang, H T; Chiou, J W; Yeh, Y C; Chen, C W; Chen, C H; Ray, Sekhar C; Wang, J; Pong, W F; Takagi, Y; Ohigashi, T; Yokoyama, T; Kosugi, N

2015-10-20

This investigation studies the various magnetic behaviors of graphene oxide (GO) and reduced graphene oxides (rGOs) and elucidates the relationship between the chemical states that involve defects therein and their magnetic behaviors in GO sheets. Magnetic hysteresis loop reveals that the GO is ferromagnetic whereas photo-thermal moderately reduced graphene oxide (M-rGO) and heavily reduced graphene oxide (H-rGO) gradually become paramagnetic behavior at room temperature. Scanning transmission X-ray microscopy and corresponding X-ray absorption near-edge structure spectroscopy were utilized to investigate thoroughly the variation of the C 2p(π*) states that are bound with oxygen-containing and hydroxyl groups, as well as the C 2p(σ*)-derived states in flat and wrinkle regions to clarify the relationship between the spatially-resolved chemical states and the magnetism of GO, M-rGO and H-rGO. The results of X-ray magnetic circular dichroism further support the finding that C 2p(σ*)-derived states are the main origin of the magnetism of GO. Based on experimental results and first-principles calculations, the variation in magnetic behavior from GO to M-rGO and to H-rGO is interpreted, and the origin of ferromagnetism is identified as the C 2p(σ*)-derived states that involve defects/vacancies rather than the C 2p(π*) states that are bound with oxygen-containing and hydroxyl groups on GO sheets.

Visualizing chemical states and defects induced magnetism of graphene oxide by spatially-resolved-X-ray microscopy and spectroscopy

PubMed Central

Wang, Y. F.; Singh, Shashi B.; Limaye, Mukta V.; Shao, Y. C.; Hsieh, S. H.; Chen, L. Y.; Hsueh, H. C.; Wang, H. T.; Chiou, J. W.; Yeh, Y. C.; Chen, C. W.; Chen, C. H.; Ray, Sekhar C.; Wang, J.; Pong, W. F.; Takagi, Y.; Ohigashi, T.; Yokoyama, T.; Kosugi, N.

2015-01-01

This investigation studies the various magnetic behaviors of graphene oxide (GO) and reduced graphene oxides (rGOs) and elucidates the relationship between the chemical states that involve defects therein and their magnetic behaviors in GO sheets. Magnetic hysteresis loop reveals that the GO is ferromagnetic whereas photo-thermal moderately reduced graphene oxide (M-rGO) and heavily reduced graphene oxide (H-rGO) gradually become paramagnetic behavior at room temperature. Scanning transmission X-ray microscopy and corresponding X-ray absorption near-edge structure spectroscopy were utilized to investigate thoroughly the variation of the C 2p(π*) states that are bound with oxygen-containing and hydroxyl groups, as well as the C 2p(σ*)-derived states in flat and wrinkle regions to clarify the relationship between the spatially-resolved chemical states and the magnetism of GO, M-rGO and H-rGO. The results of X-ray magnetic circular dichroism further support the finding that C 2p(σ*)-derived states are the main origin of the magnetism of GO. Based on experimental results and first-principles calculations, the variation in magnetic behavior from GO to M-rGO and to H-rGO is interpreted, and the origin of ferromagnetism is identified as the C 2p(σ*)-derived states that involve defects/vacancies rather than the C 2p(π*) states that are bound with oxygen-containing and hydroxyl groups on GO sheets. PMID:26481557

Photoelectron circular dichroism in the multiphoton ionization by short laser pulses. II. Three- and four-photon ionization of fenchone and camphor.

PubMed

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

2018-06-07

Angle-resolved multiphoton ionization of fenchone and camphor by short intense laser pulses is computed by the time-dependent single center method. Thereby, the photoelectron circular dichroism (PECD) in the three-photon resonance enhanced ionization and four-photon above-threshold ionization of these molecules is investigated in detail. The computational results are in satisfactory agreement with the available experimental data, measured for randomly oriented fenchone and camphor molecules at different wavelengths of the exciting pulses. We predict a significant enhancement of the multiphoton PECD for uniaxially oriented fenchone and camphor.

Photoelectron circular dichroism in the multiphoton ionization by short laser pulses. II. Three- and four-photon ionization of fenchone and camphor

NASA Astrophysics Data System (ADS)

Müller, Anne D.; Artemyev, Anton N.; Demekhin, Philipp V.

2018-06-01

Angle-resolved multiphoton ionization of fenchone and camphor by short intense laser pulses is computed by the time-dependent single center method. Thereby, the photoelectron circular dichroism (PECD) in the three-photon resonance enhanced ionization and four-photon above-threshold ionization of these molecules is investigated in detail. The computational results are in satisfactory agreement with the available experimental data, measured for randomly oriented fenchone and camphor molecules at different wavelengths of the exciting pulses. We predict a significant enhancement of the multiphoton PECD for uniaxially oriented fenchone and camphor.

Observation of the origin of d0 magnetism in ZnO nanostructures using X-ray-based microscopic and spectroscopic techniques

NASA Astrophysics Data System (ADS)

Singh, Shashi B.; Wang, Yu-Fu; Shao, Yu-Cheng; Lai, Hsuan-Yu; Hsieh, Shang-Hsien; Limaye, Mukta V.; Chuang, Chen-Hao; Hsueh, Hung-Chung; Wang, Hsaiotsu; Chiou, Jau-Wern; Tsai, Hung-Ming; Pao, Chih-Wen; Chen, Chia-Hao; Lin, Hong-Ji; Lee, Jyh-Fu; Wu, Chun-Te; Wu, Jih-Jen; Pong, Way-Faung; Ohigashi, Takuji; Kosugi, Nobuhiro; Wang, Jian; Zhou, Jigang; Regier, Tom; Sham, Tsun-Kong

2014-07-01

Efforts have been made to elucidate the origin of d0 magnetism in ZnO nanocactuses (NCs) and nanowires (NWs) using X-ray-based microscopic and spectroscopic techniques. The photoluminescence and O K-edge and Zn L3,2-edge X-ray-excited optical luminescence spectra showed that ZnO NCs contain more defects than NWs do and that in ZnO NCs, more defects are present at the O sites than at the Zn sites. Specifically, the results of O K-edge scanning transmission X-ray microscopy (STXM) and the corresponding X-ray-absorption near-edge structure (XANES) spectroscopy demonstrated that the impurity (non-stoichiometric) region in ZnO NCs contains a greater defect population than the thick region. The intensity of O K-edge STXM-XANES in the impurity region is more predominant in ZnO NCs than in NWs. The increase in the unoccupied (occupied) density of states at/above (at/below) the conduction-band minimum (valence-band maximum) or the Fermi level is related to the population of defects at the O sites, as revealed by comparing the ZnO NCs to the NWs. The results of O K-edge and Zn L3,2-edge X-ray magnetic circular dichroism demonstrated that the origin of magnetization is attributable to the O 2p orbitals rather than the Zn d orbitals. Further, the local density approximation (LDA) + U verified that vacancies in the form of dangling or unpaired 2p states (due to Zn vacancies) induced a significant local spin moment in the nearest-neighboring O atoms to the defect center, which was determined from the uneven local spin density by analyzing the partial density of states of O 2p in ZnO.Efforts have been made to elucidate the origin of d0 magnetism in ZnO nanocactuses (NCs) and nanowires (NWs) using X-ray-based microscopic and spectroscopic techniques. The photoluminescence and O K-edge and Zn L3,2-edge X-ray-excited optical luminescence spectra showed that ZnO NCs contain more defects than NWs do and that in ZnO NCs, more defects are present at the O sites than at the Zn sites

Homochiral zinc(II) coordination compounds based on in-situ-generated chiral amino acid-tetrazole ligands: circular dichroism, excitation light-induced tunable photoluminescence, and energetic performance.

PubMed

Wang, Shuai-Hua; Zheng, Fa-Kun; Zhang, Ming-Jian; Liu, Zhi-Fa; Chen, Jun; Xiao, Yu; Wu, A-Qing; Guo, Guo-Cong; Huang, Jin-Shun

2013-09-03

We employed two pairs of new in-situ-generated chiral amino acid-tetrazole ligands in constructing homochiral Zn(II) coordination compounds: [Zn(tzet)]n (1a for (S)-tzet and 1b for (R)-tzet, H2tzet = N-[2-(1H-tetrazol-5-yl)ethyl]tryptophan) and [Zn(tzep)(H2O)2]·H2O (2a for (S)-tzep and 2b for (R)-tzep, H2tzep = N-[2-(1H-tetrazol-5-yl)ethyl]proline), which were hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction. Structural analysis reveals that 1 features a 2D homochiral framework generated by both tetrazolate and carboxylate bridges in tzet(2-) ligands. The isolated structure of 2 is stabilized by extensive hydrogen bonds, which leads to formation of a supramolecular 2D architecture. The absolute configuration induced at the nitrogen atoms of 1 and 2 is strictly related to the neighboring chiral carbon atoms by hydrogen-bond interactions. To further investigate their chirality, the combined experimental and theoretical analyses of circular dichroism spectra reveal the absolute configurations and nature of the Cotton effects. Solid-state excitation and emission spectra for 1 and 2 at room temperature were investigated with relevant density of states calculation, and tunable photoluminescence emission of 1 under different excitation wavelengths was discussed. As nitrogen-rich tetrazolate compounds, 1 and 2 possess higher enthalpies of combustion and may serve as a new family of promising energetic materials.

Electronic Circular Dichroism of [16]Helicene With Simplified TD-DFT: Beyond the Single Structure Approach.

PubMed

Bannwarth, Christoph; Seibert, Jakob; Grimme, Stefan

2016-05-01

The electronic circular dichroism (ECD) spectrum of the recently synthesized [16]helicene and a derivative comprising two triisopropylsilyloxy protection groups was computed by means of the very efficient simplified time-dependent density functional theory (sTD-DFT) approach. Different from many previous ECD studies of helicenes, nonequilibrium structure effects were accounted for by computing ECD spectra on "snapshots" obtained from a molecular dynamics (MD) simulation including solvent molecules. The trajectories are based on a molecule specific classical potential as obtained from the recently developed quantum chemically derived force field (QMDFF) scheme. The reduced computational cost in the MD simulation due to the use of the QMDFF (compared to ab-initio MD) as well as the sTD-DFT approach make realistic spectral simulations feasible for these compounds that comprise more than 100 atoms. While the ECD spectra of [16]helicene and its derivative computed vertically on the respective gas phase, equilibrium geometries show noticeable differences, these are "washed" out when nonequilibrium structures are taken into account. The computed spectra with two recommended density functionals (ωB97X and BHLYP) and extended basis sets compare very well with the experimental one. In addition we provide an estimate for the missing absolute intensities of the latter. The approach presented here could also be used in future studies to capture nonequilibrium effects, but also to systematically average ECD spectra over different conformations in more flexible molecules. Chirality 28:365-369, 2016. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

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

NASA Astrophysics Data System (ADS)

Tuite, Eimer Mary; Nordén, Bengt

2018-01-01

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

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

PubMed

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

2014-04-10

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

Enhanced magnetization in VxFe3-xO4 nanoparticles

NASA Astrophysics Data System (ADS)

Pool, V. L.; Kleb, M. T.; Chorney, C. L.; Arenholz, E.; Idzerda, Y. U.

2015-12-01

Nanoparticles of VxFe3-xO4 with up to 33% vanadium doping (x=0 to 1) and a 9 nm diameter are investigated in order to determine the site preference of the vanadium and the magnetic behavior of the nanoparticles. The iron and vanadium L23-edge X-ray absorption spectroscopy (XAS) and X-ray magnetic circular dichroism (MCD) spectra are used to identify that vanadium initially substitutes into the tetrahedral iron site as V3+ and that the average iron moment is observed to increase with vanadium concentration up to 12.5% (x=.375). When the vanadium incorporation exceeds 12.5%, the XAS and MCD show that the vanadium begins substituting as V2+ in the octahedral coordination. This coincides with a rapid reduction of the average moment to zero by 25% (x=.75). The frequency-dependent alternating-current magnetic susceptibility (ACMS) displays a substantial increase in blocking temperature with vanadium concentration and indicated substantial variation in the strength of inter-particle interactions.

AM Herculis - Simultaneous X-ray, optical, and near-IR coverage

NASA Technical Reports Server (NTRS)

Szkody, P.; Tuohy, I. R.; Cordova, F. A.; Stockman, H. S.; Angel, J. R. P.; Wisniewski, W.

1980-01-01

A 6 hour X-ray pointing at AM Her using the HEAO 1 satellite is correlated with simultaneous broadband V and I photometry and visual circular polarimetry. The absence of correlations on either a flickering or an orbital time scale implies distinct regions for the visual and X-ray emission. Significant changes in the light curves are observed from one binary cycle to the next.

Structural changes in calcium-binding allergens: use of circular dichroism to study binding characteristics.

PubMed

Hebenstreit, D; Ferreira, F

2005-09-01

Several studies showed that calcium-binding proteins have a fixed place in the spectrum of allergenic substances. Often the binding of a calcium ion induces conformational changes and affects immunoglobulin E-binding to the allergen. Hence, the quantitative characterization of the binding to calcium is of importance to understand both the biologic and allergenic activity of these proteins. In the present study we describe a procedure for determining the stoichiometry and dissociation constant (K(D)) of calcium-binding allergens using circular dichroism (CD) techniques. For the experiments, we used recombinant Bet v 4, a two EF-hand allergen from birch pollen. Solutions of Bet v 4 were titrated with calcium and the change in molar ellipticity at 222 nm was monitored with a CD spectropolarimeter. The determination of the binding stoichiometry as well as of the K(D) for one EF-hand (4 microM) demonstrated the applicability of the method. CD-monitored calcium-titration of protein solutions represents a fast and easy method for determining the binding characteristics of calcium-binding allergens.

Linear dichroism and the nature of charge order in underdoped cuprates

DOE PAGES

Norman, M. R.

2015-04-21

Recent experiments have addressed the nature of the charge order seen in underdoped cuprates. In this paper, I show that x-ray absorption and linear dichroism are excellent probes of such order. Ab initio calculations reveal that a d-wave charge density wave order involving the oxygen ions is a much better description of the data than alternate models.

CubeX: The CubeSAT X-ray Telescope for Elemental Abundance Mapping of Airless Bodies and X-ray Pulsar Navigation

NASA Astrophysics Data System (ADS)

Nittler, L. R.; Hong, J.; Kenter, A.; Romaine, S.; Allen, B.; Kraft, R.; Masterson, R.; Elvis, M.; Gendreau, K.; Crawford, I.; Binzel, R.; Boynton, W. V.; Grindlay, J.; Ramsey, B.

2017-12-01

The surface elemental composition of a planetary body provides crucial information about its origin, geological evolution, and surface processing, all of which can in turn provide information about solar system evolution as a whole. Remote sensing X-ray fluorescence (XRF) spectroscopy has been used successfully to probe the major-element compositions of airless bodies in the inner solar system, including the Moon, near-Earth asteroids, and Mercury. The CubeSAT X-ray Telescope (CubeX) is a concept for a 6U planetary X-ray telescope (36U with S/C), which utilizes Miniature Wolter-I X-ray optics (MiXO), monolithic CMOS and SDD X-ray sensors for the focal plane, and a Solar X-ray Monitor (heritage from the REXIS XRF instrument on NASA's OSIRIS-REx mission). CubeX will map the surface elemental composition of diverse airless bodies by spectral measurement of XRF excited by solar X-rays. The lightweight ( 1 kg) MiXO optics provide sub-arcminute resolution with low background, while the inherently rad-hard CMOS detectors provide improved spectral resolution ( 150 eV) at 0 °C. CubeX will also demonstrate X-ray pulsar timing based deep space navigation (XNAV). Successful XNAV will enable autonomous deep navigation with little to no support from the Deep Space Network, hence lowering the operation cost for many more planetary missions. Recently selected by NASA Planetary Science Deep Space SmallSat Studies, the first CubeX concept, designed to rideshare to the Moon as a secondary spacecraft on a primary mission, is under study in collaboration with the Mission Design Center at NASA Ames Research Center. From high altitude ( 6,000 km) frozen polar circular orbits, CubeX will study > 8 regions ( 110 km) of geological interest on the Moon over one year to produce a high resolution ( 2-3 km) elemental abundance map of each region. The novel focal plane design of CubeX also allows us to evaluate the performance of absolute navigation by sequential observations of several

Synthesis and studies of axial chiral bisbenzocoumarins: Aggregation-induced emission enhancement properties and aggregation-annihilation circular dichroism effects

NASA Astrophysics Data System (ADS)

Chen, Shaojin; Liu, Wei; Ge, Zhaohai; Zhang, Wenxuan; Wang, Kunpeng; Hu, Zhiqiang

2018-03-01

Axial chiral bisbenzocoumarins were synthesized for the first time by converting naphthanol units in 1,1‧-binaphthol (BINOL) molecule to the benzocoumarin rings. The substitute groups on 3,3‧-positions of bisbenzocoumarins showed significant influence on their aggregation-induced emission enhancement (AEE) properties. It was also found that BBzC1 with ester groups on 3,3‧-positions exhibit an abnormal aggregation-annihilation circular dichroism (AACD) phenomenon, which could be caused by the decrease of the dihedral angle between adjacent benzocoumarin rings in the aggregation state. The single crystal structure of BBzC1 showed that the large dihedral angle in molecule prohibited the strong π-π stacking interactions, which could be main factors for its AEE properties.

Bioactive Formylated Flavonoids from Eugenia rigida: Isolation, Synthesis, and X-ray Crystallography.

PubMed

Zaki, Mohamed A; Nanayakkara, N P Dhammika; Hetta, Mona H; Jacob, Melissa R; Khan, Shabana I; Mohammed, Rabab; Ibrahim, Mohamed A; Samoylenko, Volodymyr; Coleman, Christina; Fronczek, Frank R; Ferreira, Daneel; Muhammad, Ilias

2016-09-23

Two new flavonoids, rac-6-formyl-5,7-dihydroxyflavanone (1) and 2',6'-dihydroxy-4'-methoxy-3'-methylchalcone (2), together with five known derivatives, rac-8-formyl-5,7-dihydroxyflavanone (3), 4',6'-dihydroxy-2'-methoxy-3'-methyldihydrochalcone (4), rac-7-hydroxy-5-methoxy-6-methylflavanone (5), 3'-formyl-2',4',6'-trihydroxy-5'-methyldihydrochalcone (6), and 3'-formyl-2',4',6'-trihydroxydihydrochalcone (7), were isolated from the leaves of Eugenia rigida. The individual (S)- and (R)-enantiomers of 1 and 3, together with the corresponding formylated flavones 8 (6-formyl-5,7-dihydroxyflavone) and 9 (8-formyl-5,7-dihydroxyflavone), as well as 2',4',6'-trihydroxychalcone (10), 3'-formyl-2',4',6'-trihydroxychalcone (11), and the corresponding 3'-formyl-2',4',6'-trihydroxydihydrochalcone (7) and 2',4',6'-trihydroxydihydrochalcone (12), were synthesized. The structures of the isolated and synthetic compounds were established via NMR, HRESIMS, and electronic circular dichroism data. In addition, the structures of 3, 5, and 8 were confirmed by single-crystal X-ray diffraction crystallography. The isolated and synthetic flavonoids were evaluated for their antimicrobial and cytotoxic activities against a panel of microorganisms and solid tumor cell lines.

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

NASA Astrophysics Data System (ADS)

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

2012-06-01

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

Soft X-ray FEL simulation in PAL-XFEL

NASA Astrophysics Data System (ADS)

Shim, Chi Hyun; Ko, In Soo; Parc, Yong Woon; Han, Jang Hui

2015-10-01

The soft X-ray beamline in the Pohang Accelerator Laboratory X-ray Free Electron Laser (PAL-XFEL) will provide a photon beam with a wavelength from 1 nm to 3 nm in the self-amplified spontaneous emission (SASE) mode by using an electron beam with a 3.15-GeV beam energy. Linearly polarized radiation will be supplied by using six planar undulators (PUs). The linearly-polarized radiation powers at 1 (3) nm can reach 10.2 (30) GW. Polarization of the radiation will be controlled by applying the reverse undulator tapering scheme to the PUs and adding two helical undulators (HUs). The circularly-polarized radiation powers at 1 (3) nm will be 3.11 (11.73) GW. The degrees of circular polarization will be larger than 0.99 for both wavelengths. Three options for the future upgrade of the beamline to increase the radiation power are proposed.

History of Chandra X-Ray Observatory

NASA Image and Video Library

2000-09-20

This Chandra image reveals, in detail, the turbulent debris created by a supernova explosion that was observed by the Danish Astronomer Tycho Brahe in the year 1572. The colors show different x-ray energies, with red, green, and blue representing low, medium, and high energies, respectively. Most likely caused by the destruction of a white dwarf star, a shock wave produced by the expanding debris is outlined by the sharp blue circular arcs of 20 million degree Celsius gas seen on the outer rim. The stellar debris, visible only by x-ray, has a temperature of about 10 million degrees, and shows up as mottled yellow, green, and red fingers of gas.

Effects of dynamic diffraction conditions on magnetic parameter determination in a double perovskite Sr2FeMoO6 using electron energy-loss magnetic chiral dichroism.

PubMed

Wang, Z C; Zhong, X Y; Jin, L; Chen, X F; Moritomo, Y; Mayer, J

2017-05-01

Electron energy-loss magnetic chiral dichroism (EMCD) spectroscopy, which is similar to the well-established X-ray magnetic circular dichroism spectroscopy (XMCD), can determine the quantitative magnetic parameters of materials with high spatial resolution. One of the major obstacles in quantitative analysis using the EMCD technique is the relatively poor signal-to-noise ratio (SNR), compared to XMCD. Here, in the example of a double perovskite Sr 2 FeMoO 6 , we predicted the optimal dynamical diffraction conditions such as sample thickness, crystallographic orientation and detection aperture position by theoretical simulations. By using the optimized conditions, we showed that the SNR of experimental EMCD spectra can be significantly improved and the error of quantitative magnetic parameter determined by EMCD technique can be remarkably lowered. Our results demonstrate that, with enhanced SNR, the EMCD technique can be a unique tool to understand the structure-property relationship of magnetic materials particularly in the high-density magnetic recording and spintronic devices by quantitatively determining magnetic structure and properties at the nanometer scale. Copyright © 2017 Elsevier B.V. All rights reserved.

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

NASA Astrophysics Data System (ADS)

Dukor, Rina K.

2017-06-01

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

Circular polarization of X-ray radiation emitted by longitudinally polarized electron impact excitation: Under a screened Coulomb interaction

NASA Astrophysics Data System (ADS)

Chen, Zhan-Bin

2017-12-01

Longitudinally polarized electron impact excitation from the ground state 1s2 to the excited state 1s2l (l =s,p) levels of highly charged He-like Fe24+ ions in weakly coupled hot-dense plasmas is investigated using a fully relativistic distorted-wave method. The Debye-Hückel potential is used to describe the plasma screening. Benchmark results such as the total cross sections, the magnetic sublevels cross sections, and the circular polarizations of corresponding X-ray radiations are presented. For the excitation process, results show that the plasma screening has an effect in reducing both the total and magnetic sublevels cross sections. For the de-excitation process, it is found that while the plasma screening as a slightly effect on the circular polarizations of radiations for the 1 s 2 s 3S1 → 1 s21S0,1 s 2 p 3P2 → 1 s21S0 , and 1 s 2 p 1P1 → 1 s21S0 transition lines, it gives a substantial contribution for the same properties of the 1 s 2 p 3P1 → 1 s21S0 line.

The effect of vacuum birefringence on the polarization of X-ray binaries and pulsars

NASA Technical Reports Server (NTRS)

Novick, R.; Weisskopf, M. C.; Angel, J. R. P.; Sutherland, P. G.

1977-01-01

In a strong magnetic field the vacuum becomes birefringent. This effect is especially important for pulsars at X-ray wavelengths. Any polarized X-ray emission from the surface of a magnetic neutron star becomes depolarized as it propagates through the magnetic field. The soft X-ray emission from AM Her, believed to be a magnetic white dwarf, may show about one radian of phase retardation. In this case, circular polarization of the X-ray flux would be a characteristic signature of vacuum birefringence.

The Imaging X-Ray Polarimetry Explorer (IXPE): Overview

NASA Technical Reports Server (NTRS)

O'Dell, Steve; Weisskopf, M.; Soffitta, P.; Baldini, L.; Bellazzini, R.; Costa, E.; Elsner, R.; Kaspi, V.; Kolodziejczak, J.; Latronico, L.;

Helical Inversion of Gel Fibrils by Elongation of Perfluoroalkyl Chains as Studied by Vibrational Circular Dichroism.

PubMed

Sato, Hisako; Yajima, Tomoko; Yamagishi, Akihiko

2016-05-01

Vibrational circular dichroism (VCD) spectroscopy was applied to gelation by a chiral low-molecular mass weight gelator, N,N'-diperfluoroalkanoyl-1,2-trans-diaminocyclohexane. Attention was focused on the winding effects of (-CF2 )n chains on the gelating ability. For this purpose, a series of gelators were synthesized with perfluoroalkyl chains of different length (n = 6-8). When gelation was studied using acetonitrile as a solvent, the fibrils took different morphologies, depending on the chain length: twisted saddle-like ribbon or helical ribbon from fibril (n = 6) and a helical ribbon from platelet (n = 8). The signs of VCD peaks assigned to the couplet of C=O stretching and to the C-F stretching were also dependent on n, indicating that a gelator molecule changed conformation on elongating perfluoroalkyl chains. A model is proposed for the aggregation modes in fibrils. Chirality 28:361-364, 2016. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

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

PubMed

Ke, Yaling; Zhao, Yi

2017-05-07

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

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

NASA Astrophysics Data System (ADS)

Ke, Yaling; Zhao, Yi

2017-05-01

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

Detection of magnetic circular dichroism in amorphous materials utilizing a single-crystalline overlayer

DOE PAGES

Lin, J.; Zhong, X. Y.; Song, C.; ...

2017-12-27

Physicists are fascinated with topological defects in solid-state materials, because by breaking the translational symmetry they offer emerging properties that are not present in their parental phases. For example, edge dislocations—the 2π phase-winding topological defects—in antiferromagnetic NiO crystals can exhibit ferromagnetic behaviors. Herein, we study how these defects could give rise to exotic topological orders when they interact with a high energy electron beam. To probe this interaction, we formed a coherent electron nanobeam in a scanning transmission electron microscope and recorded the far-field transmitted patterns as the beam steps through the edge dislocation core in [001] NiO. Surprisingly, wemore » found the amplitude patterns of the <020> Bragg disks evolve in a similar manner to the evolution of an annular solar eclipse. Using the ptychographic technique, we recovered the missing phase information in the diffraction plane and revealed the topological phase vortices in the diffracted beams. Through atomic topological defects, the wave function of electrons can be converted from plane wave to electron vortex. This approach provides a new perspective for boosting the collection efficiency of magnetic circular dichroism spectra with high spatial resolution and understanding the relationship between symmetry breaking and exotic property of individual topological defect at atomic level.« less

Detection of magnetic circular dichroism in amorphous materials utilizing a single-crystalline overlayer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lin, J.; Zhong, X. Y.; Song, C.

Physicists are fascinated with topological defects in solid-state materials, because by breaking the translational symmetry they offer emerging properties that are not present in their parental phases. For example, edge dislocations—the 2π phase-winding topological defects—in antiferromagnetic NiO crystals can exhibit ferromagnetic behaviors. Herein, we study how these defects could give rise to exotic topological orders when they interact with a high energy electron beam. To probe this interaction, we formed a coherent electron nanobeam in a scanning transmission electron microscope and recorded the far-field transmitted patterns as the beam steps through the edge dislocation core in [001] NiO. Surprisingly, wemore » found the amplitude patterns of the <020> Bragg disks evolve in a similar manner to the evolution of an annular solar eclipse. Using the ptychographic technique, we recovered the missing phase information in the diffraction plane and revealed the topological phase vortices in the diffracted beams. Through atomic topological defects, the wave function of electrons can be converted from plane wave to electron vortex. This approach provides a new perspective for boosting the collection efficiency of magnetic circular dichroism spectra with high spatial resolution and understanding the relationship between symmetry breaking and exotic property of individual topological defect at atomic level.« less

Magnetic and structural X-ray dichroïsms of metallic multilayers

NASA Astrophysics Data System (ADS)

Pizzini, Stefania; Fontaine, A.; Baudelet, F.; Minr, S.; Giorgetti, C.; Dartyge, E.; Bobo, J. F.; Piecuch, M.

1995-05-01

Fe/Cu and Co/Cu multilayers are intensively studied because of their exceptional magnetic properties, i.e., their giant magnetoresistance and the oscillations of the magnetic coupling between magnetic layers as a function of the thickness of the copper spacer [S.S. Parkin et al., Phys. Rev. Lett. 66 (1991) 2152; F. Petroff et al., Phys. Rev. B 44 (1991) 5355]. Spectroscopic approaches to the understanding of the coupling of ferromagnetic layers through a noble metal layer have been recently introduced, in particular spin-resolved photoemission [N.B. Brookes et al., Phys. Rev. Lett. 67 (1991) 354; C. Carbone et al., PRL 71 (1993) 2805] inverse photoemission [J.E. Ortega et al., Phys. Rev. Lett. 69 (1992) 844; Phys. Rev. B 47 (1993) 1540] and magnetic circular dichroism [S. Pizzini et al., MRS Symp. Proc., vol. 313 (1993); M.G. Samant et al. Phys. Rev. Lett. 72 (1994) 2152; S. Pizzini et al., Phys. Rev. Lett. 74 (1995) 1470]. X-ray absorption spectroscopy appears to be effective both for determination of the local structure, specific to the bidimensionality of the system but also for the electron symmetry-dependent evaluation of the spin polarisation of the noble metal as well as the magnetic element.

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

PubMed

Kosaka, Tomoyo; Inoue, Yoshihisa; Mori, Tadashi

2016-03-03

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.

Simulation of Electronic Circular Dichroism of Nucleic Acids: From the Structure to the Spectrum.

PubMed

Padula, Daniele; Jurinovich, Sandro; Di Bari, Lorenzo; Mennucci, Benedetta

2016-11-14

We present a quantum mechanical (QM) simulation of the electronic circular dichroism (ECD) of nucleic acids (NAs). The simulation combines classical molecular dynamics, to obtain the structure and its temperature-dependent fluctuations, with a QM excitonic model to determine the ECD. The excitonic model takes into account environmental effects through a polarizable embedding and uses a refined approach to calculate the electronic couplings in terms of full transition densities. Three NAs with either similar conformations but different base sequences or similar base sequences but different conformations have been investigated and the results were compared with experimental observations; a good agreement was seen in all cases. A detailed analysis of the nature of the ECD bands in terms of their excitonic composition was also carried out. Finally, a comparison between the QM and the DeVoe models clearly revealed the importance of including fluctuations of the excitonic parameters and of accurately determining the electronic couplings. This study demonstrates the feasibility of the ab initio simulation of the ECD spectra of NAs, that is, without the need of experimental structural or electronic data. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

X-Ray Brightening and UV Fading of Tidal Disruption Event ASASSN-15oi

NASA Astrophysics Data System (ADS)

Gezari, S.; Cenko, S. B.; Arcavi, I.

2017-12-01

We present late-time observations by Swift and XMM-Newton of the tidal disruption event (TDE) ASASSN-15oi that reveal that the source brightened in the X-rays by a factor of ∼10 one year after its discovery, while it faded in the UV/optical by a factor of ∼100. The XMM-Newton observations measure a soft X-ray blackbody component with {{kT}}{bb}∼ 45 {eV}, corresponding to radiation from several gravitational radii of a central ∼ {10}6 {M}ȯ black hole. The last Swift epoch taken almost 600 days after discovery shows that the X-ray source has faded back to its levels during the UV/optical peak. The timescale of the X-ray brightening suggests that the X-ray emission could be coming from delayed accretion through a newly forming debris disk and that the prompt UV/optical emission is from the prior circularization of the disk through stream–stream collisions. The lack of spectral evolution during the X-ray brightening disfavors ionization breakout of a TDE “veiled” by obscuring material. This is the first time a TDE has been shown to have a delayed peak in soft X-rays relative to the UV/optical peak, which may be the first clear signature of the real-time assembly of a nascent accretion disk, and provides strong evidence for the origin of the UV/optical emission from circularization, as opposed to reprocessed emission of accretion radiation.

Magnetic Cr doping of Bi2Se3: Evidence for divalent Cr from x-ray spectroscopy

NASA Astrophysics Data System (ADS)

Figueroa, A. I.; van der Laan, G.; Collins-McIntyre, L. J.; Zhang, S.-L.; Baker, A. A.; Harrison, S. E.; Schönherr, P.; Cibin, G.; Hesjedal, T.

2014-10-01

Ferromagnetically doped topological insulators with broken time-reversal symmetry are a prerequisite for observing the quantum anomalous Hall effect. Cr-doped (Bi,Sb)2(Se,Te)3 is the most successful materials system so far, as it combines ferromagnetic ordering with acceptable levels of additional bulk doping. Here, we report a study of the local electronic structure of Cr dopants in epitaxially grown Bi2Se3 thin films. Contrary to the established view that the Cr dopant is trivalent because it substitutionally replaces Bi3+, we find instead that Cr is divalent. This is evidenced by the energy positions of the Cr K and L2,3 absorption edges relative to reference samples. The extended x-ray absorption fine structure at the K edge shows that the Cr dopants substitute on octahedral sites with the surrounding Se ions contracted by Δd =-0.36 Å, in agreement with recent band structure calculations. Comparison of the Cr L2,3 x-ray magnetic circular dichroism at T =5 K with multiplet calculations gives a spin moment of 3.64 μB/Crbulk, which is close to the saturation moment for Cr2+ d4. The reduced Cr oxidation state in doped Bi2Se3 is ascribed to the formation of a covalent bond between Cr d (eg) and Se p orbitals, which is favored by the contraction of the Cr-Se distances.

Attosecond time-energy structure of X-ray free-electron laser pulses

NASA Astrophysics Data System (ADS)

Hartmann, N.; Hartmann, G.; Heider, R.; Wagner, M. S.; Ilchen, M.; Buck, J.; Lindahl, A. O.; Benko, C.; Grünert, J.; Krzywinski, J.; Liu, J.; Lutman, A. A.; Marinelli, A.; Maxwell, T.; Miahnahri, A. A.; Moeller, S. P.; Planas, M.; Robinson, J.; Kazansky, A. K.; Kabachnik, N. M.; Viefhaus, J.; Feurer, T.; Kienberger, R.; Coffee, R. N.; Helml, W.

2018-04-01

The time-energy information of ultrashort X-ray free-electron laser pulses generated by the Linac Coherent Light Source is measured with attosecond resolution via angular streaking of neon 1s photoelectrons. The X-ray pulses promote electrons from the neon core level into an ionization continuum, where they are dressed with the electric field of a circularly polarized infrared laser. This induces characteristic modulations of the resulting photoelectron energy and angular distribution. From these modulations we recover the single-shot attosecond intensity structure and chirp of arbitrary X-ray pulses based on self-amplified spontaneous emission, which have eluded direct measurement so far. We characterize individual attosecond pulses, including their instantaneous frequency, and identify double pulses with well-defined delays and spectral properties, thus paving the way for X-ray pump/X-ray probe attosecond free-electron laser science.

Role of polar compensation in interfacial ferromagnetism of LaNiO3/CaMnO3 superlattices

NASA Astrophysics Data System (ADS)

Flint, C. L.; Jang, H.; Lee, J.-S.; N'Diaye, A. T.; Shafer, P.; Arenholz, E.; Suzuki, Y.

2017-07-01

Polar compensation can play an important role in the determination of interfacial electronic and magnetic properties in oxide heterostructures. Using x-ray absorption spectroscopy, x-ray magnetic circular dichroism, bulk magnetometry, and transport measurements, we find that interfacial charge redistribution via polar compensation is essential for explaining the evolution of interfacial ferromagnetism in LaNiO3/CaMnO3 superlattices as a function of LaNiO3 layer thickness. In insulating superlattices (four unit cells or less of LaNiO3), magnetism is dominated by Ni-Mn superexchange, while itinerant electron-based Mn-Mn double exchange plays a role in thicker metallic superlattices. X-ray magnetic circular dichroism and resonant x-ray scattering show that Ni-Mn superexchange contributes to the magnetization even in metallic superlattices. This Ni-Mn superexchange interaction can be explained in terms of polar compensation at the LaNiO3-CaMnO3 interface. These results highlight the different mechanisms responsible for interfacial ferromagnetism and the importance of understanding compensation due to polar mismatch at oxide-based interfaces when engineering magnetic properties.

Determination of the absolute configurations of synthetic daunorubicin analogues using vibrational circular dichroism spectroscopy and density functional theory.

PubMed

Yang, Guochun; Tran, Ha; Fan, Eric; Shi, Wei; Lowary, Todd L; Xu, Yunjie

2010-08-01

The absolute configurations of three synthesized anthracycline analogues have been determined using vibrational circular dichroism (VCD) spectroscopy and the density functional theory (DFT) calculations. The experimental VCD spectra of the three compounds have been measured for the first time in the film state, prepared from their CDCl(3) solutions. Conformational searches for the monomers and some dimers of the three compounds have been performed at the DFT level using the B3LYP functional and the 6-311G** and 6-311++G** basis sets. The corresponding vibrational absorption and VCD spectra have been calculated. The good agreement between the experimental and the calculated spectra allows one to assign the absolute configurations of the three compounds with high confidence. In addition, the dominant conformers of the three compounds have also been identified. Copyright 2010 Wiley-Liss, Inc.

Tidal tearing of circumstellar disks in Be/X-ray and gamma-ray binaries

NASA Astrophysics Data System (ADS)

Okazaki, Atsuo T.

2017-11-01

About one half of high-mass X-ray binaries host a Be star [an OB star with a viscous decretion (slowly outflowing) disk]. These Be/X-ray binaries exhibit two types of X-ray outbursts (Stella et al. 1986), normal X-ray outbursts (L X~1036-37 erg s-1) and occasional giant X-ray outbursts (L X > 1037 erg s-1). The origin of giant X-ray outbursts is unknown. On the other hand, a half of gamma-ray binaries have a Be star as the optical counterpart. One of these systems [LS I +61 303 (P orb = 26.5 d)] shows the superorbital (1,667 d) modulation in radio through X-ray bands. No consensus has been obtained for its origin. In this paper, we study a possibility that both phenomena are caused by a long-term, cyclic evolution of a highly misaligned Be disk under the influence of a compact object, by performing 3D hydrodynamic simulations. We find that the Be disk cyclically evolves in mildly eccentric, short-period systems. Each cycle consists of the following stages: 1) As the Be disk grows with time, the initially circular disk becomes eccentric by the Kozai-Lidov mechanism. 2) At some point, the disk is tidally torn off near the base and starts precession. 3) Due to precession, a gap opens between the disk base and mass ejection region, which allows the formation of a new disk in the stellar equatorial plane (see Figure 1). 4) The newly formed disk finally replaces the precessing old disk. Such a cyclic disk evolution has interesting implications for the long-term behavior of high energy emission in Be/X-ray and gamma-ray binaries.

On the interplay between chirality and exciton coupling: a DFT calculation of the circular dichroism in π-stacked ethylene.

PubMed

Norman, Patrick; Linares, Mathieu

2014-09-01

The chirality of stacked weakly interacting π-systems was interpreted in terms of Frenkel exciton states and the formation of excitonic circular dichroism (CD) bands was monitored for ethylene stacks of varying sizes. Convergence of CD bands with respect to the system size was observed for stacks involving around 10 molecules. By means of rotation around the C-C double bond in ethylene, chirality was induced in the monomeric system and which was shown to dominate the spectral responses, even for polymer aggregates. In helical assemblies of chiral entities, there will always be a mix of excitonic and monomeric contributions to the CD signal and it is demonstrated that the complex polarization propagator approach in combination with Density Functional Theory is a suitable method to address this situation. © 2014 Wiley Periodicals, Inc.

Design and characterization of electron beam focusing for X-ray generation in novel medical imaging architecturea

PubMed Central

Bogdan Neculaes, V.; Zou, Yun; Zavodszky, Peter; Inzinna, Louis; Zhang, Xi; Conway, Kenneth; Caiafa, Antonio; Frutschy, Kristopher; Waters, William; De Man, Bruno

2014-01-01

A novel electron beam focusing scheme for medical X-ray sources is described in this paper. Most vacuum based medical X-ray sources today employ a tungsten filament operated in temperature limited regime, with electrostatic focusing tabs for limited range beam optics. This paper presents the electron beam optics designed for the first distributed X-ray source in the world for Computed Tomography (CT) applications. This distributed source includes 32 electron beamlets in a common vacuum chamber, with 32 circular dispenser cathodes operated in space charge limited regime, where the initial circular beam is transformed into an elliptical beam before being collected at the anode. The electron beam optics designed and validated here are at the heart of the first Inverse Geometry CT system, with potential benefits in terms of improved image quality and dramatic X-ray dose reduction for the patient. PMID:24826066

High Field Magnetic Circular Dichroism in Ferromagnetic InMnSb and InMnAs

NASA Astrophysics Data System (ADS)

Meeker, M. A.; Magill, B. A.; Khodaparast, G. A.; Saha, D.; Stanton, C. J.; McGill, S.; Wessels, B. W.

An understanding of the fundamental interactions in narrow gap ferromagnetic semiconductors such as InMnAs and InMnSb has been developed primarily from static magnetization and electrical transport measurements. In this study, to provide a better understanding of the coupling of the Mn impurities to the conduction and valence bands through the sp-d exchange interactions, we have performed magnetic circular dichroism measurements (MCD) on MOVPE grown InMnAs and InMnSb. In our samples, the Mn content varies from 2% to 10.7% and all the samples have Curie temperatures above 300 K. The samples were photo-excited using a Quartz Tungsten Halogen lamp with energies ranging between 0.92-1.45 eV, and in magnetic fields up to 31 T. The temperatures ranged from 15-190 K. Comparison of the observed MCD with theoretical calculations provides a direct method to probe the band structure including the temperature dependence of the spin-orbit split-off bandgap and g-factors, as well as a means to estimate the sp-d coupling constants. Supported by the AFOSR through grant FA9550-14-1-0376, NSF-Career Award DMR-0846834 , NSF-DMR-60035274 , NSF-DMR-1305666, NSF MRI program (DMR-1229217).

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

NASA Astrophysics Data System (ADS)

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

2017-06-01

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

Ferrimagnetism and disorder of epitaxial Mn2-xCoxVAl Heusler compound thin films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Meinert, Markus; Schmalhorst, Jan-Michael; Reiss, Gunter

The quaternary full Heusler compound Mn{sub 2-x}Co{sub x}VAl with x = 1 is predicted to be a half-metallic antiferromagnet. Thin films of the quaternary compounds with x = 0-2 were prepared by dc and RF magnetron co-sputtering on heated MgO (0 0 1) substrates. The magnetic structure was examined by x-ray magnetic circular dichroism and the chemical disorder was characterized by x-ray diffraction. Ferrimagnetic coupling of V to Mn was observed for Mn{sub 2}VAl (x = 0). For x = 0.5, we also found ferrimagnetic order with V and Co antiparallel to Mn. The observed reduced magnetic moments are interpretedmore » with the help of band structure calculations in the coherent potential approximation. Mn{sub 2}VAl is very sensitive to disorder involving Mn, because nearest-neighbour Mn atoms couple antiferromagnetically. Co{sub 2}VAl has B2 order and has reduced magnetization. In the cases with x {ge} 0.9 conventional ferromagnetism was observed, closely related to the atomic disorder in these compounds.« less

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zsila, Ferenc; Gedeon, Gabor

2006-08-11

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

[Characterization of structural change of ascorbate peroxidase from Chinese kale during denaturation by circular dichroism].

PubMed

Xi, Jia-Fu; Tang, Lei; Zhang, Jian-Hua; Zhang, Hong-Jian; Chen, Xu-Sheng; Mao, Zhong-Gui

2014-11-01

Circular dichroism (CD) is a special absorption spectrum. The secondary structure of protein such as α-helix, β-sheet and β-turn in the far ultraviolet region (190-250 nm) has a characteristic CD spectrum. In order to understand the activity and structural changes of ascorbate peroxidase from Chinese kale (BaAPX) during denaturation, specific activity and percentage of secondary structure of BaAPX under different time, temperature and concentration were analyzed by CD dynamically. In addition, the percentage of four secondary structures in BaAPX was calculated by CD analysis software Dichroweb. The results show that BaAPX is a full α-type enzyme whose specific activity is positively related to the percentage of α-helix. During denaturation of BaAPX, three kinds of structural changes were proposed: the one-step structural change from initial state (N state) to minimum state of α-helix (R state) under low concentration and low temperature; the one-step structural change from N state to equilibrium state (T state) under high concentration and low temperature; the two-step structural changes from N state through R state to final T state under heat treatment and low temperature renaturation.

Disentangling the Mn moments on different sublattices in the half-metallic ferrimagnet Mn3?xCoxGa

DOE Office of Scientific and Technical Information (OSTI.GOV)

Klaer, P.; Jenkins, C.A.; Alijani, V.

2011-05-03

Ferrimagnetic Mn{sub 3-x}Co{sub x}Ga compounds have been investigated by magnetic circular dichroism in x-ray absorption (XMCD). Compounds with x > 0.5 crystallize in the CuHg{sub 2}Ti structure. A tetragonal distortion of the cubic structure occurs for x {le} 0.5. For the cubic phase, magnetometry reveals a linearly increasing magnetization of 2x Bohr magnetons per formula unit obeying the generalized Slater-Pauling rule. XMCD confirms the ferrimagnetic character with Mn atoms occupying two different sublattices with antiparallel spin orientation and different degrees of spin localization and identifies the region 0.6 < x {le} 0.8 as most promising for a high spin polarizationmore » at the Fermi level. Individual Mn moments on inequivalent sites are compared to theoretical predictions.« less

Magnetic circular dichroism of thiolate-protected plasmonic gold nanoparticles: separating the effects of interband transitions and surface magnetoplasmon resonance

NASA Astrophysics Data System (ADS)

Shiratsu, Taisuke; Yao, Hiroshi

2016-10-01

Magneto-optical activity is demonstrated in thiolate-protected Au nanoparticles with magnetic circular dichroism (MCD) spectroscopy. The samples examined are decanethiolate-protected Au nanoparticles with the mean diameters ranging from 2.0 to 4.7 nm. The nanoparticles larger than 2.4 nm in diameter exhibit a derivative-like MCD signal, indicating the presence of two circular modes of surface magnetoplasmon, but the spectral shape is so asymmetric that its identification is rather difficult. This is due to the contribution of interband transitions occurring at around the localized surface plasmon resonance (LSPR) frequency. We then develop an efficient method to phenomenologically separate the effects of magnetoplasmonic intraband (= Drude) and interband transitions in the measured MCD spectra using an approximation that the optical response of the Au nanoparticle with a critical size (˜2.0 nm) for the disappearance of LSPR, which is also experimentally obtainable, is substantially dominated by the interband transitions. The consistency of the method is ensured for tiopronin-protected Au nanoparticles, and a very small bisignate magnetoplasmonic response hidden in the total MCD spectrum can be extracted. The practical advantage of the proposed method is that we can intuitively and effectively evaluate the characteristic features of the surface magnetoplasmon of thiolate-protected Au nanoparticles without performing complicated Mie or quasielectrostatic calculations.

Synchrotron radiation circular dichroism spectroscopy study of recombinant T β4 folding

NASA Astrophysics Data System (ADS)

Huang, Yung-Chin; Chu, Hsueh-Liang; Chen, Peng-Jen; Chang, Chia-Ching

Thymosin beta 4 (T β4) is a 43-amino acid small peptide, has been demonstrated that it can promote cardiac repair, wound repair, tissue protection, and involve in the proliferation of blood cell precursor stem cells of bone marrow. Moreover, T β4 has been identified as a multifunction intrinsically disordered protein, which is lacking the stable tertiary structure. Owing to the small size and disordered character, the T β4 protein degrades rapidly and the storage condition is critical. Therefore, it is not easy to reveal its folding mechanism of native T β4. However, recombinant T β4 protein (rT β4), which fused with a 5-kDa peptide in its amino-terminal, is stable and possesses identical function of T β4. Therefore, rT β4 can be used to study its folding mechanism. By using over-critical folding process, stable folding intermediates of rT β4 can be obtained. Structure analysis of folding intermediates by synchrotron radiation circular dichroism (SRCD) and fluorescence spectroscopies indicate that rT β4 is a random coli major protein and its hydrophobic region becomes compact gradually. Moreover, the rT β4 folding is a two state transition. Thermal denaturation analysis indicates that rT β4 lacks stable tertiary structure. These results indicated that rT β4, similar to T β4, is an intrinsically disordered protein. Research is supported by MOST, Taiwan. MOST 103-2112-M-009-011-MY3. Corresponding author: Chia-Ching Chang; ccchang01@faculty.nctu.edu.tw.

Vibronic coupling effect on circular dichroism spectrum: Carotenoid-retinal interaction in xanthorhodopsin

NASA Astrophysics Data System (ADS)

Fujimoto, Kazuhiro J.; Balashov, Sergei P.

2017-03-01

The role of vibronic coupling of antenna carotenoid and retinal in xanthorhodopsin (XR) in its circular dichroism (CD) spectrum is examined computationally. A vibronic exciton model combined with a transition-density-fragment interaction (TDFI) method is developed, and applied to absorption and CD spectral calculations of XR. The TDFI method is based on the electronic Coulomb and exchange interactions between transition densities for individual chromophores [K. J. Fujimoto, J. Chem. Phys. 137, 034101 (2012)], which provides a quantitative description of electronic coupling energy. The TDFI calculation reveals a dominant contribution of the Coulomb interaction to the electronic coupling energy and a negligible contribution of the exchange interaction, indicating that the antenna function of carotenoid results from the Förster type of excitation-energy transfer, not from the Dexter one. The calculated absorption and CD spectra successfully reproduce the main features of the experimental results, which allow us to investigate the mechanism of biphasic CD spectrum observed in XR. The results indicate that vibronic coupling between carotenoid and retinal plays a significant role in the shape of the CD spectrum. Further analysis reveals that the negative value of electronic coupling directly contributes to the biphasic shape of CD spectrum. This study also reveals that the C6—C7 bond rotation of salinixanthin is not the main factor for the biphasic CD spectrum although it gives a non-negligible contribution to the spectral shift. The present method is useful for analyzing the molecular mechanisms underlying the chromophore-chromophore interactions in biological systems.

Monitoring X-Ray Emission from X-Ray Bursters

NASA Technical Reports Server (NTRS)

Halpern, Jules P.; Kaaret, Philip

1999-01-01

The scientific goal of this project was to monitor a selected sample of x-ray bursters using data from the All-Sky Monitor (ASM) on the Rossi X-Ray Timing Explorer together with data from the Burst and Transient Source Experiment (BATSE) on the Compton Gamma-Ray Observatory to study the long-term temporal evolution of these sources in the x-ray and hard x-ray bands. The project was closely related to "Long-Term Hard X-Ray Monitoring of X-Ray Bursters", NASA project NAG5-3891, and and "Hard x-ray emission of x-ray bursters", NASA project NAG5-4633, and shares publications in common with both of these. The project involved preparation of software for use in monitoring and then the actual monitoring itself. These efforts have lead to results directly from the ASM data and also from Target of Opportunity Observations (TOO) made with the Rossi X-Ray Timing Explorer based on detection of transient hard x-ray outbursts with the ASM and BATSE.

Resolving hot spot microstructure using x-ray penumbral imaging (invited)

NASA Astrophysics Data System (ADS)

Bachmann, B.; Hilsabeck, T.; Field, J.; Masters, N.; Reed, C.; Pardini, T.; Rygg, J. R.; Alexander, N.; Benedetti, L. R.; Döppner, T.; Forsman, A.; Izumi, N.; LePape, S.; Ma, T.; MacPhee, A. G.; Nagel, S.; Patel, P.; Spears, B.; Landen, O. L.

2016-11-01

We have developed and fielded x-ray penumbral imaging on the National Ignition Facility in order to enable sub-10 μm resolution imaging of stagnated plasma cores (hot spots) of spherically shock compressed spheres and shell implosion targets. By utilizing circular tungsten and tantalum apertures with diameters ranging from 20 μm to 2 mm, in combination with image plate and gated x-ray detectors as well as imaging magnifications ranging from 4 to 64, we have demonstrated high-resolution imaging of hot spot plasmas at x-ray energies above 5 keV. Here we give an overview of the experimental design criteria involved and demonstrate the most relevant influences on the reconstruction of x-ray penumbral images, as well as mitigation strategies of image degrading effects like over-exposed pixels, artifacts, and photon limited source emission. We describe experimental results showing the advantages of x-ray penumbral imaging over conventional Fraunhofer and photon limited pinhole imaging and showcase how internal hot spot microstructures can be resolved.

Resolving hot spot microstructure using x-ray penumbral imaging (invited).

PubMed

Bachmann, B; Hilsabeck, T; Field, J; Masters, N; Reed, C; Pardini, T; Rygg, J R; Alexander, N; Benedetti, L R; Döppner, T; Forsman, A; Izumi, N; LePape, S; Ma, T; MacPhee, A G; Nagel, S; Patel, P; Spears, B; Landen, O L

2016-11-01

We have developed and fielded x-ray penumbral imaging on the National Ignition Facility in order to enable sub-10 μm resolution imaging of stagnated plasma cores (hot spots) of spherically shock compressed spheres and shell implosion targets. By utilizing circular tungsten and tantalum apertures with diameters ranging from 20 μm to 2 mm, in combination with image plate and gated x-ray detectors as well as imaging magnifications ranging from 4 to 64, we have demonstrated high-resolution imaging of hot spot plasmas at x-ray energies above 5 keV. Here we give an overview of the experimental design criteria involved and demonstrate the most relevant influences on the reconstruction of x-ray penumbral images, as well as mitigation strategies of image degrading effects like over-exposed pixels, artifacts, and photon limited source emission. We describe experimental results showing the advantages of x-ray penumbral imaging over conventional Fraunhofer and photon limited pinhole imaging and showcase how internal hot spot microstructures can be resolved.

Probing the binding interaction of a phenazinium dye with serum transport proteins: a combined fluorometric and circular dichroism study.

PubMed

Bose, Debosreeta; Sarkar, Deboleena; Chattopadhyay, Nitin

2010-01-01

In the present investigation, an attempt has been made to study the interaction of phenosafranin (PSF), a cationic phenazinium dye with the transport proteins, bovine serum albumin (BSA) and human serum albumin (HSA), employing steady-state and time-resolved fluorometric and circular dichroism (CD) techniques. The photophysical properties of the dye are altered on binding with the serum proteins. An explicit study with respect to the modification of the fluorescence and fluorescence anisotropy upon binding, effect of denaturant, fluorescence lifetime and CD measurements reveal that the dye binds to both BSA and HSA with almost the same affinity. Far-UV CD spectra indicate a decrease in the percentage of alpha-helicity only for BSA upon binding with the probe. Near-UV CD responses indicate an alteration in the tertiary structure of both the transport proteins because of binding.

The MIRAX x-ray astronomy transient mission

NASA Astrophysics Data System (ADS)

Braga, João; Mejía, Jorge

2006-06-01

The Monitor e Imageador de Raios-X (MIRAX) is a small (~250 kg) X-ray astronomy satellite mission designed to monitor the central Galactic plane for transient phenomena. With a field-of-view of ~1000 square degrees and an angular resolution of ~6 arcmin, MIRAX will provide an unprecedented discovery-space coverage to study X-ray variability in detail, from fast X-ray novae to long-term (~several months) variable phenomena. Chiefly among MIRAX science objectives is its capability of providing simultaneous complete temporal coverage of the evolution of a large number of accreting black holes, including a detailed characterization of the spectral state transitions in these systems. MIRAX's instruments will include a soft X-ray (2-18 keV) and two hard X-ray (10-200 keV) coded-aperture imagers, with sensitivities of ~5 and ~2.6 mCrab/day, respectively. The hard X-ray imagers will be built at the Instituto Nacional de Pesquisas Espaciais (INPE), Brazil, in close collaboration with the Center for Astrophysics & Space Sciences (CASS) of the University of California, San Diego (UCSD) and the Institut fur Astronomie und Astrophysik of the University of Tubingen (IAAT) in Germany; UCSD will provide the crossed-strip position-sensitive (0.5- mm spatial resolution) CdZnTe (CZT) hard X-ray detectors. The soft X-ray camera, provided by the Space Research Organization Netherlands (SRON), will be the spare flight unit of the Wide Field Cameras that flew on the Italian-Dutch satellite BeppoSAX. MIRAX is an approved mission of the Brazilian Space Agency (Agnecia Espacial Brasileira - AEB) and is scheduled to be launched in 2011 in a low-altitude (~550 km) circular equatorial orbit. In this paper we present recent developments in the mission planning and design, as well as Monte Carlo simulations performed on the GEANT-based package MGGPOD environment (Weidenspointner et al. 2004) and new algorithms for image digital processing. Simulated images of the central Galactic plane as it

X-ray filter for x-ray powder diffraction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sinsheimer, John Jay; Conley, Raymond P.; Bouet, Nathalie C. D.

Technologies are described for apparatus, methods and systems effective for filtering. The filters may comprise a first plate. The first plate may include an x-ray absorbing material and walls defining first slits. The first slits may include arc shaped openings through the first plate. The walls of the first plate may be configured to absorb at least some of first x-rays when the first x-rays are incident on the x-ray absorbing material, and to output second x-rays. The filters may comprise a second plate spaced from the first plate. The second plate may include the x-ray absorbing material and wallsmore » defining second slits. The second slits may include arc shaped openings through the second plate. The walls of the second plate may be configured to absorb at least some of second x-rays and to output third x-rays.« less

Depth-resolved magnetic and structural analysis of relaxing epitaxial Sr 2 CrReO 6

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lucy, J. M.; Hauser, A. J.; Liu, Y.

2015-03-01

Structural relaxation in a Sr2CrReO6 epitaxial film, which exhibits strong spin-orbit coupling, leads to depth-dependent magnetism. We combine two depth-resolved synchrotron x-ray techniques, two-dimensional reciprocal space mapping and x-ray magnetic circular dichroism, to quantitatively determine this effect. An 800 nm thick film of Sr2CrReO6, grown with tensile epitaxial strain on SrCr0:5Nb0:5O3(225 nm)/LSAT, relaxes away from the Sr2CrReO6/SrCr0:5Nb0:5O3 interface to its bulk lattice parameters, with much of the film being fully relaxed. Grazing incidence xray diffraction measurements of the film elucidate the in-plane strain relaxation near the film- substrate interface while depth-resolved x-ray magnetic circular dichroism at the Re L edgemore » reveals the magnetic contributions of the Re site. The smooth relaxation of the film near the interface correlates with changes in the magnetic anisotropy. This provides a systematic and powerful way to probe the depth-varying structural and magnetic properties of a complex oxide with synchrotronsource x-ray techniques.« less

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

PubMed Central

Greenfield, Norma J.

2009-01-01

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

Conformational study of bovine lactoferricin in membrane-micking conditions by molecular dynamics simulation and circular dichroism.

PubMed

Daidone, Isabella; Magliano, Alessandro; Di Nola, Alfredo; Mignogna, Giuseppina; Clarkson, Matilda Manuela; Lizzi, Anna Rita; Oratore, Arduino; Mazza, Fernando

2011-04-01

Lactoferricins are potent antimicrobial peptides released by pepsin cleavage of Lactoferrins. Bovine Lactoferricin (LfcinB) has higher activity than the intact bovine Lactoferrin, and is the most active among the other Lactoferricins of human, murine and caprine origin. In the intact protein the fragment corresponding to LfcinB is in an helical conformation, while in water LfcinB adopts an amphipathic β-hairpin structure. However, whether any of these structural motifs is the antibacterial active conformation, i.e., the one interacting with bacterial membrane components, remains to be seen. Here we present Circular Dichroism (CD) spectra and Molecular Dynamics (MD) simulations indicating that in membrane-mimicking solvents the LfcinB adopts an amphipathic β-hairpin structure similar to that observed in water, but differing in the dynamic behavior of the side-chains of the two tryptophan residues. In the membrane-mimicking solvent these side-chains show a high propensity to point towards the hydrophobic environment, rather than being in the hydrophobic core as seen in water, while the backbone preserves the hairpin conformation as found in water. These results suggest that the tryptophans might act as anchors pulling the stable, solvent-invariant hairpin structure into the membrane.

Vibrational and electronic circular dichroism study of the interactions of cationic porphyrins with (dG-dC)10 and (dA-dT)10.

PubMed

Nový, Jakub; Urbanová, Marie

2007-03-01

The interactions of two different porphyrins, without axial ligands-5,10,15,20-tetrakis(1-methylpyridinium-4-yl)porphyrin-Cu(II) tetrachloride (Cu(II)TMPyP) and with bulky meso substituents-5,10,15,20-tetrakis(N,N,N-trimethylanilinium-4-yl)porphyrin tetrachloride (TMAP), with (dG-dC)10 and (dA-dT)10 were studied by combination of vibrational circular dichroism (VCD) and electronic circular dichroism (ECD) spectroscopy at different [oligonucleotide]/[porphyrin] ratios, where [oligonucleotide] and [porphyrin] are the concentrations of oligonucleotide per base-pair and porphyrin, respectively. The combination of VCD and ECD spectroscopy enables us to identify the types of interactions, and to specify the sites of interactions: The intercalative binding mode of Cu(II)TMPyP with (dG-dC)(10), which has been well described, was characterized by a new VCD "marker" and it was shown that the interaction of Cu(II)TMPyP with (dA-dT)10 via external binding to the phosphate backbone and major groove binding caused transition from the B to the non-B conformer. TMAP interacted with the major groove of (dG-dC)10, was semi-intercalated into (dA-dT)10, and caused significant variation in the structure of both oligonucleotides at the higher concentration of porphyrin. The spectroscopic techniques used in this study revealed that porphyrin binding with AT sequences caused substantial variation of the DNA structure. It was shown that VCD spectroscopy is an effective tool for the conformational studies of nucleic acid-porphyrin complexes in solution. (c) 2007 Wiley Periodicals, Inc.

Vibrationally induced inversion of photoelectron forward-backward asymmetry in chiral molecule photoionization by circularly polarized light

PubMed Central

Garcia, Gustavo A.; Nahon, Laurent; Daly, Steven; Powis, Ivan

2013-01-01

Electron–nuclei coupling accompanying excitation and relaxation processes is a fascinating phenomenon in molecular dynamics. A striking and unexpected example of such coupling is presented here in the context of photoelectron circular dichroism measurements on randomly oriented, chiral methyloxirane molecules, unaffected by any continuum resonance. Here, we report that the forward-backward asymmetry in the electron angular distribution, with respect to the photon axis, which is associated with photoelectron circular dichroism can surprisingly reverse direction according to the ion vibrational mode excited. This vibrational dependence represents a clear breakdown of the usual Franck–Condon assumption, ascribed to the enhanced sensitivity of photoelectron circular dichroism (compared with other observables like cross-sections or the conventional anisotropy parameter-β) to the scattering phase off the chiral molecular potential, inducing a dependence on the nuclear geometry sampled in the photoionization process. Important consequences for the interpretation of such dichroism measurements within analytical contexts are discussed. PMID:23828557

The effect of nonenzymatic glycation on the stability and conformation of two deoxyoligonucleotide duplexes: a spectroscopic analysis by circular dichroism.

PubMed

Dutta, Udayan; Cohenford, Menashi A; Dain, Joel A

2007-01-15

Advanced glycation end products (AGEs) play a significant role in the pathophysiology of diabetes leading to such conditions as atherosclerosis, cataract formation, and renal dysfunction. While the formation of nucleoside AGEs was previously demonstrated, no extensive studies have been performed to assess the effect of AGEs on DNA structure and folding. The objective of this study was to investigate the nonenzymatic glycation of two DNA oligonucleotide duplexes with one duplex consisting of deoxy-poly(A)15 and deoxy-poly(T)15 and the other consisting of deoxy-poly(GA)15 and deoxy-poly(CT)15. With D-glucose, D-galactose, D/L-glyceraldehyde, and D-glucosamine serving as the model glycating carbohydrates, D-glucosamine was found to exhibit the greatest effect on the stability and structure of the oligonucleotide duplexes, a finding that was confirmed by circular dichroism. The nonenzymatic glycation of deoxy-poly(AT) by D-glucosamine destabilized the deoxy-poly(AT) structure and changed its conformation from A form to X form. D-glucosamine also altered the conformation of deoxy-poly(GA)15 and deoxy-poly(CT)15 from A form to B form. Capillary electrophoresis and ultraviolet and fluorescence spectroscopy revealed that, of the various purines and pyrimidines, 2'-deoxyguanosine and guanine were most reactive with D-glucosamine. The nonenzymatic modification of nucleic acids warrants further investigation because this phenomenon may occur in vivo, altering DNA structure and/or function.

Vibrational circular dichroism of a 2,5-diketopiperazine (DKP) peptide: Evidence for dimer formation in cyclo LL or LD diphenylalanine in the solid state.

PubMed

Pérez-Mellor, Ariel; Zehnacker, Anne

2017-02-01

The diastereomer diketopiperazine (DKP) peptides built on phenylalanine, namely, cyclo diphenylalanine LPhe-LPhe and LPhe-DPhe, were studied in the solid phase by vibrational circular dichroism (VCD) coupled to quantum chemical calculations. The unit structure of cyclo LPhe-LPhe in KBr pellets is a dimer bridged by two strong NH…O hydrogen bonds. The intense bisignate signature in the CO stretch region is interpreted in terms of two contributions arising from the free COs of the dimer and the antisymmetrical combination of the bound COs. In contrast, cyclo LPhe-DPhe shows no VCD signal in relation to its symmetric nature. © 2017 Wiley Periodicals, Inc.

A multiwavelength study of the Eridanus soft X-ray enhancement

NASA Technical Reports Server (NTRS)

Burrows, D. N.; Singh, K. P.; Nousek, J. A.; Garmire, G. P.; Good, J.

1993-01-01

We present soft X-ray, N(H), and IR maps of the Eridanus soft X-ray enhancement. Soft X-ray maps from the HEAO 1 A-2 LED experiment, processed with a maximum entropy method (MEM) algorithm, show that the enhancement consists of two distinct components: a large hook-shaped component and a small circular component at different temperatures. Both of these are located in 'holes' in the IR emission, and they correspond to N(H) features at very different velocities. The dust surrounding the X-ray enhancements appears to be associated with several high-latitude molecular clouds, which allow us to obtain a probable distance of about 130 pc to the near edge of the main enhancement. The total power emitted by the hot gas is then about 10 exp 35 to 10 exp 36 ergs/s. We consider alternative interpretations of these objects as adiabatic supernova remnants or as stellar wind bubbles and conclude that they are more likely to be stellar wind bubbles, possibly reheated by a SN explosion in the case of the main, hook-shaped object.

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

PubMed

Sen, Ananya; Bouchet, Aude; Lepère, Valeria; Le Barbu-Debus, Katia; Scuderi, D; Piuzzi, F; Zehnacker-Rentien, A

2012-08-16

Laser-desorbed quinine and quinidine have been studied in the gas phase by combining supersonic expansion with laser spectroscopy, namely, laser-induced fluorescence (LIF), resonance-enhanced multiphoton ionization (REMPI), and IR-UV double resonance experiments. Density funtional theory (DFT) calculations have been done in conjunction with the experimental work. The first electronic transition of quinine and quinidine is of π-π* nature, and the studied molecules weakly fluoresce in the gas phase, in contrast to what was observed in solution (Qin, W. W.; et al. J. Phys. Chem. C2009, 113, 11790). The two pseudo enantiomers quinine and quinidine show limited differences in the gas phase; their main conformation is of open type as it is in solution. However, vibrational circular dichroism (VCD) experiments in solution show that additional conformers exist in condensed phase for quinidine, which are not observed for quinine. This difference in behavior between the two pseudo enantiomers is discussed.

Investigation of human serum albumin (HSA) binding specificity of certain photosensitizers related to pyropheophorbide-a and bacteriopurpurinimide by circular dichroism spectroscopy and its correlation with in vivo photosensitizing efficacy.

PubMed

Chen, Yihui; Miclea, Razvan; Srikrishnan, Thamarapu; Balasubramanian, Sathyamangalam; Dougherty, Thomas J; Pandey, Ravindra K

2005-07-01

A series of pyropheophorbide-a and bacteriopurpurinimides were investigated to understand the correlation between HSA (site II) binding affinity and in vivo photosensitizing activity. In our study, photosensitizers that bound to site II of HSA produced a significant difference in the circular dichroism spectra of the corresponding complexes, especially at Soret band region of the photosensitizers. Our results suggest that CD spectroscopy of the photosensitizer-HSA complexes could be a valuable tool in screening new photosensitizers before evaluating them for in vivo efficacy.

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

NASA Astrophysics Data System (ADS)

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

2012-01-01

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

Use of a synchronization card for XMCD measurements at the XMaS Beamline

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bouchenoire, L.; Brown, S. D.; Thompson, P. B. J.

X-ray Magnetic Circular Dichroism (XMCD) spectra from a 5 {mu}m polycrystalline Gd foil were measured in transmission across the Gd L{sub 2,3} edges using the Multipurpose Unit for Synchronisation, Sequencing and Triggering (MUSST) card developed at the European Synchrotron Radiation Facility (ESRF). The circularly polarized x-rays were produced by a diamond phase-plate and their helicity was rapidly reversed through the use of a piezo driven device. The signal measured for each helicity was recorded by the MUSST card synchronized to the helicity reversal. The results are compared to those obtained using an analogue lock-in technique.

Use of a synchronization card for XMCD measurements at the XMaS Beamline

NASA Astrophysics Data System (ADS)

Bouchenoire, L.; Brown, S. D.; Thompson, P. B. J.; Hase, T. P. A.; Normile, P.; Bikondoa, O.; Hino, R.; Guijarro, M.; Stewart, M.; Cain, M. G.; Kervin, J.

2010-06-01

X-ray Magnetic Circular Dichroism (XMCD) spectra from a 5 μm polycrystalline Gd foil were measured in transmission across the Gd L2,3 edges using the Multipurpose Unit for Synchronisation, Sequencing and Triggering (MUSST) card developed at the European Synchrotron Radiation Facility (ESRF). The circularly polarized x-rays were produced by a diamond phase-plate and their helicity was rapidly reversed through the use of a piezo driven device. The signal measured for each helicity was recorded by the MUSST card synchronized to the helicity reversal. The results are compared to those obtained using an analogue lock-in technique.

Accuracy of Td-DFT in the Ultraviolet and Circular Dichroism Spectra of Deoxyguanosine and Uridine.

PubMed

Miyahara, Tomoo; Nakatsuji, Hiroshi

2018-01-11

Accuracy of the time-dependent density functional theory (Td-DFT) was examined for the ultraviolet (UV) and circular dichroism (CD) spectra of deoxyguanosine (dG) and uridine, using 11 different DFT functionals and two different basis sets. The Td-DFT results of the UV and CD spectra were strongly dependent on the functionals used. The basis-set dependence was observed only for the CD spectral calculations. For the UV spectra, the B3LYP and PBE0 functionals gave relatively good results. For the CD spectra, the B3LYP and PBE0 with 6-311G(d,p) basis gave relatively permissible result only for dG. The results of other functionals were difficult to be used for the studies of the UV and CD spectra, though the symmetry adapted cluster-configuration interaction (SAC-CI) method reproduced well the experimental spectra of these molecules. To obtain valuable information from the theoretical calculations of the UV and CD spectra, the theoretical tool must be able to reproduce correctly both of the intensities and peak positions of the UV and CD spectra. Then, we can analyze the reasons of the changes of the intensity and/or the peak position to clarify the chemistry involved. It is difficult to recommend Td-DFT as such tools of science, at least from the examinations using dG and uridine.

X-ray focal spot reconstruction by circular penumbra analysis-Application to digital radiography systems.

PubMed

Di Domenico, Giovanni; Cardarelli, Paolo; Contillo, Adriano; Taibi, Angelo; Gambaccini, Mauro

2016-01-01

The quality of a radiography system is affected by several factors, a major one being the focal spot size of the x-ray tube. In fact, the measurement of such size is recognized to be of primary importance during acceptance tests and image quality evaluations of clinical radiography systems. The most common device providing an image of the focal spot emission distribution is a pin-hole camera, which requires a high tube loading in order to produce a measurable signal. This work introduces an alternative technique to obtain an image of the focal spot, through the processing of a single radiograph of a simple test object, acquired with a suitable magnification. The radiograph of a magnified sharp edge is a well-established method to evaluate the extension of the focal spot profile along the direction perpendicular to the edge. From a single radiograph of a circular x-ray absorber, it is possible to extract simultaneously the radial profiles of several sharp edges with different orientations. The authors propose a technique that allows to obtain an image of the focal spot through the processing of these radial profiles by means of a pseudo-CT reconstruction technique. In order to validate this technique, the reconstruction has been applied to the simulated radiographs of an ideal disk-shaped absorber, generated by various simulated focal spot distributions. Furthermore, the method has been applied to the focal spot of a commercially available mammography unit. In the case of simulated radiographs, the results of the reconstructions have been compared to the original distributions, showing an excellent agreement for what regards both the overall distribution and the full width at half maximum measurements. In the case of the experimental test, the method allowed to obtain images of the focal spot that have been compared with the results obtained through standard techniques, namely, pin-hole camera and slit camera. The method was proven to be effective for simulated

A high-performance liquid chromatography-electronic circular dichroism online method for assessing the absolute enantiomeric excess and conversion ratio of asymmetric reactions

NASA Astrophysics Data System (ADS)

Zhang, Xiang; Wang, Mingchao; Li, Li; Yin, Dali

2017-03-01

Asymmetric reactions often need to be evaluated during the synthesis of chiral compounds. However, traditional evaluation methods require the isolation of the individual enantiomer, which is tedious and time-consuming. Thus, it is desirable to develop simple, practical online detection methods. We developed a method based on high-performance liquid chromatography-electronic circular dichroism (HPLC-ECD) that simultaneously analyzes the material conversion ratio and absolute optical purity of each enantiomer. In particular, only a reverse-phase C18 column instead of a chiral column is required in our method because the ECD measurement provides a g-factor that describes the ratio of each enantiomer in the mixtures. We used our method to analyze the asymmetric hydrosilylation of β-enamino esters, and we discussed the advantage, feasibility, and effectiveness of this new methodology.

Coherent Raman detected electron spin resonance spectroscopy of metalloproteins: linking electron spin resonance and magnetic circular dichroism.

PubMed

Bingham, Stephen J; Wolverson, Daniel; Thomson, Andrew J

2008-12-01

The simultaneous excitation of paramagnetic molecules with optical (laser) and microwave radiation in the presence of a magnetic field can cause an amplitude, or phase, modulation of the transmitted light at the microwave frequency. The detection of this modulation indicates the presence of coupled optical and ESR transitions. The phenomenon can be viewed as a coherent Raman effect or, in most cases, as a microwave frequency modulation of the magnetic circular dichroism by the precessing magnetization. By allowing the optical and magnetic properties of a transition metal ion centre to be correlated, it becomes possible to deconvolute the overlapping optical or ESR spectra of multiple centres in a protein or of multiple chemical forms of a particular centre. The same correlation capability also allows the relative orientation of the magnetic and optical anisotropies of each species to be measured, even when the species cannot be obtained in a crystalline form. Such measurements provide constraints on electronic structure calculations. The capabilities of the method are illustrated by data from the dimeric mixed-valence Cu(A) centre of nitrous oxide reductase (N(2)OR) from Paracoccus pantotrophus.

Magnetic circular dichroism of UCl 6– in the ligand-to-metal charge-transfer spectral region

DOE PAGES

Gendron, Frederic; Fleischauer, Valerie R.; Duignan, Thomas J.; ...

2017-06-23

Here, we present a combined ab initio theoretical and experimental study of the magnetic circular dichroism (MCD) spectrum of the octahedral UCl 6- complex ion in the UV-Vis spectral region. The ground state is an orbitally non-degenerate doublet E 5/2u and the MCD is a $C$-term spectrum caused by spin–orbit coupling. Calculations of the electronic spectrum at various levels of theory indicate that differential dynamic electron correlation has a strong influence on the energies of the dipole-allowed transitions and the envelope of the MCD spectrum. The experimentally observed bands are assigned to dipole-allowed ligand-to-metal charge transfer into the 5f shell,more » and 5f to 6d transitions. Charge transfer excitations into the U 6d shell appear at much higher energies. The MCD-allowed transitions can be assigned via their signs of the $C$-terms: Under O h double group symmetry, E 5/2u → E 5/2g transitions have negative $C$-terms whereas E 5/2u → F 3/2g transitions have positive $C$-terms if the ground state g-factor is negative, as it is the case for UCl 6-.« less

X-Rays

MedlinePlus

X-rays are a type of radiation called electromagnetic waves. X-ray imaging creates pictures of the inside of ... different amounts of radiation. Calcium in bones absorbs x-rays the most, so bones look white. Fat ...

Preliminary Understanding of Surface Plasmon-Enhanced Circular Dichroism Spectroscopy by Single Particle Imaging

NASA Astrophysics Data System (ADS)

Zhan, Kangshu

Monitoring chiral optical signals of biomolecules as their conformation changes is an important means to study their structures, properties, and functions. Most measurements, however, are ensemble measurements because chiral optical signals from a single biomolecule is often too weak to be detected. In this dissertation, I present my early attempts to study conformational changes of adsorbed proteins by taking advantage of the enhanced electromagnetic (EM) field around a well-designed plasmonic nanofeature. In particular, I discuss the detection of protein adsorption and denaturation on metallic nanoparticles using single particle scattering and CD spectroscopic imaging. Particles of two distinctively different sizes were compared and two different sample protein molecules were studied. A combination of experimental and computational tools was used to simulate and interpret the collected scattering and CD results. The first chapter provides a brief overview of the state-of-art research in CD spectroscopic studies at the single particle level. Three different means to make particles capable of chiral detection are discussed. Various applications beyond single particle imaging are presented to showcase the potential of the described research project, beyond our immediate goals. The second chapter describes my initial characterization of large, metallic, anisotropic nanorods and the establishment of experimental procedures used later for spectrum reconstruction, data visualization and analysis. The physical shape and structure of the particles were imaged by scanning electron microscopy (SEM), the chemical composition by energy dispersive X-ray Spectroscopy (EDS), and the optical properties by darkfield microscopy. An experimental protocol was developed to connect information collected from separate techniques for the same particle, with the aims of discovering any possible structural-property correlation. The reproducibility of the single particle imaging method was

Absolute configuration determination through the unique intramolecular excitonic coupling in the circular dichroisms of o,p'-DDT and o,p'-DDD. A combined experimental and theoretical study.

PubMed

Tanaka, Hiroki; Inoue, Yoshihisa; Nakano, Takeshi; Mori, Tadashi

2017-04-12

Circular dichroisms (CDs) of the o,p'-isomers of 1,1,1-trichloro- and 1,1-dichloro-2,2-bis(chlorophenyl)ethanes (DDT and DDD) were investigated experimentally and theoretically. A series of strong Cotton effect peaks in a characteristic negative-negative-positive-negative, or its mirror-imaged, pattern were observed in the CD spectra of these persistent organic pollutants. The theoretical CD spectra at the SAC-CI/B95(d) and RI-CC2/def2-TZVPP levels well reproduced the experimental ones, enabling us to unambiguously assign the absolute configuration of (+)-DDT and (-)-DDD as S.

IGR J170626143 is an Accreting Millisecond X-Ray Pulsar

NASA Technical Reports Server (NTRS)

Strohmayer, Tod E.; Keek, Laurens

2017-01-01

We present the discovery of 163.65 Hz X-ray pulsations from IGR J17062-6143 in the only observation obtained from the source with the Rossi X-ray Timing Explorer. This detection makes IGR J17062-6143 the lowest frequency accreting millisecond X-ray pulsar presently known. The pulsations are detected in the 2-12 keV band with an overall significance of 4.3sigma and an observed pulsed amplitude of 5.54% +/-0.67% (in this band). Both dynamic power spectral and coherent phase timing analysis indicate that the pulsation frequency is decreasing during the approx. =1.2 ks observation in a manner consistent with orbital motion of the neutron star. Because the observation interval is short, we cannot precisely measure the orbital period; however, periods shorter than 17 minutes are excluded at 90% confidence. For the range of acceptable circular orbits the inferred binary mass function substantially overlaps the observed range for the AMXP population as a whole.

Imidazolium tagged acridines: Synthesis, characterization and applications in DNA binding and anti-microbial activities

NASA Astrophysics Data System (ADS)

Raju, Gembali; Vishwanath, S.; Prasad, Archana; Patel, Basant K.; Prabusankar, Ganesan

2016-03-01

New water soluble 4,5-bis imidazolium tagged acridines have been synthesized and structurally characterized by multinuclear NMR and single crystal X-ray diffraction techniques. The DNA binding and anti-microbial activities of these acridine derivatives were investigated by fluorescence and far-UV circular dichroism studies.

An in-plane magnetic chiral dichroism approach for measurement of intrinsic magnetic signals using transmitted electrons

PubMed Central

Song, Dongsheng; Tavabi, Amir H.; Li, Zi-An; Kovács, András; Rusz, Ján; Huang, Wenting; Richter, Gunther; Dunin-Borkowski, Rafal E.; Zhu, Jing

2017-01-01

Electron energy-loss magnetic chiral dichroism is a powerful technique that allows the local magnetic properties of materials to be measured quantitatively with close-to-atomic spatial resolution and element specificity in the transmission electron microscope. Until now, the technique has been restricted to measurements of the magnetic circular dichroism signal in the electron beam direction. However, the intrinsic magnetization directions of thin samples are often oriented in the specimen plane, especially when they are examined in magnetic-field-free conditions in the transmission electron microscope. Here, we introduce an approach that allows in-plane magnetic signals to be measured using electron magnetic chiral dichroism by selecting a specific diffraction geometry. We compare experimental results recorded from a cobalt nanoplate with simulations to demonstrate that an electron magnetic chiral dichroism signal originating from in-plane magnetization can be detected successfully. PMID:28504267

Soft x-ray coherent diffraction imaging on magnetic nanostructures

NASA Astrophysics Data System (ADS)

Shi, Xiaowen; Lee, James; Mishra, Shrawan; Parks, Daniel; Tyliszczak, Tolek; Shapiro, David; Roy, Sujoy; Kevan, Steve; Stxm Team At Als Collaboration; Soft X-Ray Microscopy Group At Als Collaboration; Soft X-ray scattering at ALS, LBL Team

2014-03-01

Coherent soft X-rays diffraction imaging enable coherent magnetic resonance scattering at transition metal L-edge to be probed so that magnetic domains could be imaged with very high spatial resolution with phase contrast, reaching sub-10nm. One of the overwhelming advantages of using coherent X-rays is the ability to resolve phase contrast images with linearly polarized light with both phase and absorption contrast comparing to real-space imaging, which can only be studied with circularly polarized light with absorption contrast only. Here we report our first results on high-resolution of magnetic domains imaging of CoPd multilayer thin film with coherent soft X-ray ptychography method. We are aiming to resolve and understand magnetic domain wall structures with the highest obtainable resolution here at Advanced Light Source. In principle types of magnetic domain walls could be studied so that Neel or Bloch walls can be distinguished by imaging. This work at LBNL was supported by the Director, Office of Science, Office of Basic Energy Sciences, of the US Department of Energy (contract no. DE-AC02- 05CH11231).

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dhesi, S. S.; Cavill, S. A.; Potenza, A.

The Nanoscience beamline (I06) is one of seven Diamond Phase-I beamlines which has been operational since January 2007 delivering polarised soft x-rays, for a PhotoEmission Electron Microscope (PEEM) and branchline, in the energy range 80-2100 eV. The beamline is based on a collimated plane grating monochromator with sagittal focusing elements, utilising two APPLE II helical undulator sources, and has been designed for high flux density at the PEEM sample position. A {approx}5 {mu}m ({sigma}) diameter beam is focussed onto the sample in the PEEM allowing a range of experiments using x-ray absorption spectroscopy (XAS), x-ray magnetic circular dichroism (XMCD) andmore » x-ray magnetic linear dichroism (XMLD) as contrast mechanisms. The beamline is also equipped with a branchline housing a 6T superconducting magnet for XMCD and XMLD experiments. The magnet is designed to move on and off the branchline which allows a diverse range of experiments.« less

Swift/XRT Monitoring of the Candidate Supergiant Fast X-ray Transient IGR J16418-4532

NASA Technical Reports Server (NTRS)

Romano, P.; Mangano, V.; Ducci, L.; Esposito, P.; Evans, P. A.; Vercellone, S.; Kennea, J. A.; Burrows, D. N.; Gehrels, N.

2011-01-01

We report on the Swift monitoring of the candidate supergiant fast X-ray transient (SFXT) IGR J16418.4532, for which both orbital and spin periods are known (approx. 3.7d and approx. 1250 s, respectively). Our observations, for a total of approx. 43 ks, span over three orbital periods and represent the most intense and complete sampling of the light curve of this source with a sensitive X-ray instrument. With this unique set of observations we can address the nature of this transient. By applying the clumpy wind model for blue supergiants to the observed X-ray light curve, and assuming a circular orbit, the X-ray emission from this source can be explained in terms of the accretion from a spherically symmetric clumpy wind, composed of clumps with different masses, ranging from 5 X 10(exp 16) g to 10(exp 21) g. Our data suggest, based on the X-ray behaviour, that this is an intermediate SFXT

Valley Zeeman splitting of monolayer MoS2 probed by low-field magnetic circular dichroism spectroscopy at room temperature

NASA Astrophysics Data System (ADS)

Wu, Y. J.; Shen, C.; Tan, Q. H.; Shi, J.; Liu, X. F.; Wu, Z. H.; Zhang, J.; Tan, P. H.; Zheng, H. Z.

2018-04-01

The valley Zeeman splitting of monolayer two-dimensional (2D) materials in the magnetic field plays an important role in the valley and spin manipulations. In general, a high magnetic field (6-65 T) and low temperature (2-30 K) were two key measurement conditions to observe the resolvable valley Zeeman splitting of monolayer 2D materials in current reported experiments. In this study, we experimentally demonstrate an effective measurement scheme by employing magnetic circular dichroism (MCD) spectroscopy, which enables us to distinguish the valley Zeeman splitting under a relatively low magnetic field of 1 T at room temperature. MCD peaks related to both A and B excitonic transitions in monolayer MoS2 can be clearly observed. Based on the MCD spectra under different magnetic fields (-3 to 3 T), we obtained the valley Zeeman splitting energy and the g-factors of A and B excitons, respectively. Our results show that MCD spectroscopy is a high-sensitive magneto-optical technique to explore the valley and spin manipulation in 2D materials.

The Effect of the π-Electron Delocalization Curvature on the Two-Photon Circular Dichroism of Molecules with Axial Chirality.

PubMed

Diaz, Carlos; Lin, Na; Toro, Carlos; Passier, Remy; Rizzo, Antonio; Hernández, Florencio E

2012-07-05

Herein we report on the theoretical-experimental study of the effect of curvature of the π-electron delocalization on the two-photon circular dichroism (TPCD) of a family of optically active biaryl derivatives (S-BINOL, S-VANOL, and S-VAPOL). The comparative analysis of the influence of the different transition moments to their corresponding TPCD rotatory strength reveals an enhanced contribution of the magnetic transition dipole moment on VAPOL. This effect is hereby attributed to the additional twist in the π-electron delocalization on this compound. TPCD measurements were done using the double L-scan technique in the picosecond regime. Theoretical calculations were completed using modern analytical response theory, within a time-dependent density functional theory (TD-DFT) approach, at both, B3LYP and CAM-B3LYP levels, with the aug-cc-pVDZ basis set for S-BINOL and S-VANOL, and 6-31G* for S-VAPOL. Solvent effects were included by means of the polarizable continuum model (PCM) in CH2Cl2.

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

NASA Astrophysics Data System (ADS)

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

2017-04-01

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

X-ray beamsplitter

DOEpatents

Ceglio, Natale M.; Stearns, Daniel S.; Hawryluk, Andrew M.; Barbee, Jr., Troy W.

1989-01-01

An x-ray beamsplitter which splits an x-ray beam into two coherent parts by reflecting and transmitting some fraction of an incident beam has applications for x-ray interferometry, x-ray holography, x-ray beam manipulation, and x-ray laser cavity output couplers. The beamsplitter is formed of a wavelength selective multilayer thin film supported by a very thin x-ray transparent membrane. The beamsplitter resonantly transmits and reflects x-rays through thin film interference effects. A thin film is formed of 5-50 pairs of alternate Mo/Si layers with a period of 20-250 A. The support membrane is 10-200 nm of silicon nitride or boron nitride. The multilayer/support membrane structure is formed across a window in a substrate by first forming the structure on a solid substrate and then forming a window in the substrate to leave a free-standing structure over the window.

Search for Hard X-Ray Emission from the Soft X-Ray Transient Aquila X-1

NASA Astrophysics Data System (ADS)

Harmon, B. A.; Zhang, S. N.; Paciesas, W. S.; Tavani, M.; Kaaret, P.; Ford, E.

1994-12-01

We are investigating the possibility of hard x-ray emission from the recurrent soft x-ray transient and x-ray burst source Aquila X-1 (Aql X-1). Outbursts of this source are relatively frequent with a spacing of ~ 4-10 months (Kitamoto, S. et al. 1993, ApJ, 403, 315). The recent detections of hard tails (\\(>\\)20 keV) in low luminosity x-ray bursters (Barret, D. & Vedrenne, G. 1994, ApJ Supp. S. 92, 505) suggest that neutron star transient systems such as Aql X-1 can produce hard x-ray emission which is detectable by BATSE. We are correlating reported optical and soft x-ray observations since 1991 of Aql X-1 with BATSE observations in order to search for hard x-ray emission episodes, and to study their temporal and spectral evolution. We will present preliminary results of this search in the 20-1000 keV band using the Earth occultation technique applied to the large area detectors. If this work is successful, we hope to alert the astronomical community for the next Aql X-1 outburst expected in 1995. Simultaneous x-ray/hard x-ray and optical observations of Aql X-1 during outburst would be of great importance for the modeling of soft x-ray transients and related systems.

Similarities and Differences between RNA and DNA Double-Helical Structures in Circular Dichroism Spectroscopy: A SAC-CI Study.

PubMed

Miyahara, Tomoo; Nakatsuji, Hiroshi; Sugiyama, Hiroshi

2016-11-17

The helical structures of DNA and RNA are investigated experimentally using circular dichroism (CD) spectroscopy. The signs and the shapes of the CD spectra are much different between the right- and left-handed structures as well as between DNA and RNA. The main difference lies in the sign at around 295 nm of the CD spectra: it is positive for the right-handed B-DNA and the left-handed Z-RNA but is negative for the left-handed Z-DNA and the right-handed A-RNA. We calculated the SAC-CI CD spectra of DNA and RNA using the tetramer models, which include both hydrogen-bonding and stacking interactions that are important in both DNA and RNA. The SAC-CI results reproduced the features at around 295 nm of the experimental CD spectra of each DNA and RNA, and elucidated that the strong stacking interaction between the two base pairs is the origin of the negative peaks at 295 nm of the CD spectra for both DNA and RNA. On the basis of these facts, we discuss the similarities and differences between RNA and DNA double-helical structures in the CD spectroscopy based on the ChiraSac methodology.

X-ray beamsplitter

DOEpatents

Ceglio, N.M.; Stearns, D.G.; Hawryluk, A.M.; Barbee, T.W. Jr.

1987-08-07

An x-ray beamsplitter which splits an x-ray beam into two coherent parts by reflecting and transmitting some fraction of an incident beam has applications for x-ray interferometry, x-ray holography, x-ray beam manipulation, and x-ray laser cavity output couplers. The beamsplitter is formed of a wavelength selective multilayer thin film supported by a very thin x-ray transparent membrane. The beamsplitter resonantly transmits and reflects x-rays through thin film interference effects. A thin film is formed of 5--50 pairs of alternate Mo/Si layers with a period of 20--250 A. The support membrane is 10--200 nm of silicon nitride or boron nitride. The multilayer/support membrane structure is formed across a window in a substrate by first forming the structure on a solid substrate and then forming a window in the substrate to leave a free-standing structure over the window. 6 figs.

The circular dichroism properties of phi W-14 DNA containing alpha-putrescinylthymine.

PubMed

Spetter, S; Chen, C; Warren, R A; Hanlon, S

1985-03-08

The circular dichroism properties of phi W-14 DNA containing alpha-putrescinylthymine and its acetylated derivative have been examined in a number of aqueous solvents. Native phi W-14 DNA exhibits a B-type CD spectrum whose characteristics do not entirely conform to what would be expected for its GC content (51%). The conformationally sensitive positive band above 260 nm has a rotational strength greater than that normally found in prokaryotic DNAs of comparable GC content, such as Escherichia coli DNA. The rotational strength of this band in the spectrum of the heat-denatured form of phi W-14 DNA, however, is similar to that of heat denatured E. coli DNA. Abolition of the positive charge on the putrescine residues of native phi W-14 DNA by reaction with CH2O or by acetylation reduces the rotational strength to a level appropriate for its GC content. Increases in the electrolyte content of the solvent have the same effect, although the rotational strength of this band in phi W-14 DNA does not become comparable to that of E. coli DNA until 6-7 M LiCl. Titration to pH 10.6 in solvents of modest electrolyte content, however, fails to appreciably affect the CD spectral properties of either native phi W-14 DNA or the derivative in which half of the secondary and all of the primary amino groups have been acetylated. On the basis of these results we have concluded that the enhanced rotational strength of the positive band above 260 nm in the CD spectrum of phi W-14 DNA is due to a conformational difference caused by an ion-pair interaction of the positively charged primary amino groups of putrescine with the phosphate backbone. The CD spectral properties, however, reveal that these differences, averaged over the entire basepair population, appear to be relatively small. The average conformation, at least in dilute aqueous solutions, seems to be an unexceptional B variant with conformational properties which would be more appropriate for a DNA of higher CG content.

General Relativistic Effects and QPOs in X-Ray Binaries

NASA Astrophysics Data System (ADS)

Markovic, D.; Lamb, F. K.

We have investigated whether general relativistic effects may be responsible for some of the quasi-periodic X-ray brightness oscillations (QPOs) observed in low-mass binary systems containing accreting neutron stars and black hole candidates. In particular, we have computed the motions of accreting gas in the strong gravitational fields near such objects and have explored possible mechanisms for producing X-ray flux oscillations. We have discovered a family of weakly damped global gravitomagnetic (Lense-Thirring) warping modes of the inner (viscous) accretion disk that have precession frequencies ranging up to the single-particle gravitomagnetic precession frequency at the inner edge of the disk, which is about 30 Hz if the disk extends inward to the innermost stable circular orbit around a compact object of solar mass with dimensionless angular momentum cJ/GM2 ~ 0.2. Precession of regions of enhanced viscous dissipation or modulation of the accretion flow by the precession may produce observable periodic variation of the X-ray flux. Detectable effects might also be produced if the gas in the inner disk breaks up into a collection of distinct clumps. We have analyzed the dynamics of such clumps as well as the conditions required for their formation and survival on time scales long enough to produce QPOs with the coherence observed in low-mass X-ray binaries.

Lanthanide tris(β-diketonates) as useful probes for chirality determination of biological amino alcohols in vibrational circular dichroism: ligand to ligand chirality transfer in lanthanide coordination sphere.

PubMed

Miyake, Hiroyuki; Terada, Keiko; Tsukube, Hiroshi

2014-06-01

A series of lanthanide tris(β-diketonates) functioned as useful chirality probes in the vibrational circular dichroism (VCD) characterization of biological amino alcohols. Various chiral amino alcohols induced intense VCD signals upon ternary complexation with racemic lanthanide tris(β-diketonates). The VCD signals observed around 1500 cm(-1) (β-diketonate IR absorption region) correlated well with the stereochemistry and enantiomeric purity of the targeted amino alcohol, while the corresponding monoalcohol, monoamine, and diol substrates induced very weak VCD signals. The high-coordination number and dynamic property of the lanthanide complex offer an effective chirality VCD probing of biological substrates. © 2014 Wiley Periodicals, Inc.

Element Specific Spin and Orbital Moments in Fe1-x Vx Alloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

Guan, Y.; Scheck, C; Bailey, W

2009-01-01

We present transmission-mode X-ray magnetic circular dichroism (XMCD) measurements of element-specific magnetic moments for Fe and V at the L2,3 edges in polycrystalline Fe1-xVx ultrathin films. We find that the orbital-to-spin moment ratio of Fe does not change within experimental error. The V XMCD is not very informative, and a nearly pure-spin type V impurity moment ({approx}1.0 {mu}{sub B}/atom, antiparallel to the Fe host moment) is assumed to match known magnetization data. Data are further reduced to a two-sublattice model and found to be compatible with known spectroscopic splitting g-factor data in the alloy. The results confirm that the verymore » low Gilbert damping, attained through the introduction of V into epitaxial Fe1-xVx films and found by ferromagnetic resonance (FMR), does not result from the reduction of orbital moment content in the alloy.« less

Orbital Parameters for the X-Ray Pulsar IGR J16393-4643

NASA Astrophysics Data System (ADS)

Thompson, Thomas W. J.; Tomsick, John A.; Rothschild, Richard E.; in't Zand, J. J. M.; Walter, Roland

2006-09-01

With recent and archival Rossi X-Ray Timing Explorer (RXTE) X-ray measurements of the heavily obscured X-ray pulsar IGR J16393-4643, we carried out a pulse timing analysis to determine the orbital parameters. Assuming a circular orbit, we phase-connected data spanning over 1.5 yr. The most likely orbital solution has a projected semimajor axis of 43+/-2 lt-s and an orbital period of 3.6875+/-0.0006 days. This implies a mass function of 6.5+/-1.1 Msolar and confirms that this INTEGRAL source is a high-mass X-ray binary (HMXB) system. By including eccentricity in the orbital model, we find e<0.25 at the 2 σ level. The 3.7 day orbital period and the previously known ~910 s pulse period place the system in the region of the Corbet diagram populated by supergiant wind accretors, and the low eccentricity is also consistent with this type of system. Finally, it should be noted that although the 3.7 day solution is the most likely one, we cannot completely rule out two other solutions with orbital periods of 50.2 and 8.1 days.

Quantitative analysis of magnetic spin and orbital moments from an oxidized iron (1 1 0) surface using electron magnetic circular dichroism.

PubMed

Thersleff, Thomas; Rusz, Jan; Rubino, Stefano; Hjörvarsson, Björgvin; Ito, Yasuo; J Zaluzec, Nestor; Leifer, Klaus

2015-08-17

Understanding the ramifications of reduced crystalline symmetry on magnetic behavior is a critical step in improving our understanding of nanoscale and interfacial magnetism. However, investigations of such effects are often controversial largely due to the challenges inherent in directly correlating nanoscale stoichiometry and structure to magnetic behavior. Here, we describe how to use Transmission Electron Microscope (TEM) to obtain Electron Magnetic Circular Dichroism (EMCD) signals as a function of scattering angle to locally probe the magnetic behavior of thin oxide layers grown on an Fe (1 1 0) surface. Experiments and simulations both reveal a strong dependence of the magnetic orbital to spin ratio on its scattering vector in reciprocal space. We exploit this variation to extract the magnetic properties of the oxide cladding layer, showing that it locally may exhibit an enhanced orbital to spin moment ratio. This finding is supported here by both spatially and angularly resolved EMCD measurements, opening up the way for compelling investigations into how magnetic properties are affected by nanoscale features.

DOE Office of Scientific and Technical Information (OSTI.GOV)

DiLullo, Andrew; Shirato, Nozomi; Cummings, Marvin

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 FeL 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.

Be/X-ray Binary Science for Future X-ray Timing Missions

NASA Technical Reports Server (NTRS)

Wilson-Hodge, Colleen A.

2011-01-01

For future missions, the Be/X-ray binary community needs to clearly define our science priorities for the future to advocate for their inclusion in future missions. In this talk, I will describe current designs for two potential future missions and Be X-ray binary science enabled by these designs. The Large Observatory For X-ray Timing (LOFT) is an X-ray timing mission selected in February 2011 for the assessment phase from the 2010 ESA M3 call for proposals. The Advanced X-ray Timing ARray (AXTAR) is a NASA explorer concept X-ray timing mission. This talk is intended to initiate discussions of our science priorities for the future.

Optical Metrology for the Segmented Optics on the Constellation-X Spectroscopy X-Ray Telescope

NASA Technical Reports Server (NTRS)

Content, David; Colella, David; Fleetwood, Charles; Hadjimichael, Theo; Lehan, John; McMann, Joseph; Reid, Paul; Saha, Timo; Wright, Geraldine; Zhang, William

2004-01-01

We present the metrology requirements and metrology implementation necessary to prove out the reflector technology for the Constellation X(C-X) spectroscopy X-ray telescope (SXT). This segmented, 1.6m diameter highly nested Wolter-1 telescope presents many metrology and alignment challenges. In particular, these mirrors have a stringent imaging error budget as compared to their intrinsic stiffness; This is required for Constellation-X to have sufficient effective area with the weight requirement. This has implications for the metrology that can be used. A variety of contract and noncontact optical profiling and interferometric methods are combined to test the formed glass substrates before replication and the replicated reflector segments.The reflectors are tested both stand-alone and in-situ in an alignment tower.Some of these methods have not been used on prior X-ray telescopes and some are feasible only because of the segmented approach used on the SXT. Methods discussed include high precision coordinate measurement machines using very low force or optical probe axial interferometric profiling azimuthal circularity profiling and use of advanced null optics such as conical computer generated hologram (CGHs).

Abdomen X-Ray (Radiography)

MedlinePlus

... News Physician Resources Professions Site Index A-Z X-ray (Radiography) - Abdomen Abdominal x-ray uses a ... of an abdominal x-ray? What is abdominal x-ray? An x-ray (radiograph) is a noninvasive ...

A search for X-ray polarization in cosmic X-ray sources. [binary X-ray sources and supernovae remnants

NASA Technical Reports Server (NTRS)

Hughes, J. P.; Long, K. S.; Novick, R.

1983-01-01

Fifteen strong X-ray sources were observed by the X-ray polarimeters on board the OSO-8 satellite from 1975 to 1978. The final results of this search for X-ray polarization in cosmic sources are presented in the form of upper limits for the ten sources which are discussed elsewhere. These limits in all cases are consistent with a thermal origin for the X-ray emission.

X-Ray Emission from the Soft X-Ray Transient Aquila X-1

NASA Technical Reports Server (NTRS)

Tavani, Marco

1998-01-01

Aquila X-1 is the most prolific of soft X-ray transients. It is believed to contain a rapidly spinning neutron star sporadically accreting near the Eddington limit from a low-mass companion star. The interest in studying the repeated X-ray outbursts from Aquila X-1 is twofold: (1) studying the relation between optical, soft and hard X-ray emission during the outburst onset, development and decay; (2) relating the spectral component to thermal and non-thermal processes occurring near the magnetosphere and in the boundary layer of a time-variable accretion disk. Our investigation is based on the BATSE monitoring of Aquila X-1 performed by our group. We observed Aquila X-1 in 1997 and re-analyzed archival information obtained in April 1994 during a period of extraordinary outbursting activity of the source in the hard X-ray range. Our results allow, for the first time for this important source, to obtain simultaneous spectral information from 2 keV to 200 keV. A black body (T = 0.8 keV) plus a broken power-law spectrum describe accurately the 1994 spectrum. Substantial hard X-ray emission is evident in the data, confirming that the accretion phase during sub-Eddington limit episodes is capable of producing energetic hard emission near 5 x 10(exp 35) ergs(exp -1). A preliminary paper summarizes our results, and a more comprehensive account is being written. We performed a theoretical analysis of possible emission mechanisms, and confirmed that a non-thermal emission mechanism triggered in a highly sheared magnetosphere at the accretion disk inner boundary can explain the hard X-ray emission. An anticorrelation between soft and hard X-ray emission is indeed prominently observed as predicted by this model.

Application of Circular Dichroism Spectroscopy to the Analysis of the Interaction Between the Estrogen Receptor Alpha and Coactivators: The Case of Calmodulin.

PubMed

Miclet, Emeric; Bourgoin-Voillard, Sandrine; Byrne, Cillian; Jacquot, Yves

2016-01-01

The estrogen receptor α ligand-binding domain (ERα-LBD) binds the natural hormone 17β-estradiol (E2) to induce transcription and cell proliferation. This process occurs with the contribution of protein and peptide partners (also called coactivators) that can modulate the structure of ERα, and therefore its specificity of action. As with most transcription factors, ERα exhibits a high content of α helix, making it difficult to routinely run spectroscopic studies capable of deciphering the secondary structure of the different partners under binding conditions. Ca(2+)-calmodulin, a protein also highly structured in α-helix, is a key coactivator for ERα activity. Here, we show how circular dichroism can be used to study the interaction of ERα with Ca(2+)-calmodulin. Our approach allows the determination not only of the conformational changes induced upon complex formation but also the dissociation constant (K d) of this interaction.

Electronic and magnetic properties of manganite thin films with different compositions and its correlation with transport properties: An X-ray resonant magnetic scattering study

DOE PAGES

Singh, Surendra; Freeland, J. W.; Fitzsimmons, M. R.; ...

2014-12-08

Here, we present x-ray resonant magnetic dichroism and x-ray resonant magnetic scattering measurements of the temperature dependence of magnetism in Pr-doped La-Ca-Mn-O films grown on (110) NdGaO3 substrates. We observed thermal hysteresis of the ferromagnetism in one film that also showed large thermal hysteresis of ~18K in transport measurements. While in a second film of a different nominal chemistry, which showed very small thermal hysteresis ~3K in transport measurements, no thermal hysteresis of the ferromagnetism was observed. As a result, these macroscopic properties are correlated with evolution of surface magnetization across metal insulator transition for these films as observed bymore » soft x-ray resonant magnetic scattering measurements.« less

"X-Ray Transients in Star-Forming Regions" and "Hard X-Ray Emission from X-Ray Bursters"

NASA Technical Reports Server (NTRS)

Halpern, Jules P.; Kaaret, Philip

1999-01-01

This grant funded work on the analysis of data obtained with the Burst and Transient Experiment (BATSE) on the Compton Gamma-Ray Observatory. The goal of the work was to search for hard x-ray transients in star forming regions using the all-sky hard x-ray monitoring capability of BATSE. Our initial work lead to the discovery of a hard x-ray transient, GRO J1849-03. Follow-up observations of this source made with the Wide Field Camera on BeppoSAX showed that the source should be identified with the previously known x-ray pulsar GS 1843-02 which itself is identified with the x-ray source X1845-024 originally discovered with the SAS-3 satellite. Our identification of the source and measurement of the outburst recurrence time, lead to the identification of the source as a Be/X-ray binary with a spin period of 94.8 s and an orbital period of 241 days. The funding was used primarily for partial salary and travel support for John Tomsick, then a graduate student at Columbia University. John Tomsick, now Dr. Tomsick, received his Ph.D. from Columbia University in July 1999, based partially on results obtained under this investigation. He is now a postdoctoral research scientist at the University of California, San Diego.

Lumbosacral spine x-ray

MedlinePlus

X-ray - lumbosacral spine; X-ray - lower spine ... The test is done in a hospital x-ray department or your health care provider's office by an x-ray technician. You will be asked to lie on the x-ray ...

X-ray ptychography

NASA Astrophysics Data System (ADS)

Pfeiffer, Franz

2018-01-01

X-ray ptychographic microscopy combines the advantages of raster scanning X-ray microscopy with the more recently developed techniques of coherent diffraction imaging. It is limited neither by the fabricational challenges associated with X-ray optics nor by the requirements of isolated specimen preparation, and offers in principle wavelength-limited resolution, as well as stable access and solution to the phase problem. In this Review, we discuss the basic principles of X-ray ptychography and summarize the main milestones in the evolution of X-ray ptychographic microscopy and tomography over the past ten years, since its first demonstration with X-rays. We also highlight the potential for applications in the life and materials sciences, and discuss the latest advanced concepts and probable future developments.

X-ray absorption spectroscopy study of annealing process on Sr1-xLaxCuO2 electron-doped cuprate thin films

NASA Astrophysics Data System (ADS)

Galdi, A.; Orgiani, P.; Sacco, C.; Gobaut, B.; Torelli, P.; Aruta, C.; Brookes, N. B.; Minola, M.; Harter, J. W.; Shen, K. M.; Schlom, D. G.; Maritato, L.

2018-03-01

The superconducting properties of Sr1-xLaxCuO2 thin films are strongly affected by sample preparation procedures, including the annealing step, which are not always well controlled. We have studied the evolution of Cu L2,3 and O K edge x-ray absorption spectra (XAS) of Sr1-xLaxCuO2 thin films as a function of reducing annealing, both qualitatively and quantitatively. By using linearly polarized radiation, we are able to identify the signatures of the presence of apical oxygen in the as-grown sample and its gradual removal as a function of duration of 350 °C Ar annealing performed on the same sample. Even though the as-grown sample appears to be hole doped, we cannot identify the signature of the Zhang-Rice singlet in the O K XAS, and it is extremely unlikely that the interstitial excess oxygen can give rise to a superconducting or even a metallic ground state. XAS and x-ray linear dichroism analyses are, therefore, shown to be valuable tools to improving the control over the annealing process of electron doped superconductors.

UNDERSTANDING X-RAY STARS:. The Discovery of Binary X-ray Sources

NASA Astrophysics Data System (ADS)

Schreier, E. J.; Tananbaum, H.

2000-09-01

The discovery of binary X-ray sources with UHURU introduced many new concepts to astronomy. It provided the canonical model which explained X-ray emission from a large class of galactic X-ray sources: it confirmed the existence of collapsed objects as the source of intense X-ray emission; showed that such collapsed objects existed in binary systems, with mass accretion as the energy source for the X-ray emission; and provided compelling evidence for the existence of black holes. This model also provided the basis for explaining the power source of AGNs and QSOs. The process of discovery and interpretation also established X-ray astronomy as an essential sub-discipline of astronomy, beginning its incorporation into the mainstream of astronomy.

Thoracic spine x-ray

MedlinePlus

Vertebral radiography; X-ray - spine; Thoracic x-ray; Spine x-ray; Thoracic spine films; Back films ... The test is done in a hospital radiology department or in the health care provider's office. You will lie on the x-ray table in different positions. If the x-ray ...

X-ray binaries

NASA Technical Reports Server (NTRS)

1976-01-01

Satellite X-ray experiments and ground-based programs aimed at observation of X-ray binaries are discussed. Experiments aboard OAO-3, OSO-8, Ariel 5, Uhuru, and Skylab are included along with rocket and ground-based observations. Major topics covered are: Her X-1, Cyg X-3, Cen X-3, Cyg X-1, the transient source A0620-00, other possible X-ray binaries, and plans and prospects for future observational programs.

Skull x-ray

MedlinePlus

X-ray - head; X-ray - skull; Skull radiography; Head x-ray ... Chernecky CC, Berger BJ. Radiography of skull, chest, and cervical spine - diagnostic. In: Chernecky CC, Berger BJ, eds. Laboratory Tests and Diagnostic Procedures . 6th ed. ...

Full-field transmission x-ray imaging with confocal polycapillary x-ray optics

PubMed Central

Sun, Tianxi; MacDonald, C. A.

2013-01-01

A transmission x-ray imaging setup based on a confocal combination of a polycapillary focusing x-ray optic followed by a polycapillary collimating x-ray optic was designed and demonstrated to have good resolution, better than the unmagnified pixel size and unlimited by the x-ray tube spot size. This imaging setup has potential application in x-ray imaging for small samples, for example, for histology specimens. PMID:23460760

X-ray generator

DOEpatents

Dawson, John M.

1976-01-01

Apparatus and method for producing coherent secondary x-rays that are controlled as to direction by illuminating a mixture of high z and low z gases with an intense burst of primary x-rays. The primary x-rays are produced with a laser activated plasma, and these x-rays strip off the electrons of the high z atoms in the lasing medium, while the low z atoms retain their electrons. The neutral atoms transfer electrons to highly excited states of the highly striped high z ions giving an inverted population which produces the desired coherent x-rays. In one embodiment, a laser, light beam provides a laser spark that produces the intense burst of coherent x-rays that illuminates the mixture of high z and low z gases, whereby the high z atoms are stripped while the low z ones are not, giving the desired mixture of highly ionized and neutral atoms. To this end, the laser spark is produced by injecting a laser light beam, or a plurality of beams, into a first gas in a cylindrical container having an adjacent second gas layer co-axial therewith, the laser producing a plasma and the intense primary x-rays in the first gas, and the second gas containing the high and low atomic number elements for receiving the primary x-rays, whereupon the secondary x-rays are produced therein by stripping desired ions in a neutral gas and transfer of electrons to highly excited states of the stripped ions from the unionized atoms. Means for magnetically confining and stabilizing the plasma are disclosed for controlling the direction of the x-rays.

X-ray lithography masking

NASA Technical Reports Server (NTRS)

Smith, Henry I. (Inventor); Lim, Michael (Inventor); Carter, James (Inventor); Schattenburg, Mark (Inventor)

1998-01-01

X-ray masking apparatus includes a frame having a supporting rim surrounding an x-ray transparent region, a thin membrane of hard inorganic x-ray transparent material attached at its periphery to the supporting rim covering the x-ray transparent region and a layer of x-ray opaque material on the thin membrane inside the x-ray transparent region arranged in a pattern to selectively transmit x-ray energy entering the x-ray transparent region through the membrane to a predetermined image plane separated from the layer by the thin membrane. A method of making the masking apparatus includes depositing back and front layers of hard inorganic x-ray transparent material on front and back surfaces of a substrate, depositing back and front layers of reinforcing material on the back and front layers, respectively, of the hard inorganic x-ray transparent material, removing the material including at least a portion of the substrate and the back layers of an inside region adjacent to the front layer of hard inorganic x-ray transparent material, removing a portion of the front layer of reinforcing material opposite the inside region to expose the surface of the front layer of hard inorganic x-ray transparent material separated from the inside region by the latter front layer, and depositing a layer of x-ray opaque material on the surface of the latter front layer adjacent to the inside region.

Including thermal disorder of hydrogen bonding to describe the vibrational circular dichroism spectrum of zwitterionic L-alanine in water.

PubMed

Orestes, Ednilsom; Bistafa, Carlos; Rivelino, Roberto; Canuto, Sylvio

2015-05-28

The vibrational circular dichroism (VCD) spectrum of l-alanine amino acid in aqueous solution in ambient conditions has been studied. The emphasis has been placed on the inclusion of the thermal disorder of the solute-solvent hydrogen bonds that characterize the aqueous solution condition. A combined and sequential use of molecular mechanics and quantum mechanics was adopted. To calculate the average VCD spectrum, the DFT B3LYP/6-311++G(d,p) level of calculation was employed, over one-hundred configurations composed of the solute plus all water molecules making hydrogen bonds with the solute. Simplified considerations including only four explicit solvent molecules and the polarizable continuum model were also made for comparison. Considering the large number of vibration frequencies with only limited experimental results a direct comparison is presented, when possible, and in addition a statistical analysis of the calculated values was performed. The results are found to be in line with the experiment, leading to the conclusion that including thermal disorder may improve the agreement of the vibrational frequencies with experimental results, but the thermal effects may be of greater value in the calculations of the rotational strengths.

Investigation of guanosine-quartet assemblies by vibrational and electronic circular dichroism spectroscopy, a novel approach for studying supramolecular entities.

PubMed

Setnicka, Vladimír; Urbanová, Marie; Volka, Karel; Nampally, Sreenivasachary; Lehn, Jean-Marie

2006-11-24

The self-assembly of guanosine-5'-hydrazide G-1 in D(2)O, in the presence and absence of sodium cations, has been investigated by chiroptical techniques: electronic (ECD) and the newly introduced vibrational (VCD) circular dichroism spectroscopy. Using a combination of ECD and VCD with other methods such as IR, electron microscopy, and electrospray ionization mass spectrometry (ESI-MS) it was found that G-1 produces long-range chiral aggregates consisting of G-quartets, (G-1)(4), subsequently stacked into columns, [(G-1)(4)](n), induced by binding of metal cations between the (G-1)(4) species. This process, accompanied by gelation of the sample, is highly efficient in the presence of an excess of sodium cations, leading to aggregates with strong quartet-quartet interaction. Thermally induced conformational changes and conformational stability of guanosine-5'-hydrazide assemblies were studied by chiroptical techniques and the melting temperature of the hydrogels formed was obtained. The temperature-dependent experiments indicate that the long-range supramolecular aggregates are dissociated by increasing temperature into less ordered species, monomers, or other intermediates in equilibrium, as indicated by MS experiments.

Sinus x-ray

MedlinePlus

Paranasal sinus radiography; X-ray - sinuses ... sinus x-ray is taken in a hospital radiology department. Or the x-ray may be taken ... Brown J, Rout J. ENT, neck, and dental radiology. In: Adam A, Dixon AK, Gillard JH, Schaefer- ...

General Relativistic Effects and QPOs in X-Ray Binaries

NASA Astrophysics Data System (ADS)

Markovic, D.; Lamb, F.

1999-05-01

We have investigated whether general relativistic effects may be responsible for some of the quasi-periodic X-ray brightness oscillations (QPOs) with frequencies 20--300 Hz observed in low-mass binary systems containing accreting neutron stars and black hole candidates. In particular, we have computed the motions of accreting gas in the strong gravitational fields near such objects and have explored possible mechanisms for producing X-ray flux oscillations. We have discovered a family of global gravitomagnetic (Lense-Thirring) warping modes of the inner accretion disk that have precession frequencies ranging up to the single-particle gravitomagnetic precession frequency at the inner edge of the disk, which is 30 Hz if the disk extends inward to the innermost stable circular orbit around a compact object of solar mass with dimensionless angular momentum cJ/GM2 0.2. The highest-frequency warping modes are very localized spiral corrugations of the inner disk and are weakly damped, with Q values 2--50. Precession of regions of enhanced viscous dissipation or modulation of the accretion flow by the precession may produce observable periodic variation of the X-ray flux. Detectable effects might also be produced if the gas in the inner disk breaks up into a collection of distinct clumps. We have analyzed the dynamics of such clumps as well as the conditions required for their formation and survival on time scales long enough to produce oscillations with the coherence observed in X-ray binaries.

Gamma-ray vortices from nonlinear inverse Thomson scattering of circularly polarized light.

PubMed

Taira, Yoshitaka; Hayakawa, Takehito; Katoh, Masahiro

2017-07-10

Inverse Thomson scattering is a well-known radiation process that produces high-energy photons both in nature and in the laboratory. Nonlinear inverse Thomson scattering occurring inside an intense light field is a process which generates higher harmonic photons. In this paper, we theoretically show that the higher harmonic gamma-ray produced by nonlinear inverse Thomson scattering of circularly polarized light is a gamma-ray vortex, which means that it possesses a helical wave front and carries orbital angular momentum. Our work explains a recent experimental result regarding nonlinear inverse Thomson scattering that clearly shows an annular intensity distribution as a remarkable feature of a vortex beam. Our work implies that gamma-ray vortices should be produced in various situations in astrophysics in which high-energy electrons and intense circularly polarized light fields coexist. Nonlinear inverse Thomson scattering is a promising radiation process for realizing a gamma-ray vortex source based on currently available laser and accelerator technologies, which would be an indispensable tool for exploring gamma-ray vortex science.

X-Ray Data Booklet

Science.gov Websites

X-RAY DATA BOOKLET Center for X-ray Optics and Advanced Light Source Lawrence Berkeley National Laboratory Introduction X-Ray Properties of Elements Electron Binding Energies X-Ray Energy Emission Energies Table of X-Ray Properties Synchrotron Radiation Characteristics of Synchrotron Radiation History of X

Characterization of Aptamer BC 007 Substance and Product Using Circular Dichroism and Nuclear Magnetic Resonance Spectroscopy.

PubMed

Weisshoff, Hardy; Wenzel, Katrin; Schulze-Rothe, Sarah; Nikolenko, Heike; Davideit, Hanna; Becker, Niels-Peter; Göttel, Peter; Srivatsa, G Susan; Dathe, Margitta; Müller, Johannes; Haberland, Annekathrin

2018-04-18

Possible unwanted folding of biopharmaceuticals during manufacturing and storage has resulted in analysis schemes compared to small molecules that include bioanalytical characterization besides chemical characterization. Whether bioanalytical characterization is required for nucleotide-based drugs, may be decided on a case-by-case basis. Nucleotide-based pharmaceuticals, if chemically synthesized, occupy an intermediate position between small-molecule drugs and biologics. Here, we tested whether a physicochemical characterization of a nucleotide-based drug substance, BC 007, was adequate, using circular dichroism (CD) spectroscopy. Nuclear magnetic resonance confirmed CD data in one experimental setup. BC 007 forms a quadruplex structure under specific external conditions, which was characterized for its stability and structural appearance also after denaturation using CD and nuclear magnetic resonance. The amount of the free energy (ΔG 0 ) involved in quadruplex formation of BC 007 was estimated at +8.7 kJ/mol when dissolved in water and +1.4 kJ/mol in 154 mM NaCl, indicating structural instability under these conditions. However, dissolution of the substance in 5 mM of KCl reduced the ΔG 0 to -5.6 kJ/mol due to the stabilizing effect of cations. These results show that positive ΔG 0 of quadruplex structure formation in water and aqueous NaCl prevents BC 007 from preforming stable 3-dimensional structures, which could potentially affect drug function. Copyright © 2018 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Recent X-ray Variability of Eta Car Approaching The X-ray Eclipse

NASA Technical Reports Server (NTRS)

Corcoran, M.; Swank, J. H.; Ishibashi, K.; Gull, T.; Humphreys, R.; Damineli, A.; Walborn, N.; Hillier, D. J.; Davidson, K.; White, S. M.

2002-01-01

We discuss recent X-ray spectral variability of the supermassive star Eta Car in the interval since the last X-ray eclipse in 1998. We concentrate on the interval just prior to the next X-ray eclipse which is expected to occur in June 2003. We compare the X-ray behavior during the 2001-2003 cycle with the previous cycle (1996-1998) and note similarities and differences in the temporal X-ray behavior. We also compare a recent X-ray observation of Eta Car obtained with the Chandra high energy transmission grating in October 2002 with an earlier observation from Nov 2002, and interpret these results in terms of the proposed colliding wind binary model for the star. In addition we discuss planned observations for the upcoming X-ray eclipse.

Studies of protein-protein and protein-water interactions by small angle x-ray scattering, terahertz spectroscopy, ASMOS, and computer simulation

NASA Astrophysics Data System (ADS)

Kim, Seung Joong

The protein folding problem has been one of the most challenging subjects in biological physics due to its complexity. Energy landscape theory based on statistical mechanics provides a thermodynamic interpretation of the protein folding process. We have been working to answer fundamental questions about protein-protein and protein-water interactions, which are very important for describing the energy landscape surface of proteins correctly. At first, we present a new method for computing protein-protein interaction potentials of solvated proteins directly from SAXS data. An ensemble of proteins was modeled by Metropolis Monte Carlo and Molecular Dynamics simulations, and the global X-ray scattering of the whole model ensemble was computed at each snapshot of the simulation. The interaction potential model was optimized and iterated by a Levenberg-Marquardt algorithm. Secondly, we report that terahertz spectroscopy directly probes hydration dynamics around proteins and determines the size of the dynamical hydration shell. We also present the sequence and pH-dependence of the hydration shell and the effect of the hydrophobicity. On the other hand, kinetic terahertz absorption (KITA) spectroscopy is introduced to study the refolding kinetics of ubiquitin and its mutants. KITA results are compared to small angle X-ray scattering, tryptophan fluorescence, and circular dichroism results. We propose that KITA monitors the rearrangement of hydrogen bonding during secondary structure formation. Finally, we present development of the automated single molecule operating system (ASMOS) for a high throughput single molecule detector, which levitates a single protein molecule in a 10 microm diameter droplet by the laser guidance. I also have performed supporting calculations and simulations with my own program codes.

Observation of circular dichroism in photoelectron angular distributions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Appling, J.R.; White, M.G.; Orlando, T.M.

1986-12-01

The first observations of dichroic effects in photoelectron angular distributions are reported for photoionization of aligned molecular excited states with circularly polarized light. Photoelectron angular distributions resulting from the two-color, (2+1) REMPI of NO via the A /sup 2/summation/sup +/, v = 0, J = 3/2,5/2 excited states exhibit significant left--right asymmetry. The experimental CD angular distributions are found to be well described by the general theoretical framework recently developed by Dubs, Dixit, and McKoy and are in good qualitative agreement with their calculated REMPI--CD distributions.

Observation of circular dichroism in photoelectron angular distributions

NASA Astrophysics Data System (ADS)

Appling, Jeffrey R.; White, Michael G.; Orlando, Thomas M.; Anderson, Scott L.

1986-12-01

The first observations of dichroic effects in photoelectron angular distributions are reported for photoionization of aligned molecular excited states with circularly polarized light. Photoelectron angular distributions resulting from the two-color, (2+1) REMPI of NO via the A 2∑+, v=0, J=3/2,5/2 excited states exhibit significant left-right asymmetry. The experimental CD angular distributions are found to be well described by the general theoretical framework recently developed by Dubs, Dixit, and McKoy and are in good qualitative agreement with their calculated REMPI-CD distributions.

Large area soft x-ray collimator to facilitate x-ray optics testing

NASA Technical Reports Server (NTRS)

Espy, Samuel L.

1994-01-01

The first objective of this program is to design a nested conical foil x-ray optic which will collimate x-rays diverging from a point source. The collimator could then be employed in a small, inexpensive x-ray test stand which would be used to test various x-ray optics and detector systems. The second objective is to demonstrate the fabrication of the x-ray reflectors for this optic using lacquer-smoothing and zero-stress electroforming techniques.

Development of x-ray laminography under an x-ray microscopic condition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hoshino, Masato; Uesugi, Kentaro; Takeuchi, Akihisa

2011-07-15

An x-ray laminography system under an x-ray microscopic condition was developed to obtain a three-dimensional structure of laterally-extended planar objects which were difficult to observe by x-ray tomography. An x-ray laminography technique was introduced to an x-ray transmission microscope with zone plate optics. Three prototype sample holders were evaluated for x-ray imaging laminography. Layered copper grid sheets were imaged as a laminated sample. Diatomite powder on a silicon nitride membrane was measured to confirm the applicability of this method to non-planar micro-specimens placed on the membrane. The three-dimensional information of diatom shells on the membrane was obtained at a spatialmore » resolution of sub-micron. Images of biological cells on the membrane were also obtained by using a Zernike phase contrast technique.« less

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

PubMed

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

2015-05-28

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

X-ray Binaries in the Galaxy and the Magellanic Clouds

NASA Astrophysics Data System (ADS)

Cowley, Anne P.

1993-05-01

For more than two decades astronomers have been aware that the most X-ray luminous stellar sources (L_x > 10(35) erg s(-1) ) are interacting binaries where one component is a neutron star or black hole. While other types of single and multiple stars are known X-ray sources, none compare in X-ray luminosity with the ``classical" X-ray binaries. In these systems X-ray emission results from accretion of material from a non-degenerate companion onto the compact star through several alternate mechanisms including Roche lobe overflow, stellar winds, or periastron effects in non-circular orbits. It has been recognized for many years that X-ray binaries divide into two broad groups, characterized primarily by the mass of the non-degenerate star: 1) massive X-ray binaries (MXRB), in which the optical primary is a bright, early-type star, and 2) low-mass X-ray binaries (LMXB), where a lower main-sequence or subgiant star is the mass donor. A broad variety of observational characteristics further subdivide these classes. In the Galaxy these two groups appear to be spatially and kinematically associated with the disk and the halo populations, respectively. A few dozen MXRB are known in the Galaxy. A great deal of information about their physical properties has been learned from observational study. Their optical primaries can be investigated by conventional techniques. Furthermore, most MXRB contain X-ray pulsars, allowing accurate determination of their orbital parameters. From these data masses have been determined for the neutron stars, all of which are ~ 1.4 Msun, within measurement errors. By contrast, the LMXB have been much more difficult to study. Although there are ~ 150 LMXB in the Galaxy, most are distant and faint, requiring use of large telescopes for their study. Their optical light is almost always dominated by an accretion disk, rather than the mass-losing star, making interpretation of their spectral and photometric properties difficult. Their often uncertain

Laser plasma x-ray source for ultrafast time-resolved x-ray absorption spectroscopy

DOE PAGES

Miaja-Avila, L.; O'Neil, G. C.; Uhlig, J.; ...

2015-03-02

We describe a laser-driven x-ray plasma source designed for ultrafast x-ray absorption spectroscopy. The source is comprised of a 1 kHz, 20 W, femtosecond pulsed infrared laser and a water target. We present the x-ray spectra as a function of laser energy and pulse duration. Additionally, we investigate the plasma temperature and photon flux as we vary the laser energy. We obtain a 75 μm FWHM x-ray spot size, containing ~10 6 photons/s, by focusing the produced x-rays with a polycapillary optic. Since the acquisition of x-ray absorption spectra requires the averaging of measurements from >10 7 laser pulses, wemore » also present data on the source stability, including single pulse measurements of the x-ray yield and the x-ray spectral shape. In single pulse measurements, the x-ray flux has a measured standard deviation of 8%, where the laser pointing is the main cause of variability. Further, we show that the variability in x-ray spectral shape from single pulses is low, thus justifying the combining of x-rays obtained from different laser pulses into a single spectrum. Finally, we show a static x-ray absorption spectrum of a ferrioxalate solution as detected by a microcalorimeter array. Altogether, our results demonstrate that this water-jet based plasma source is a suitable candidate for laboratory-based time-resolved x-ray absorption spectroscopy experiments.« less

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

NASA Astrophysics Data System (ADS)

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

2006-07-01

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Antropov, Vladimir P; Antonov, Victor N

We present a first-principles investigation of the electronic structure and physical properties of doped lithium nitridometalates Li 2(Li 1-xM x)N (LiMN) with M = Cr, Mn, Fe, Co, and Ni. The diverse properties include the equilibrium magnetic moments, magneto-crystalline anisotropy, magneto-optical Kerr spectra, and x-ray magnetic circular dichroism. We explain the colossal magnetic anisotropy in LiFeN by its unique electronic structure which ultimately leads to a series of unusual physical properties. The most unique property is a complete suppression of relativistic effects and freezing of orbital moments for in-plane orientation of the magnetization. This leads to the colossal spatial anisotropymore » of many magnetic properties including energy, Kerr, and dichroism effects. LiFeN is identified as an ultimate single-ion anisotropy system where a nearly insulating state can be produced by a spin orbital coupling alone. A very nontrivial strongly fluctuating and sign changing character of the magnetic anisotropy with electronic 3d-atomic doping is predicted theoretically. A large and highly anisotropic Kerr effect due to the interband transitions between atomic-like Fe 3d bands is found for LiFeN. A giant anisotropy of the x-ray magnetic circular dichroism for the Fe K spectrum and a very weak one for the Fe L 2,3 spectra in LiFeN are also predicted.« less

Panoramic Dental X-Ray

MedlinePlus

... Physician Resources Professions Site Index A-Z Panoramic Dental X-ray Panoramic dental x-ray uses a very small dose of ... x-ray , is a two-dimensional (2-D) dental x-ray examination that captures the entire mouth ...

Circularly polarized luminescence of syndiotactic polystyrene

NASA Astrophysics Data System (ADS)

Rizzo, Paola; Abbate, Sergio; Longhi, Giovanna; Guerra, Gaetano

2017-11-01

Syndiotactic polystyrene (s-PS) films, when crystallized from the amorphous state by temporary sorption of non-racemic guest molecules (like carvone) not only exhibit unusually high optical activity, both in the UV-Visible and Infrared ranges, but also present circularly polarized luminescence (CPL) with high dissymmetry ratios (g = ΔI/I values in the range 0.02-0.03). Experimental evidences provide support, rather than to the usual molecular circular dichroism, to a supramolecular chiral optical response being extrinsic to the site of photon absorption and emission, possibly associated with a helical morphology of s-PS crystallites.

Circular Dichroism reveals evidence of coupling between immunoglobulin constant and variable region secondary structure.

PubMed

Janda, Alena; Casadevall, Arturo

2010-04-01

Antibodies (Ab) are bifunctional molecules with two domains, a constant region (C) that confers effector properties and a variable (V) region responsible of antigen (Ag) binding. Historically the C and V regions were considered to be functionally independent, with Ag specificity being solely determined by the V region. However, recent studies suggest that the C region can affect Ab fine specificity. This has led to the proposal that the C(H) domain influences the structure of the V region, thus affecting Ab affinity and fine specificity. An inference from this proposal is that V region identical monoclonal Abs (mAbs) differing in C region (eg isotype) would manifest different secondary structures arising from isotype-induced variation in the V-C regions after Ag binding. We hypothesized that such effects could translate into differences in Circular Dichroism (CD) upon Ag-Ab complexes formation. Consequently we studied the interaction of a set of V region identical IgG(1), IgG(2a), IgG(2b) and IgG(3) mAbs with glucuronoxylomannan (GXM). The native CD spectra of the pairs IgG(1)/IgG(2a) and IgG(3)/IgG(2b) were strikingly similar, implying similar secondary structure content. GXM binding by IgG(1), IgG(2a), IgG(2b) and IgG(3) produced different CD changes, with the pairs IgG(1)/IgG(2a) and IgG(3)/IgG(2b) again manifesting qualitatively similar trends in secondary structure changes. The magnitude of the changes differed among the isotypes with IgG(2a)>IgG(3)>IgG(2b)>IgG(1). These differences in CD changes were interpreted to reflect differences in V-C secondary structures. Copyright 2010 Elsevier Ltd. All rights reserved.

X-ray Spectral Formation In High-mass X-ray Binaries: The Case Of Vela X-1

NASA Astrophysics Data System (ADS)

Akiyama, Shizuka; Mauche, C. W.; Liedahl, D. A.; Plewa, T.

2007-05-01

We are working to develop improved models of radiatively-driven mass flows in the presence of an X-ray source -- such as in X-ray binaries, cataclysmic variables, and active galactic nuclei -- in order to infer the physical properties that determine the X-ray spectra of such systems. The models integrate a three-dimensional time-dependent hydrodynamics capability (FLASH); a comprehensive and uniform set of atomic data, improved calculations of the line force multiplier that account for X-ray photoionization and non-LTE population kinetics, and X-ray emission-line models appropriate to X-ray photoionized plasmas (HULLAC); and a Monte Carlo radiation transport code that simulates Compton scattering and recombination cascades following photoionization. As a test bed, we have simulated a high-mass X-ray binary with parameters appropriate to Vela X-1. While the orbital and stellar parameters of this system are well constrained, the physics of X-ray spectral formation is less well understood because the canonical analytical wind velocity profile of OB stars does not account for the dynamical and radiative feedback effects due to the rotation of the system and to the irradiation of the stellar wind by X-rays from the neutron star. We discuss the dynamical wind structure of Vela X-1 as determined by the FLASH simulation, where in the binary the X-ray emission features originate, and how the spatial and spectral properties of the X-ray emission features are modified by Compton scattering, photoabsorption, and fluorescent emission. This work was performed under the auspices of the U.S. Department of Energy by University of California, Lawrence Livermore National Laboratory under Contract W-7405-Eng-48.

Searching for Models Exhibiting High Circularly Polarized Luminescence: the Electroactive Inherently Chiral Oligothiophenes.

PubMed

Benincori, Tiziana; Appoloni, Giulio; Mussini, Patrizia Romana; Arnaboldi, Serena; Cirilli, Roberto; Quartapelle Procopio, Elsa; Panigati, Monica; Abbate, Sergio; Mazzeo, Giuseppe; Longhi, Giovanna

2018-05-02

Two new inherently chiral oligothiophenes characterized by the atropisomeric 3,3'-bithianaphtene scaffold functionalized with fused ring bithiophene derivatives, namely 4H-cyclopenta [2,1-b3:4b']dithiophene (CPDT) and dithieno[3,3-b:2',3'-d]pyrrole (DTP), were synthesized. The racemates were fully characterized and resolved into antipodes by enantioselective HPLC. The enantiomers were analyzed through different chiroptical techniques: electronic circular dichroism (ECD) and vibrational circular dichroism (VCD) were employed to attribute the absolute configuration (AC). Comparison of experimental and calculated VCD spectra confirmed the DFT calculated conformational characteristics. The compound functionalized with two CPDT units was oxidized with FeCl3 and ECD and CPL of the resulting material were measured. Circularly Polarized Luminescence (CPL) was measured in order to verify if inherently chiral oligothiophenes could be promising systems for chiral photonics applications. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

NASA Astrophysics Data System (ADS)

Nahon, Laurent

2017-06-01

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

X-ray beam finder

DOEpatents

Gilbert, H.W.

1983-06-16

An X-ray beam finder for locating a focal spot of an X-ray tube includes a mass of X-ray opaque material having first and second axially-aligned, parallel-opposed faces connected by a plurality of substantially identical parallel holes perpendicular to the faces and a film holder for holding X-ray sensitive film tightly against one face while the other face is placed in contact with the window of an X-ray head.

X-ray and gamma ray astronomy detectors

NASA Technical Reports Server (NTRS)

Decher, Rudolf; Ramsey, Brian D.; Austin, Robert

1994-01-01

X-ray and gamma ray astronomy was made possible by the advent of space flight. Discovery and early observations of celestial x-rays and gamma rays, dating back almost 40 years, were first done with high altitude rockets, followed by Earth-orbiting satellites> once it became possible to carry detectors above the Earth's atmosphere, a new view of the universe in the high-energy part of the electromagnetic spectrum evolved. Many of the detector concepts used for x-ray and gamma ray astronomy were derived from radiation measuring instruments used in atomic physics, nuclear physics, and other fields. However, these instruments, when used in x-ray and gamma ray astronomy, have to meet unique and demanding requirements related to their operation in space and the need to detect and measure extremely weak radiation fluxes from celestial x-ray and gamma ray sources. Their design for x-ray and gamma ray astronomy has, therefore, become a rather specialized and rapidly advancing field in which improved sensitivity, higher energy and spatial resolution, wider spectral coverage, and enhanced imaging capabilities are all sought. This text is intended as an introduction to x-ray and gamma ray astronomy instruments. It provides an overview of detector design and technology and is aimed at scientists, engineers, and technical personnel and managers associated with this field. The discussion is limited to basic principles and design concepts and provides examples of applications in past, present, and future space flight missions.

X-ray imaging crystal spectrometer for extended X-ray sources

DOEpatents

Bitter, Manfred L.; Fraenkel, Ben; Gorman, James L.; Hill, Kenneth W.; Roquemore, A. Lane; Stodiek, Wolfgang; von Goeler, Schweickhard E.

2001-01-01

Spherically or toroidally curved, double focusing crystals are used in a spectrometer for X-ray diagnostics of an extended X-ray source such as a hot plasma produced in a tokomak fusion experiment to provide spatially and temporally resolved data on plasma parameters using the imaging properties for Bragg angles near 45. For a Bragg angle of 45.degree., the spherical crystal focuses a bundle of near parallel X-rays (the cross section of which is determined by the cross section of the crystal) from the plasma to a point on a detector, with parallel rays inclined to the main plain of diffraction focused to different points on the detector. Thus, it is possible to radially image the plasma X-ray emission in different wavelengths simultaneously with a single crystal.

Nonlinear QED effects in X-ray emission of pulsars

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shakeri, Soroush; Haghighat, Mansour; Xue, She-Sheng, E-mail: Soroush.Shakeri@ph.iut.ac.ir, E-mail: m.haghighat@shirazu.ac.ir, E-mail: xue@icra.it

2017-10-01

In the presence of strong magnetic fields near pulsars, the QED vacuum becomes a birefringent medium due to nonlinear QED interactions. Here, we explore the impact of the effective photon-photon interaction on the polarization evolution of photons propagating through the magnetized QED vacuum of a pulsar. We solve the quantum Boltzmann equation within the framework of the Euler-Heisenberg Lagrangian to find the evolution of the Stokes parameters. We find that linearly polarized X-ray photons propagating outward in the magnetosphere of a rotating neutron star can acquire high values for the circular polarization parameter. Meanwhile, it is shown that the polarizationmore » characteristics of photons besides photon energy depend strongly on parameters of the pulsars such as magnetic field strength, inclination angle and rotational period. Our results are clear predictions of QED vacuum polarization effects in the near vicinity of magnetic stars which can be tested with the upcoming X-ray polarimetric observations.« less

Quantitative analysis of magnetic spin and orbital moments from an oxidized iron (1 1 0) surface using electron magnetic circular dichroism

DOE PAGES

Thersleff, Thomas; Rusz, Jan; Rubino, Stefano; ...

2015-08-17

Understanding the ramifications of reduced crystalline symmetry on magnetic behavior is a critical step in improving our understanding of nanoscale and interfacial magnetism. However, investigations of such effects are often controversial largely due to the challenges inherent in directly correlating nanoscale stoichiometry and structure to magnetic behavior. Here, we describe how to use Transmission Electron Microscope (TEM) to obtain Electron Magnetic Circular Dichroism (EMCD) signals as a function of scattering angle to locally probe the magnetic behavior of thin oxide layers grown on an Fe (1 1 0) surface. Experiments and simulations both reveal a strong dependence of the magneticmore » orbital to spin ratio on its scattering vector in reciprocal space. We exploit this variation to extract the magnetic properties of the oxide cladding layer, showing that it locally may exhibit an enhanced orbital to spin moment ratio. This finding is supported here by both spatially and angularly resolved EMCD measurements, opening up the way for compelling investigations into how magnetic properties are affected by nanoscale features.« less

Experimental evidence of Cr magnetic moments at low temperature in Cr2A(A=Al, Ge)C.

PubMed

Jaouen, M; Bugnet, M; Jaouen, N; Ohresser, P; Mauchamp, V; Cabioc'h, T; Rogalev, A

2014-04-30

From x-ray magnetic circular dichroism experiments performed at low temperature on Cr2AlC and Cr2GeC thin films, it is evidenced that Cr atoms carry a net magnetic moment in these ternary phases. It is shown that the Cr magnetization of the Al-based compound nearly vanished at 100 K in agreement with what has been recently observed on bulk. X-ray linear dichroism measurements performed at various angles of incidence and temperatures clearly demonstrate the existence of a charge ordering along the c axis of the structure of Cr2AlC. All these experimental observations support, in part, theoretical calculations claiming that Cr dd correlations have to be considered to correctly describe the structure and properties of these Cr-based ternary phases.

X-ray lithography source

DOEpatents

Piestrup, M.A.; Boyers, D.G.; Pincus, C.

1991-12-31

A high-intensity, inexpensive X-ray source for X-ray lithography for the production of integrated circuits is disclosed. Foil stacks are bombarded with a high-energy electron beam of 25 to 250 MeV to produce a flux of soft X-rays of 500 eV to 3 keV. Methods of increasing the total X-ray power and making the cross section of the X-ray beam uniform are described. Methods of obtaining the desired X-ray-beam field size, optimum frequency spectrum and eliminating the neutron flux are all described. A method of obtaining a plurality of station operation is also described which makes the process more efficient and economical. The satisfying of these issues makes transition radiation an excellent moderate-priced X-ray source for lithography. 26 figures.

X-ray lithography source

DOEpatents

Piestrup, Melvin A.; Boyers, David G.; Pincus, Cary

1991-01-01

A high-intensity, inexpensive X-ray source for X-ray lithography for the production of integrated circuits. Foil stacks are bombarded with a high-energy electron beam of 25 to 250 MeV to produce a flux of soft X-rays of 500 eV to 3 keV. Methods of increasing the total X-ray power and making the cross section of the X-ray beam uniform are described. Methods of obtaining the desired X-ray-beam field size, optimum frequency spectrum and elminating the neutron flux are all described. A method of obtaining a plurality of station operation is also described which makes the process more efficient and economical. The satisfying of these issues makes transition radiation an exellent moderate-priced X-ray source for lithography.

Bone cartilage imaging with x-ray interferometry using a practical x-ray tube

NASA Astrophysics Data System (ADS)

Kido, Kazuhiro; Makifuchi, Chiho; Kiyohara, Junko; Itou, Tsukasa; Honda, Chika; Momose, Atsushi

2010-04-01

The purpose of this study was to design an X-ray Talbot-Lau interferometer for the imaging of bone cartilage using a practical X-ray tube and to develop that imaging system for clinical use. Wave-optics simulation was performed to design the interferometer with a practical X-ray tube, a source grating, two X-ray gratings, and an X-ray detector. An imaging system was created based on the results of the simulation. The specifications were as follows: the focal spot size was 0.3 mm of an X-ray tube with a tungsten anode (Toshiba, Tokyo, Japan). The tube voltage was set at 40 kVp with an additive aluminum filter, and the mean energy was 31 keV. The pixel size of the X-ray detector, a Condor 486 (Fairchild Imaging, California, USA), was 15 μm. The second grating was a Ronchi-type grating whose pitch was 5.3 μm. Imaging performance of the system was examined with X-ray doses of 0.5, 3 and 9 mGy so that the bone cartilage of a chicken wing was clearly depicted with X-ray doses of 3 and 9 mGy. This was consistent with the simulation's predictions. The results suggest that X-ray Talbot-Lau interferometry would be a promising tool in detecting soft tissues in the human body such as bone cartilage for the X-ray image diagnosis of rheumatoid arthritis. Further optimization of the system will follow to reduce the X-ray dose for clinical use.

Bandpass x-ray diode and x-ray multiplier detector

DOEpatents

Wang, C.L.

1982-09-27

An absorption-edge of an x-ray absorption filter and a quantum jump of a photocathode determine the bandpass characteristics of an x-ray diode detector. An anode, which collects the photoelectrons emitted by the photocathode, has enhanced amplification provided by photoelectron-multiplying means which include dynodes or a microchannel-plate electron-multiplier. Suppression of undesired high frequency response for a bandpass x-ray diode is provided by subtracting a signal representative of energies above the passband from a signal representative of the overall response of the bandpass diode.

X-ray astronomical spectroscopy

NASA Technical Reports Server (NTRS)

Holt, Stephen S.

1987-01-01

The contributions of the Goddard group to the history of X-ray astronomy are numerous and varied. One role that the group has continued to play involves the pursuit of techniques for the measurement and interpretation of the X-ray spectra of cosmic sources. The latest development is the selection of the X-ray microcalorimeter for the Advanced X-ray Astrophysics Facility (AXAF) study payload. This technology is likely to revolutionize the study of cosmic X-ray spectra.

Antiferromagnetic exchange bias of a ferromagnetic semiconductor by a ferromagnetic metal

DOE Office of Scientific and Technical Information (OSTI.GOV)

Olejnik, K.; Wadley, P.; Haigh, J.

2009-11-05

We demonstrate an exchange bias in (Ga,Mn)As induced by antiferromagnetic coupling to a thin overlayer of Fe. Bias fields of up to 240 Oe are observed. Using element-specific x-ray magnetic circular dichroism measurements, we distinguish an interface layer that is strongly pinned antiferromagnetically to the Fe. The interface layer remains polarized at room temperature.

X-ray and microwave observations of active regions

NASA Technical Reports Server (NTRS)

Webb, D. F.; Davis, J. M.; Kundu, M. R.; Velusamy, T.

1983-01-01

Coordinated high-resolution (1-3 arcsec) observations of two active solar regions (H 421 and H 419) on November 16, 1979, are reported: soft-X-ray filtergrams from a sounding rocket flight, VLA total-intensity and circular-polarization microwave (6-cm) radio maps, KPNO full-disk photospheric magnetograms, and BBSO H-alpha data. The images were converted to 4.8-arcsec/mm-scale transparencies and coaligned on the basis of sunspot positions for comparison. The two active regions are characterized in detail, and intensity, size, and polarization data for the brightest microwave components (BMC) are listed. It is found that 19 of the 32 BMC are farther than 5 arcsec from any sunspot, and that X-ray-emitting structures only rarely correspond to sunspots, or BMC. About one third of the BMC are located at the feet or legs of coronal loops smaller than about 50,000 km. The limitations implied by these obervations for proposed thermal-bremsstrahlung, thermal-gyro-resonance, and nonthermal microwave-emission mechanisms are discussed.

X-Ray

MedlinePlus

... of gray. For some types of X-ray tests, a contrast medium — such as iodine or barium — is introduced into your body to provide greater detail on the images. Why it's done X-ray technology is used to examine many parts of the ...

X-ray luminescence computed tomography using a focused x-ray beam.

PubMed

Zhang, Wei; Lun, Michael C; Nguyen, Alex Anh-Tu; Li, Changqing

2017-11-01

Due to the low x-ray photon utilization efficiency and low measurement sensitivity of the electron multiplying charge coupled device camera setup, the collimator-based narrow beam x-ray luminescence computed tomography (XLCT) usually requires a long measurement time. We, for the first time, report a focused x-ray beam-based XLCT imaging system with measurements by a single optical fiber bundle and a photomultiplier tube (PMT). An x-ray tube with a polycapillary lens was used to generate a focused x-ray beam whose x-ray photon density is 1200 times larger than a collimated x-ray beam. An optical fiber bundle was employed to collect and deliver the emitted photons on the phantom surface to the PMT. The total measurement time was reduced to 12.5 min. For numerical simulations of both single and six fiber bundle cases, we were able to reconstruct six targets successfully. For the phantom experiment, two targets with an edge-to-edge distance of 0.4 mm and a center-to-center distance of 0.8 mm were successfully reconstructed by the measurement setup with a single fiber bundle and a PMT. (2017) COPYRIGHT Society of Photo-Optical Instrumentation Engineers (SPIE).

Note: Derivation of two-photon circular dichroism—Addendum to “Two-photon circular dichroism” [J. Chem. Phys. 62, 1006 (1975)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Friese, Daniel H., E-mail: daniel.h.friese@uit.no

2015-09-07

This addendum shows the detailed derivation of the fundamental equations for two-photon circular dichroism which are given in a very condensed form in the original publication [I. Tinoco, J. Chem. Phys. 62, 1006 (1975)]. In addition, some minor errors are corrected and some of the derivations in the original publication are commented.

X-ray Observations of Cosmic Ray Acceleration

NASA Technical Reports Server (NTRS)

Petre, Robert

2012-01-01

Since the discovery of cosmic rays, detection of their sources has remained elusive. A major breakthrough has come through the identification of synchrotron X-rays from the shocks of supernova remnants through imaging and spectroscopic observations by the most recent generation of X-ray observatories. This radiation is most likely produced by electrons accelerated to relativistic energy, and thus has offered the first, albeit indirect, observational evidence that diffusive shock acceleration in supernova remnants produces cosmic rays to TeV energies, possibly as high as the "knee" in the cosmic ray spectrum. X-ray observations have provided information about the maximum energy to which these shOCks accelerate electrons, as well as indirect evidence of proton acceleration. Shock morphologies measured in X-rays have indicated that a substantial fraction of the shock energy can be diverted into particle acceleration. This presentation will summarize what we have learned about cosmic ray acceleration from X-ray observations of supernova remnants over the past two decades.

X-Ray Attenuation Coefficients from 10 Kev to 100 Mev,

DTIC Science & Technology

1957-04-30

is u&Ung"w APR n 4 1994 94-10025 0 Z1UNITED STATES DEPARTMENT OF COMMERCE NATIONAL BUREAU OF STANDARDS 94 .4 1 096 Data on Radiation Physics Graphs...OF COMMERCE • Sinclair Weeks, Secretary NATIONAL BUREAU OF STANDARDS , A. V. Astin, Dirvcew X-ray Attenuation Coefficients From 10 key to 100 Mev...Dit. ibtion I Availabiilty Codes Avai# and/or Dist Special National Bureau of Standards Circular 583 Issuw1 April 30, 1957 Fo e teSpr dt

Method for spatially modulating X-ray pulses using MEMS-based X-ray optics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lopez, Daniel; Shenoy, Gopal; Wang, Jin

A method and apparatus are provided for spatially modulating X-rays or X-ray pulses using microelectromechanical systems (MEMS) based X-ray optics. A torsionally-oscillating MEMS micromirror and a method of leveraging the grazing-angle reflection property are provided to modulate X-ray pulses with a high-degree of controllability.

X-ray monitoring optical elements

DOEpatents

Stoupin, Stanislav; Shvydko, Yury; Katsoudas, John; Blank, Vladimir D.; Terentyev, Sergey A.

2016-12-27

An X-ray article and method for analyzing hard X-rays which have interacted with a test system. The X-ray article is operative to diffract or otherwise process X-rays from an input X-ray beam which have interacted with the test system and at the same time provide an electrical circuit adapted to collect photoelectrons emitted from an X-ray optical element of the X-ray article to analyze features of the test system.

Optical and X-ray studies of Compact X-ray Binaries in NGC 5904

NASA Astrophysics Data System (ADS)

Bhalotia, Vanshree; Beck-Winchatz, Bernhard

2018-06-01

Due to their high stellar densities, globular cluster systems trigger various dynamical interactions, such as the formation of compact X-ray binaries. Stellar collisional frequencies have been correlated to the number of X-ray sources detected in various clusters and we hope to measure this correlation for NGC 5904. Optical fluxes of sources from archival HST images of NGC 5904 have been measured using a DOLPHOT PSF photometry in the UV, optical and near-infrared. We developed a data analysis pipeline to process the fluxes of tens of thousands of objects using awk, python and DOLPHOT. We plot color magnitude diagrams in different photometric bands in order to identify outliers that could be X-ray binaries, since they do not evolve the same way as singular stars. Aligning previously measured astrometric data for X-ray sources in NGC 5904 from Chandra with archival astrometric data from HST will filter out the outlier objects that are not X-ray producing, and provide a sample of compact binary systems that are responsible for X-ray emission in NGC 5904. Furthermore, previously measured X-ray fluxes of NGC 5904 from Chandra have also been used to measure the X-ray to optical flux ratio and identify the types of compact X-ray binaries responsible for the X-ray emissions in NGC 5904. We gratefully acknowledge the support from the Illinois Space Grant Consortium.

Ag(I)-mediated homo and hetero pairs of guanosine and cytidine: monitoring by circular dichroism spectroscopy.

PubMed

Goncharova, Iryna

2014-01-24

Ag(I)-containing compounds are attractive as antibacterial and antifungal agents. The renewed interest in the application of silver(I) compounds has led to the need for detailed knowledge of the mechanism of their action. One of the possible ways is the coordination of Ag(I) to G-C pairs of DNA, where Ag(+) ions form Ag(I)-mediated base pairs and inhibit the transcription. Herein, a systematic chiroptical study on silver(I)-mediated homo and mixed pairs of the C-G complementary-base derivatives cytidine(C) and 5'-guanosine monophosphate(G) in water is presented. Ag(I)-mediated homo and hetero pairs of G and C and their self-assembled species were studied under two pH levels (7.0 and 10.0) by vibrational (VCD) and electronic circular dichroism(ECD). VCD was used for the first time in this field and showed itself to be a powerful method for obtaining specific structural information in solution. Based on results of the VCD experiments, the different geometries of the homo pairs were proposed under pH 7.0 and 10.0. ECD was used as a diagnostic tool to characterize the studied systems and as a contact point between the previously defined structures of the metal or proton mediated pairs of nucleobases and the systems studied here. On the basis of the obtained data, the formation of the self-assembled species of cytidine with a structure similar to the i-motif structure in DNA was proposed at pH 10.0. Copyright © 2013 Elsevier B.V. All rights reserved.

Ag(I)-mediated homo and hetero pairs of guanosine and cytidine: Monitoring by circular dichroism spectroscopy

NASA Astrophysics Data System (ADS)

Goncharova, Iryna

2014-01-01

Ag(I)-containing compounds are attractive as antibacterial and antifungal agents. The renewed interest in the application of silver(I) compounds has led to the need for detailed knowledge of the mechanism of their action. One of the possible ways is the coordination of Ag(I) to G-C pairs of DNA, where Ag+ ions form Ag(I)-mediated base pairs and inhibit the transcription. Herein, a systematic chiroptical study on silver(I)-mediated homo and mixed pairs of the C-G complementary-base derivatives cytidine(C) and 5‧-guanosine monophosphate(G) in water is presented. Ag(I)-mediated homo and hetero pairs of G and C and their self-assembled species were studied under two pH levels (7.0 and 10.0) by vibrational (VCD) and electronic circular dichroism(ECD). VCD was used for the first time in this field and showed itself to be a powerful method for obtaining specific structural information in solution. Based on results of the VCD experiments, the different geometries of the homo pairs were proposed under pH 7.0 and 10.0. ECD was used as a diagnostic tool to characterize the studied systems and as a contact point between the previously defined structures of the metal or proton mediated pairs of nucleobases and the systems studied here. On the basis of the obtained data, the formation of the self-assembled species of cytidine with a structure similar to the i-motif structure in DNA was proposed at pH 10.0.

The Cambridge-Cambridge X-ray Serendipity Survey: I X-ray luminous galaxies

NASA Technical Reports Server (NTRS)

Boyle, B. J.; Mcmahon, R. G.; Wilkes, B. J.; Elvis, M.

1994-01-01

We report on the first results obtained from a new optical identification program of 123 faint X-ray sources with S(0.5-2 keV) greater than 2 x 10(exp -14) erg/s/sq cm serendipitously detected in ROSAT PSPC pointed observations. We have spectroscopically identified the optical counterparts to more than 100 sources in this survey. Although the majority of the sample (68 objects) are QSO's, we have also identified 12 narrow emission line galaxies which have extreme X-ray luminosities (10(exp 42) less than L(sub X) less than 10(exp 43.5) erg/s). Subsequent spectroscopy reveals them to be a mixture of star-burst galaxies and Seyfert 2 galaxies in approximately equal numbers. Combined with potentially similar objects identified in the Einstein Extended Medium Sensitivity Survey, these X-ray luminous galaxies exhibit a rate of cosmological evolution, L(sub X) varies as (1 + z)(exp 2.5 +/- 1.0), consistent with that derived for X-ray QSO's. This evolution, coupled with the steep slope determined for the faint end of the X-ray luminosity function (Phi(L(sub X)) varies as L(sub X)(exp -1.9)), implies that such objects could comprise 15-35% of the soft (1-2 keV) X-ray background.

Compact X-ray sources: X-rays from self-reflection

NASA Astrophysics Data System (ADS)

Mangles, Stuart P. D.

2012-05-01

Laser-based particle acceleration offers a way to reduce the size of hard-X-ray sources. Scientists have now developed a simple scheme that produces a bright flash of hard X-rays by using a single laser pulse both to generate and to scatter an electron beam.

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

NASA Astrophysics Data System (ADS)

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

2017-02-01

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

Understanding the X-ray spectrum of anomalous X-ray pulsars and soft gamma-ray repeaters

NASA Astrophysics Data System (ADS)

Guo, Yan-Jun; Dai, Shi; Li, Zhao-Sheng; Liu, Yuan; Tong, Hao; Xu, Ren-Xin

2015-04-01

Hard X-rays above 10 keV are detected from several anomalous X-ray pulsars (AXPs) and soft gamma-ray repeaters (SGRs), and different models have been proposed to explain the physical origin within the frame of either a magnetar model or a fallback disk system. Using data from Suzaku and INTEGRAL, we study the soft and hard X-ray spectra of four AXPs/SGRs: 1RXS J170849-400910, 1E 1547.0-5408, SGR 1806-20 and SGR 0501+4516. It is found that the spectra could be well reproduced by the bulk-motion Comptonization (BMC) process as was first suggested by Trümper et al., showing that the accretion scenario could be compatible with X-ray emission from AXPs/SGRs. Simulated results from the Hard X-ray Modulation Telescope using the BMC model show that the spectra would have discrepancies from the power-law, especially the cutoff at ˜200 keV. Thus future observations will allow researchers to distinguish different models of the hard X-ray emission and will help us understand the nature of AXPs/SGRs. Supported by the National Natural Science Foundation of China.

X-ray crystallography

NASA Technical Reports Server (NTRS)

2001-01-01

X-rays diffracted from a well-ordered protein crystal create sharp patterns of scattered light on film. A computer can use these patterns to generate a model of a protein molecule. To analyze the selected crystal, an X-ray crystallographer shines X-rays through the crystal. Unlike a single dental X-ray, which produces a shadow image of a tooth, these X-rays have to be taken many times from different angles to produce a pattern from the scattered light, a map of the intensity of the X-rays after they diffract through the crystal. The X-rays bounce off the electron clouds that form the outer structure of each atom. A flawed crystal will yield a blurry pattern; a well-ordered protein crystal yields a series of sharp diffraction patterns. From these patterns, researchers build an electron density map. With powerful computers and a lot of calculations, scientists can use the electron density patterns to determine the structure of the protein and make a computer-generated model of the structure. The models let researchers improve their understanding of how the protein functions. They also allow scientists to look for receptor sites and active areas that control a protein's function and role in the progress of diseases. From there, pharmaceutical researchers can design molecules that fit the active site, much like a key and lock, so that the protein is locked without affecting the rest of the body. This is called structure-based drug design.

Finding a 24 Day Orbital Period for the X-Ray Binary 1A 1118-616

NASA Technical Reports Server (NTRS)

Staubert, R.; Pottschmidt, K.; Doroshenko, V.; Wilms, J.; Suchy, S.; Rothschild, R.; Santangelo, A.

2010-01-01

We report the first determination of the binary period and the orbital ephemeris of the Be X-ray binary containing the pulsar IA 1118-616 (35 years after the discovery of the source). The orbital period is found to be P(sub orb) = 24.0+/-0.4 days. The source was observed by RXTE during its last big X-ray outburst in January 2009, peaking at MJD 54845.4. This outburst was sampled by taking short observations every few days, covering an elapsed time comparable to the orbital period. Using the phase connection technique, pulse arrival time delays could be measured and an orbital solution determined. The data are consistent with a circular orbit, the time of 90 degrees longitude was found to be T,/2 = MJD 54845.37(10), coincident with the peak X-ray flux.

Vector optical activity in the Weyl semimetal TaAs

DOE PAGES

Norman, M. R.

2015-12-15

Here, it is shown that the Weyl semimetal TaAs can have a significant polar vector contribution to its optical activity. This is quantified by ab initio calculations of the resonant x-ray diffraction at the Ta L1 edge. For the Bragg vector (400), this polar vector contribution to the circular intensity differential between left and right polarized x-rays is predicted to be comparable to that arising from linear dichroism. Implications this result has in regards to optical effects predicted for topological Weyl semimetals are discussed.

Enhancement of the Co magnetic moment in bcc Co1-xMnx on MgO

NASA Astrophysics Data System (ADS)

Snow, Ryan; Bhatkar, Harsh; N'diaye, Alpha; Arenholz, Elke; Idzerda, Yves; Montana State University Team; Lawrence Berkeley National Laboratries Team

Using X-ray absorption spectroscopy (XAS) and X-ray magnetic circular dichroism (MCD), we show that the elemental Co moment for MBE grown thin films of bcc Co1-xMnx grown on MgO(001) is enhanced by 40% to a maximum value of 2.1 μB at x =0.24. The net Mn moment is found to align parallel with Co for all concentrations and remains roughly constant until x =0.3, then drops steadily, up to x =0.7, where the total moment of the film abruptly collapses to zero. Using a low-concentration Mn moment of 3.0 μB, the average magnetization lies directly on the Slater-Pauling (SP) curve for concentrations up to about x =.25, where it reaches a maximum moment of 2.3 μB /atom. This peak is slightly shifted and the slope is steeper on the high-Mn concentration side of the peak relative to the standard SP curve. This is in stark contrast to the fcc CoMn and hcp CoCr bulk behavior which shows only a rapid total moment reduction with Mn concentration. This material is based upon work supported by the National Science Foundation under Grant ECCS-1542210. The Advanced Light Source is supported by the Director, Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy under Con.

The Advanced X-Ray Astrophysics Facility. Observing the Universe in X-Rays

NASA Technical Reports Server (NTRS)

Neal, V.

1984-01-01

An overview of the Advanced X ray Astronophysics Facility (AXAF) program is presented. Beginning with a brief introduction to X ray astrophysics, the AXAF observatory is described including the onboard instrumentation and system capabilities. Possible X ray sources suitable for AXAF observation are identified and defined.

The Mapping X-ray Fluorescence Spectrometer (MapX)

NASA Astrophysics Data System (ADS)

Sarrazin, P.; Blake, D. F.; Marchis, F.; Bristow, T.; Thompson, K.

2017-12-01

Many planetary surface processes leave traces of their actions as features in the size range 10s to 100s of microns. The Mapping X-ray Fluorescence Spectrometer (MapX) will provide elemental imaging at 100 micron spatial resolution, yielding elemental chemistry at a scale where many relict physical, chemical, or biological features can be imaged and interpreted in ancient rocks on planetary bodies and planetesimals. MapX is an arm-based instrument positioned on a rock or regolith with touch sensors. During an analysis, an X-ray source (tube or radioisotope) bombards the sample with X-rays or alpha-particles / gamma-rays, resulting in sample X-ray Fluorescence (XRF). X-rays emitted in the direction of an X-ray sensitive CCD imager pass through a 1:1 focusing lens (X-ray micro-pore Optic (MPO)) that projects a spatially resolved image of the X-rays onto the CCD. The CCD is operated in single photon counting mode so that the energies and positions of individual X-ray photons are recorded. In a single analysis, several thousand frames are both stored and processed in real-time. Higher level data products include single-element maps with a lateral spatial resolution of 100 microns and quantitative XRF spectra from ground- or instrument- selected Regions of Interest (ROI). XRF spectra from ROI are compared with known rock and mineral compositions to extrapolate the data to rock types and putative mineralogies. When applied to airless bodies and implemented with an appropriate radioisotope source for alpha-particle excitation, MapX will be able to analyze biogenic elements C, N, O, P, S, in addition to the cations of the rock-forming elements >Na, accessible with either X-ray or gamma-ray excitation. The MapX concept has been demonstrated with a series of lab-based prototypes and is currently under refinement and TRL maturation.

Applications of synchrotron-based spectroscopic techniques in studying nucleic acids and nucleic acid-functionalized nanomaterials

PubMed Central

Wu, Peiwen; Yu, Yang; McGhee, Claire E.; Tan, Li Huey

2014-01-01

In this review, we summarize recent progresses in the application of synchrotron-based spectroscopic techniques for nucleic acid research that takes advantage of high-flux and high-brilliance electromagnetic radiation from synchrotron sources. The first section of the review focuses on the characterization of the structure and folding processes of nucleic acids using different types of synchrotron-based spectroscopies, such as X-ray absorption spectroscopy, X-ray emission spectroscopy, X-ray photoelectron spectroscopy, synchrotron radiation circular dichroism, X-ray footprinting and small-angle X-ray scattering. In the second section, the characterization of nucleic acid-based nanostructures, nucleic acid-functionalized nanomaterials and nucleic acid-lipid interactions using these spectroscopic techniques is summarized. Insights gained from these studies are described and future directions of this field are also discussed. PMID:25205057

Applications of synchrotron-based spectroscopic techniques in studying nucleic acids and nucleic acid-functionalized nanomaterials

DOE PAGES

Wu, Peiwen; Yu, Yang; McGhee, Claire E.; ...

2014-09-10

In this paper, we summarize recent progress in the application of synchrotron-based spectroscopic techniques for nucleic acid research that takes advantage of high-flux and high-brilliance electromagnetic radiation from synchrotron sources. The first section of the review focuses on the characterization of the structure and folding processes of nucleic acids using different types of synchrotron-based spectroscopies, such as X-ray absorption spectroscopy, X-ray emission spectroscopy, X-ray photoelectron spectroscopy, synchrotron radiation circular dichroism, X-ray footprinting and small-angle X-ray scattering. In the second section, the characterization of nucleic acid-based nanostructures, nucleic acid-functionalized nanomaterials and nucleic acid-lipid interactions using these spectroscopic techniques is summarized. Insightsmore » gained from these studies are described and future directions of this field are also discussed.« less

Cosmic x ray physics

NASA Technical Reports Server (NTRS)

Mccammon, Dan; Cox, D. P.; Kraushaar, W. L.; Sanders, W. T.

1990-01-01

The annual progress report on Cosmic X Ray Physics is presented. Topics studied include: the soft x ray background, proportional counter and filter calibrations, the new sounding rocket payload: X Ray Calorimeter, and theoretical studies.

Focusing X-Ray Telescopes

NASA Technical Reports Server (NTRS)

O'Dell, Stephen; Brissenden, Roger; Davis, William; Elsner, Ronald; Elvis, Martin; Freeman, Mark; Gaetz, Terrance; Gorenstein, Paul; Gubarev, Mikhall; Jerlus, Diab;

Cosmic x ray physics

NASA Technical Reports Server (NTRS)

Mccammon, Dan; Cox, D. P.; Kraushaar, W. L.; Sanders, W. T.

1991-01-01

The annual progress report on Cosmic X Ray Physics for the period 1 Jan. to 31 Dec. 1990 is presented. Topics studied include: soft x ray background, new sounding rocket payload: x ray calorimeter, and theoretical studies.

The Maximal C³ Self-Complementary Trinucleotide Circular Code X in Genes of Bacteria, Archaea, Eukaryotes, Plasmids and Viruses.

PubMed

Michel, Christian J

2017-04-18

In 1996, a set X of 20 trinucleotides was identified in genes of both prokaryotes and eukaryotes which has on average the highest occurrence in reading frame compared to its two shifted frames. Furthermore, this set X has an interesting mathematical property as X is a maximal C 3 self-complementary trinucleotide circular code. In 2015, by quantifying the inspection approach used in 1996, the circular code X was confirmed in the genes of bacteria and eukaryotes and was also identified in the genes of plasmids and viruses. The method was based on the preferential occurrence of trinucleotides among the three frames at the gene population level. We extend here this definition at the gene level. This new statistical approach considers all the genes, i.e., of large and small lengths, with the same weight for searching the circular code X . As a consequence, the concept of circular code, in particular the reading frame retrieval, is directly associated to each gene. At the gene level, the circular code X is strengthened in the genes of bacteria, eukaryotes, plasmids, and viruses, and is now also identified in the genes of archaea. The genes of mitochondria and chloroplasts contain a subset of the circular code X . Finally, by studying viral genes, the circular code X was found in DNA genomes, RNA genomes, double-stranded genomes, and single-stranded genomes.

X-ray lasers

NASA Astrophysics Data System (ADS)

Elton, Raymond C.

Theoretical and practical aspects of X-ray lasers are discussed in an introduction emphasizing recent advances. Chapters are devoted to the unique optical properties of the X-ray spectral region, the principles of short-wavelength lasers, pumping by exciting plasma ions, pumping by electron capture into excited ionic states, pumping by ionization of atoms and ions, and alternative approaches. The potential scientific, technical, biological, and medical applications of X-ray lasers are briefly characterized.

The superslow pulsation X-ray pulsars in high mass X-ray binaries

NASA Astrophysics Data System (ADS)

Wang, Wei

2013-03-01

There exists a special class of X-ray pulsars that exhibit very slow pulsation of P spin > 1000 s in the high mass X-ray binaries (HMXBs). We have studied the temporal and spectral properties of these superslow pulsation neutron star binaries in hard X-ray bands with INTEGRAL observations. Long-term monitoring observations find spin period evolution of two sources: spin-down trend for 4U 2206+54 (P spin ~ 5560 s with Ṗ spin ~ 4.9 × 10-7 s s-1) and long-term spin-up trend for 2S 0114+65 (P spin ~ 9600 s with Ṗ spin ~ -1 × 10-6 s s-1) in the last 20 years. A Be X-ray transient, SXP 1062 (P spin ~ 1062 s), also showed a fast spin-down rate of Ṗ spin ~ 3 × 10-6 s s-1 during an outburst. These superslow pulsation neutron stars cannot be produced in the standard X-ray binary evolution model unless the neutron star has a much stronger surface magnetic field (B > 1014 G). The physical origin of the superslow spin period is still unclear. The possible origin and evolution channels of the superslow pulsation X-ray pulsars are discussed. Superslow pulsation X-ray pulsars could be younger X-ray binary systems, still in the fast evolution phase preceding the final equilibrium state. Alternatively, they could be a new class of neutron star system - accreting magnetars.

Miniature x-ray source

DOEpatents

Trebes, James E.; Stone, Gary F.; Bell, Perry M.; Robinson, Ronald B.; Chornenky, Victor I.

2002-01-01

A miniature x-ray source capable of producing broad spectrum x-ray emission over a wide range of x-ray energies. The miniature x-ray source comprises a compact vacuum tube assembly containing a cathode, an anode, a high voltage feedthru for delivering high voltage to the anode, a getter for maintaining high vacuum, a connection for an initial vacuum pump down and crimp-off, and a high voltage connection for attaching a compact high voltage cable to the high voltage feedthru. At least a portion of the vacuum tube wall is highly x-ray transparent and made, for example, from boron nitride. The compact size and potential for remote operation allows the x-ray source, for example, to be placed adjacent to a material sample undergoing analysis or in proximity to the region to be treated for medical applications.

Wide-area phase-contrast X-ray imaging using large X-ray interferometers

NASA Astrophysics Data System (ADS)

Momose, Atsushi; Takeda, Tohoru; Yoneyama, Akio; Koyama, Ichiro; Itai, Yuji

2001-07-01

Large X-ray interferometers are developed for phase-contrast X-ray imaging aiming at medical applications. A monolithic X-ray interferometer and a separate one are studied, and currently a 25 mm×20 mm view area can be generated. This paper describes the strategy of our research program and some recent developments.

Cooperative use of VCD and XRD for the determination of tetrahydrobenzoisoquinolines absolute configuration: a reliable proof of memory of chirality and retention of configuration in enediyne rearrangements.

PubMed

Mondal, Shovan; Naubron, Jean-Valère; Campolo, Damien; Giorgi, Michel; Bertrand, Michéle P; Nechab, Malek

2013-12-01

The absolute configurations (AC) of azaheterocylic compounds resulting from the cascade rearrangement of enediynes involving only light atoms were unambiguously assigned by the joint use of vibrational circular dichroism (VCD) and copper radiation single crystal X-ray diffraction (XRD). These AC determinations proved that the rearrangements of enediynes proceeded with memory of chirality and retention of configuration. © 2013 Wiley Periodicals, Inc.

High-Energy Vacuum Birefringence and Dichroism in an Ultrastrong Laser Field

NASA Astrophysics Data System (ADS)

Bragin, Sergey; Meuren, Sebastian; Keitel, Christoph H.; Di Piazza, Antonino

2017-12-01

A long-standing prediction of quantum electrodynamics, yet to be experimentally observed, is the interaction between real photons in vacuum. As a consequence of this interaction, the vacuum is expected to become birefringent and dichroic if a strong laser field polarizes its virtual particle-antiparticle dipoles. Here, we derive how a generally polarized probe photon beam is influenced by both vacuum birefringence and dichroism in a strong linearly polarized plane-wave laser field. Furthermore, we consider an experimental scheme to measure these effects in the nonperturbative high-energy regime, where the Euler-Heisenberg approximation breaks down. By employing circularly polarized high-energy probe photons, as opposed to the conventionally considered linearly polarized ones, the feasibility of quantitatively confirming the prediction of nonlinear QED for vacuum birefringence at the 5 σ confidence level on the time scale of a few days is demonstrated for upcoming 10 PW laser systems. Finally, dichroism and anomalous dispersion in vacuum are shown to be accessible at these facilities.

X-Pinch And Its Applications In X-ray Radiograph

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zou Xiaobing; Wang Xinxin; Liu Rui

2009-07-07

An X-pinch device and the related diagnostics of x-ray emission from X-pinch were briefly described. The time-resolved x-ray measurements with photoconducting diodes show that the x-ray pulse usually consists of two subnanosecond peaks with a time interval of about 0.5 ns. Being consistent with these two peaks of the x-ray pulse, two point x-ray sources of size ranging from 100 mum to 5 mum and depending on cut-off x-ray photon energy were usually observed on the pinhole pictures. The x-pinch was used as x-ray source for backlighting of the electrical explosion of single wire and the evolution of X-pinch, andmore » for phase-contrast imaging of soft biological objects such as a small shrimp and a mosquito.« less

Evolution of X-ray astronomy

NASA Technical Reports Server (NTRS)

Rossj, B.

1981-01-01

The evolution of X-ray astronomy up to the launching of the Einstein observatory is presented. The evaluation proceeded through the following major steps: (1) discovery of an extrasolar X-ray source, Sco X-1, orders of magnitude stronger than astronomers believed might exist; (2) identification of a strong X-ray source with the Crab Nebula; (3) identification of Sco X-1 with a faint, peculiar optical object; (4) demonstration that X-ray stars are binary systems, each consisting of a collapsed object accreting matter from an ordinary star; (5) discovery of X-ray bursts; (6) discovery of exceedingly strong X-ray emission from active galaxies, quasars and clusters of galaxies; (7) demonstration that the principal X-ray source is a hot gas filling the space between galaxies.

Optical/UV-to-X-Ray Echoes from the Tidal Disruption Flare ASASSN-14li

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pasham, Dheeraj R.; Sadowski, Aleksander; Cenko, S. Bradley

We carried out the first multi-wavelength (optical/UV and X-ray) photometric reverberation mapping of a tidal disruption flare (TDF) ASASSN-14li. We find that its X-ray variations are correlated with and lag the optical/UV fluctuations by 32 ± 4 days. Based on the direction and the magnitude of the X-ray time lag, we rule out X-ray reprocessing and direct emission from a standard circular thin disk as the dominant source of its optical/UV emission. The lag magnitude also rules out an AGN disk-driven instability as the origin of ASASSN-14li and thus strongly supports the tidal disruption picture for this event and similarmore » objects. We suggest that the majority of the optical/UV emission likely originates from debris stream self-interactions. Perturbations at the self-interaction sites produce optical/UV variability and travel down to the black hole where they modulate the X-rays. The time lag between the optical/UV and the X-rays variations thus correspond to the time taken by these fluctuations to travel from the self-interaction site to close to the black hole. We further discuss these time lags within the context of the three variants of the self-interaction model. High-cadence monitoring observations of future TDFs will be sensitive enough to detect these echoes and would allow us to establish the origin of optical/UV emission in TDFs in general.« less

Active x-ray optics for Generation-X, the next high resolution x-ray observatory

NASA Astrophysics Data System (ADS)

Elvis, Martin; Brissenden, R. J.; Fabbiano, G.; Schwartz, D. A.; Reid, P.; Podgorski, W.; Eisenhower, M.; Juda, M.; Phillips, J.; Cohen, L.; Wolk, S.

2006-06-01

X-rays provide one of the few bands through which we can study the epoch of reionization, when the first galaxies, black holes and stars were born. To reach the sensitivity required to image these first discrete objects in the universe needs a major advance in X-ray optics. Generation-X (Gen-X) is currently the only X-ray astronomy mission concept that addresses this goal. Gen-X aims to improve substantially on the Chandra angular resolution and to do so with substantially larger effective area. These two goals can only be met if a mirror technology can be developed that yields high angular resolution at much lower mass/unit area than the Chandra optics, matching that of Constellation-X (Con-X). We describe an approach to this goal based on active X-ray optics that correct the mid-frequency departures from an ideal Wolter optic on-orbit. We concentrate on the problems of sensing figure errors, calculating the corrections required, and applying those corrections. The time needed to make this in-flight calibration is reasonable. A laboratory version of these optics has already been developed by others and is successfully operating at synchrotron light sources. With only a moderate investment in these optics the goals of Gen-X resolution can be realized.

Development of X-ray CCD camera based X-ray micro-CT system

NASA Astrophysics Data System (ADS)

Sarkar, Partha S.; Ray, N. K.; Pal, Manoj K.; Baribaddala, Ravi; Agrawal, Ashish; Kashyap, Y.; Sinha, A.; Gadkari, S. C.

2017-02-01

Availability of microfocus X-ray sources and high resolution X-ray area detectors has made it possible for high resolution microtomography studies to be performed outside the purview of synchrotron. In this paper, we present the work towards the use of an external shutter on a high resolution microtomography system using X-ray CCD camera as a detector. During micro computed tomography experiments, the X-ray source is continuously ON and owing to the readout mechanism of the CCD detector electronics, the detector registers photons reaching it during the read-out period too. This introduces a shadow like pattern in the image known as smear whose direction is defined by the vertical shift register. To resolve this issue, the developed system has been incorporated with a synchronized shutter just in front of the X-ray source. This is positioned in the X-ray beam path during the image readout period and out of the beam path during the image acquisition period. This technique has resulted in improved data quality and hence the same is reflected in the reconstructed images.

Chandra X-ray Observatory - NASA's flagship X-ray telescope

Science.gov Websites

astronomy, taking its place in the fleet of "Great Observatories." Who we are NASA's Chandra X-ray astronomy, distances are measured in units of light years, where one light year is the distance that light gravity? The answer is still out there. By studying clusters of galaxies, X-ray astronomy is tackling this

Diffraction leveraged modulation of X-ray pulses using MEMS-based X-ray optics

DOEpatents

Lopez, Daniel; Shenoy, Gopal; Wang, Jin; Walko, Donald A.; Jung, Il-Woong; Mukhopadhyay, Deepkishore

2016-08-09

A method and apparatus are provided for implementing Bragg-diffraction leveraged modulation of X-ray pulses using MicroElectroMechanical systems (MEMS) based diffractive optics. An oscillating crystalline MEMS device generates a controllable time-window for diffraction of the incident X-ray radiation. The Bragg-diffraction leveraged modulation of X-ray pulses includes isolating a particular pulse, spatially separating individual pulses, and spreading a single pulse from an X-ray pulse-train.

Two rare-class tricyclic diterpenes with antitubercular activity from the Caribbean sponge Svenzea flava. Application of vibrational circular dichroism spectroscopy for determining absolute configuration.

PubMed

Avilés, Edward; Rodríguez, Abimael D; Vicente, Jan

2013-11-15

Two new natural products, 3 and 4, and their predecessor 7-isocyanoisoneoamphilecta-1(14),15-diene (2), of the rare isoneoamphilectane class of marine diterpenes, along with the known amphilectane diterpenes 6-8, were isolated from the n-hexane extract of the marine sponge Svenzea flava collected at Great Inagua Island, Bahamas. The molecular structures of compounds 3 and 4 were established by spectroscopic (1D/2D NMR, IR, UV, HRMS) methods and confirmed by a series of chemical correlation studies. In a first ever case study of the assignment of the absolute configuration of a molecule based on the isoneoamphilectane carbon skeleton, the absolute configuration of compound 5 was established as 3S,4R,7S,8S,11R,12S,13R by application of vibrational circular dichroism (VCD). In vitro anti-TB screenings revealed that metabolites 2-4 and, in particular, semisynthetic analogue 5, are strong growth inhibitors of Mycobacterium tuberculosis H37Rv.

13.1 micrometers hard X-ray focusing by a new type monocapillary X-ray optic designed for common laboratory X-ray source

NASA Astrophysics Data System (ADS)

Sun, Xuepeng; zhang, Xiaoyun; Zhu, Yu; Wang, Yabing; Shang, Hongzhong; Zhang, Fengshou; Liu, Zhiguo; Sun, Tianxi

2018-04-01

A new type of monocapillary X-ray optic, called 'two bounces monocapillary X-ray optics' (TBMXO), is proposed for generating a small focal spot with high power-density gain for micro X-ray analysis, using a common laboratory X-ray source. TBMXO is consists of two parts: an ellipsoidal part and a tapered part. Before experimental testing, the TBMXO was simulated by the ray tracing method in MATLAB. The simulated results predicted that the proposed TBMXO would produce a smaller focal spot with higher power-density gain than the ellipsoidal monocapillary X-ray optic (EMXO). In the experiment, the TBMXO performance was tested by both an optical device and a Cu target X-ray tube with focal spot of 100 μm. The results indicated that the TBMXO had a slope error of 57.6 μrad and a 13.1 μm focal spot and a 1360 gain in power density were obtained.

A Comparison of the Extra Nuclear X-ray and Radio Features in M87

NASA Technical Reports Server (NTRS)

Harris, D. E.; Owen, F.; Biretta, J. A.; Junor, W.

2000-01-01

ROSAT High Resolution Imager (HRI) data from eight observations have been co-added to obtain an effective exposure of 230 ksec. We have identified a number of features and regions with excess X-ray brightness over that from a circularly symmetric model of the well known hot gas component. A prominent 'spur' extends 4feet from the vicinity of knot A towards the south-west. The brightness to the south and east of this spur is significantly higher than that to the north and west. Excess brightness is also found to the East of the nucleus, with a local maximum centered on the eastern radio lobe 3 feet from the core. There are two well known relationships between radio and X-ray emission for radio galaxies in clusters: coincidence of emissions because the X-rays come from inverse Compton or synchrotron processes; and anti-coincidence caused by exclusion of hot gas from radio entities. We present a radio/X-ray comparison to determine if either of these relationships can be isolated in M87. The greatest obstacle we face is the unknown projection which affects both bands.

X-Ray Exam: Hip

MedlinePlus

... Staying Safe Videos for Educators Search English Español X-Ray Exam: Hip KidsHealth / For Parents / X-Ray Exam: Hip What's in this article? What ... Have Questions Print What It Is A hip X-ray is a safe and painless test that ...

X-Ray Exam: Forearm

MedlinePlus

... Staying Safe Videos for Educators Search English Español X-Ray Exam: Forearm KidsHealth / For Parents / X-Ray Exam: Forearm What's in this article? What ... Have Questions Print What It Is A forearm X-ray is a safe and painless test that ...

X-Ray Exam: Ankle

MedlinePlus

... Staying Safe Videos for Educators Search English Español X-Ray Exam: Ankle KidsHealth / For Parents / X-Ray Exam: Ankle What's in this article? What ... Have Questions Print What It Is An ankle X-ray is a safe and painless test that ...

X-Ray Exam: Foot

MedlinePlus

... Staying Safe Videos for Educators Search English Español X-Ray Exam: Foot KidsHealth / For Parents / X-Ray Exam: Foot What's in this article? What ... Have Questions Print What It Is A foot X-ray is a safe and painless test that ...

X-Ray Exam: Wrist

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... Staying Safe Videos for Educators Search English Español X-Ray Exam: Wrist KidsHealth / For Parents / X-Ray Exam: Wrist What's in this article? What ... Have Questions Print What It Is A wrist X-ray is a safe and painless test that ...

X-Ray Exam: Finger

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... Staying Safe Videos for Educators Search English Español X-Ray Exam: Finger KidsHealth / For Parents / X-Ray Exam: Finger What's in this article? What ... Have Questions Print What It Is A finger X-ray is a safe and painless test that ...

X-Ray Exam: Pelvis

MedlinePlus

... Staying Safe Videos for Educators Search English Español X-Ray Exam: Pelvis KidsHealth / For Parents / X-Ray Exam: Pelvis What's in this article? What ... Have Questions Print What It Is A pelvis X-ray is a safe and painless test that ...

X-ray based extensometry

NASA Technical Reports Server (NTRS)

Jordan, E. H.; Pease, D. M.

1988-01-01

A totally new method of extensometry using an X-ray beam was proposed. The intent of the method is to provide a non-contacting technique that is immune to problems associated with density variations in gaseous environments that plague optical methods. X-rays are virtually unrefractable even by solids. The new method utilizes X-ray induced X-ray fluorescence or X-ray induced optical fluorescence of targets that have melting temperatures of over 3000 F. Many different variations of the basic approaches are possible. In the year completed, preliminary experiments were completed which strongly suggest that the method is feasible. The X-ray induced optical fluorescence method appears to be limited to temperatures below roughly 1600 F because of the overwhelming thermal optical radiation. The X-ray induced X-ray fluorescence scheme appears feasible up to very high temperatures. In this system there will be an unknown tradeoff between frequency response, cost, and accuracy. The exact tradeoff can only be estimated. It appears that for thermomechanical tests with cycle times on the order of minutes a very reasonable system may be feasible. The intended applications involve very high temperatures in both materials testing and monitoring component testing. Gas turbine engines, rocket engines, and hypersonic vehicles (NASP) all involve measurement needs that could partially be met by the proposed technology.

Applications of phase-contrast x-ray imaging to medicine using an x-ray interferometer

NASA Astrophysics Data System (ADS)

Momose, Atsushi; Yoneyama, Akio; Takeda, Tohoru; Itai, Yuji; Tu, Jinhong; Hirano, Keiichi

1999-10-01

We are investigating possible medical applications of phase- contrast X-ray imaging using an X-ray interferometer. This paper introduces the strategy of the research project and the present status. The main subject is to broaden the observation area to enable in vivo observation. For this purpose, large X-ray interferometers were developed, and 2.5 cm X 1.5 cm interference patterns were generated using synchrotron X-rays. An improvement of the spatial resolution is also included in the project, and an X-ray interferometer designed for high-resolution phase-contrast X-ray imaging was fabricated and tested. In parallel with the instrumental developments, various soft tissues are observed by phase- contrast X-ray CT to find correspondence between the generated contrast and our histological knowledge. The observation done so far suggests that cancerous tissues are differentiated from normal tissues and that blood can produce phase contrast. Furthermore, this project includes exploring materials that modulate phase contrast for selective imaging.

An X-ray halo around Cassiopeia A

NASA Astrophysics Data System (ADS)

Stewart, G. C.; Fabian, A. C.; Seward, F. D.

The large-scale X-ray emission of Cas A is characterized, and mechanisms are proposed to explain it. The Einstein HRI image of Murray et al. (1979) is binned into 16-arcsec pixels, a point-spread function based on the 2.04-keV monochromatic Zr source is applied, and the data are modeled as a series of circularly symmetric rings of emission. A significant excess extending to a radius of 6 arcmin (roughly the size of the optical H II region) is found to have a total 0.5-3-keV luminosity of about 5 x 10 to the 34th erg/s, or about 2 percent of the total luminosity of Cas A, which is assumed to lie at a distance of 3 kpc. Thermal bremsstrahlung, synchrotron radiation, and dust scattering of the main-shell emission are examined and found to be plausible emission mechanisms; further observations are required to identify the one active in Cas A.

X-ray nova and LMXB V404 Cyg in rare outburst

NASA Astrophysics Data System (ADS)

Waagen, Elizabeth O.

2015-06-01

V404 Cyg, an X-ray nova and a low mass X-ray binary (LMXB) with black hole component, is undergoing its first reported X-ray and optical outburst since 1989. Large scale, rapid variations are being reported in wavelengths from X-ray to radio by professional and amateur astronomers worldwide. Satellite and ground-based observations have been and are continuing to be made by many members of the professional community, including S. D. Barthelmy et al. (GCN Circular 17929, 15 June 2015, Swift BAT initial detection); H. Negoro et al. (ATel #7646, 17 Jun 2015); E. Kuulkers et al. (ATel #7647, 17 June 2015, Swift observations); K. Gazeas et al. (ATel #7650, 17 June 2015, optical photometry); R. M. Wagner et al. (ATel #7655, 18 June, optical spectroscopy); K. Mooley et al. (ATel #7658, 18 June, radio observations). T. Munoz-Darias et al. report P Cyg profiles were seen on 18 Jun 2015 (ATel #7659). They note that P-Cyg profiles were also observed during the 1989 outburst (Casares et al. 1991, MNRAS, 250, 712), and that V404 Cyg is so far the only black hole X-ray transient that has shown this phenomenology. Observations in all bands are requested. Filtered observations are preferred. Please use a cadence as high as possible while obtaining a suitable s/n. If spectroscopy is possible with your equipment, it is requested. Finder charts with sequence may be created using the AAVSO Variable Star Plotter (https://www.aavso.org/vsp). Observations should be submitted to the AAVSO International Database. Precise observing instructions and other details are given in the full Alert Notice.

Frontiers of X-Ray Astronomy

NASA Astrophysics Data System (ADS)

Fabian, Andrew C.; Pounds, Kenneth A.; Blandford, Roger D.

2004-07-01

Preface; 1. Forty years on from Aerobee 150: a personal perspective K. Pounds; 2. X-ray spectroscopy of astrophysical plasmas S. M. Kahn, E. Behar, A. Kinkhabwala and D. W. Savin; 3. X-rays from stars M. Gudel; 4. X-ray observations of accreting white-dwarf systems M. Cropper, G. Ramsay, C. Hellier, K. Mukai, C. Mauche and D. Pandel; 5. Accretion flows in X-ray binaries C. Done; 6. Recent X-ray observations of supernova remnants C. R. Canizares; 7. Luminous X-ray sources in spiral and star-forming galaxies M. Ward; 8. Cosmological constraints from Chandra observations of galaxy clusters S. W. Allen; 9. Clusters of galaxies: a cosmological probe R. Mushotzky; 10. Obscured active galactic nuclei: the hidden side of the X-ray Universe G. Matt; 11. The Chandra Deep Field-North Survey and the cosmic X-ray background W. N. Brandt, D. M. Alexander, F. E. Bauer and A. E. Hornschemeier; 12. Hunting the first black holes G. Hasinger; 13. X-ray astronomy in the new millennium: a summary R. D. Blandford.

X-ray laser microscope apparatus

DOEpatents

Suckewer, Szymon; DiCicco, Darrell S.; Hirschberg, Joseph G.; Meixler, Lewis D.; Sathre, Robert; Skinner, Charles H.

1990-01-01

A microscope consisting of an x-ray contact microscope and an optical microscope. The optical, phase contrast, microscope is used to align a target with respect to a source of soft x-rays. The source of soft x-rays preferably comprises an x-ray laser but could comprise a synchrotron or other pulse source of x-rays. Transparent resist material is used to support the target. The optical microscope is located on the opposite side of the transparent resist material from the target and is employed to align the target with respect to the anticipated soft x-ray laser beam. After alignment with the use of the optical microscope, the target is exposed to the soft x-ray laser beam. The x-ray sensitive transparent resist material whose chemical bonds are altered by the x-ray beam passing through the target mater GOVERNMENT LICENSE RIGHTS This invention was made with government support under Contract No. De-FG02-86ER13609 awarded by the Department of Energy. The Government has certain rights in this invention.

Compound refractive X-ray lens

DOEpatents

Nygren, David R.; Cahn, Robert; Cederstrom, Bjorn; Danielsson, Mats; Vestlund, Jonas

2000-01-01

An apparatus and method for focusing X-rays. In one embodiment, his invention is a commercial-grade compound refractive X-ray lens. The commercial-grade compound refractive X-ray lens includes a volume of low-Z material. The volume of low-Z material has a first surface which is adapted to receive X-rays of commercially-applicable power emitted from a commercial-grade X-ray source. The volume of low-Z material also has a second surface from which emerge the X-rays of commercially-applicable power which were received at the first surface. Additionally, the commercial-grade compound refractive X-ray lens includes a plurality of openings which are disposed between the first surface and the second surface. The plurality of openings are oriented such that the X-rays of commercially-applicable power which are received at the first surface, pass through the volume of low-Z material and through the plurality openings. In so doing, the X-rays which emerge from the second surface are refracted to a focal point.

Cosmic X-ray physics

NASA Technical Reports Server (NTRS)

Mccammon, D.; Cox, D. P.; Kraushaar, W. L.; Sanders, W. T.

1985-01-01

A progress report of research activities carried out in the area of cosmic X-ray physics is presented. The Diffuse X-ray Spectrometer DXS which has been flown twice as a rocket payload is described. The observation times proved to be too small for meaningful X-ray data to be obtained. Data collection and reduction activities from the Ultra-Soft X-ray background (UXT) instrument are described. UXT consists of three mechanically-collimated X-ray gas proportional counters with window/filter combinations which allow measurements in three energy bands, Be (80-110 eV), B (90-187 eV), and O (e84-532 eV). The Be band measurements provide an important constraint on local absorption of X-rays from the hot component of the local interstellar medium. Work has also continued on the development of a calorimetric detector for high-resolution spectroscopy in the 0.1 keV - 8keV energy range.

Aromatic Cluster Sensor of Protein Folding: Near-UV Electronic Circular Dichroism Bands Assigned to Fold Compactness.

PubMed

Farkas, Viktor; Jákli, Imre; Tóth, Gábor K; Perczel, András

2016-09-19

Both far- and near-UV electronic circular dichroism (ECD) spectra have bands sensitive to thermal unfolding of Trp and Tyr residues containing proteins. Beside spectral changes at 222 nm reporting secondary structural variations (far-UV range), L b bands (near-UV range) are applicable as 3D-fold sensors of protein's core structure. In this study we show that both L b (Tyr) and L b (Trp) ECD bands could be used as sensors of fold compactness. ECD is a relative method and thus requires NMR referencing and cross-validation, also provided here. The ensemble of 204 ECD spectra of Trp-cage miniproteins is analysed as a training set for "calibrating" Trp↔Tyr folded systems of known NMR structure. While in the far-UV ECD spectra changes are linear as a function of the temperature, near-UV ECD data indicate a non-linear and thus, cooperative unfolding mechanism of these proteins. Ensemble of ECD spectra deconvoluted gives both conformational weights and insight to a protein folding↔unfolding mechanism. We found that the L b 293 band is reporting on the 3D-structure compactness. In addition, the pure near-UV ECD spectrum of the unfolded state is described here for the first time. Thus, ECD folding information now validated can be applied with confidence in a large thermal window (5≤T≤85 °C) compared to NMR for studying the unfolding of Trp↔Tyr residue pairs. In conclusion, folding propensities of important proteins (RNA polymerase II, ubiquitin protein ligase, tryptase-inhibitor etc.) can now be analysed with higher confidence. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

X-ray (image)

MedlinePlus

X-rays are a form of electromagnetic radiation, just like visible light. Structures that are dense (such as bone) will block most of the x-ray particles, and will appear white. Metal and contrast media ( ...

X-Ray Lasers

ERIC Educational Resources Information Center

Chapline, George; Wood, Lowell

1975-01-01

Outlines the prospects of generating coherent x rays using high-power lasers and indentifies problem areas in their development. Indicates possible applications for coherent x rays in the fields of chemistry, biology, and crystallography. (GS)

Nonlinear X-Ray and Auger Spectroscopy at X-Ray Free-Electron Laser Sources

NASA Astrophysics Data System (ADS)

Rohringer, Nina

2015-05-01

X-ray free-electron lasers (XFELs) open the pathway to transfer non-linear spectroscopic techniques to the x-ray domain. A promising all x-ray pump probe technique is based on coherent stimulated electronic x-ray Raman scattering, which was recently demonstrated in atomic neon. By tuning the XFEL pulse to core-excited resonances, a few seed photons in the spectral tail of the XFEL pulse drive an avalanche of resonant inelastic x-ray scattering events, resulting in exponential amplification of the scattering signal by of 6-7 orders of magnitude. Analysis of the line profile of the emitted radiation permits to demonstrate the cross over from amplified spontaneous emission to coherent stimulated resonance scattering. In combination with statistical covariance mapping, a high-resolution spectrum of the resonant inelastic scattering process can be obtained, opening the path to coherent stimulated x-ray Raman spectroscopy. An extension of these ideas to molecules and a realistic feasibility study of stimulated electronic x-ray Raman scattering in CO will be presented. Challenges to realizing stimulated electronic x-ray Raman scattering at present-day XFEL sources will be discussed, corroborated by results of a recent experiment at the LCLS XFEL. Due to the small gain cross section in molecular targets, other nonlinear spectroscopic techniques such as nonlinear Auger spectroscopy could become a powerful alternative. Theory predictions of a novel pump probe technique based on resonant nonlinear Auger spectroscopic will be discussed and the method will be compared to stimulated x-ray Raman spectroscopy.

Tunable X-ray source

DOEpatents

Boyce, James R [Williamsburg, VA

2011-02-08

A method for the production of X-ray bunches tunable in both time and energy level by generating multiple photon, X-ray, beams through the use of Thomson scattering. The method of the present invention simultaneously produces two X-ray pulses that are tunable in energy and/or time.

Introducing a New Capability at SSRL: Resonant Soft X-ray Scattering

NASA Astrophysics Data System (ADS)

Lee, Jun-Sik; Jang, Hoyoung; Lu, Donghui; Kao, Chi-Chang

Stanford Synchrotron Radiation Lightsource (SSRL) at SLAC recently developed a setup for the resonant soft x-ray scattering (RSXS). In general, the RSXS technique uniquely probes not only structural information, but also chemical specific information. This is because this technique can explore the spatial periodicities of charge, orbital, spin, and lattice with spectroscopic aspect. Moreover, the soft x-ray range is particularly relevant for a study of soft materials as it covers the K-edge of C, N, F, and O, as well as the L-edges of transition metals and M-edges of rare-earth elements. Hence, the RSXS capability has been regarded as a very powerful technique for investigating the intrinsic properties of materials such as quantum- and energy-materials. The RSXS capability at the SSRL composes of in-vacuum 4-circle diffractometer. There are also the fully motorized sample-motion manipulations. Also, the sample can be cooled down to 25 K via the liquid helium. This capability has been installed at BL 13-3, where the photon source is from elliptically polarized undulator (EPU). Covering the photon energies is from 230 eV to 1400 eV. Furthermore, this EPU system offers more degree of freedoms for controlling x-ray polarizations (linear and circular). Using the advance of controlling x-ray polarization, we can also investigate a morphology effect of local domain/grain in materials. The detailed introduction of the RSXS end-station and several results will be touched in this poster presentation.

X-Ray Diffraction Apparatus

NASA Technical Reports Server (NTRS)

Blake, David F. (Inventor); Bryson, Charles (Inventor); Freund, Friedmann (Inventor)

1996-01-01

An x-ray diffraction apparatus for use in analyzing the x-ray diffraction pattern of a sample is introduced. The apparatus includes a beam source for generating a collimated x-ray beam having one or more discrete x-ray energies, a holder for holding the sample to be analyzed in the path of the beam, and a charge-coupled device having an array of pixels for detecting, in one or more selected photon energy ranges, x-ray diffraction photons produced by irradiating such a sample with said beam. The CCD is coupled to an output unit which receives input information relating to the energies of photons striking each pixel in the CCD, and constructs the diffraction pattern of photons within a selected energy range striking the CCD.

X-ray shearing interferometer

DOEpatents

Koch, Jeffrey A [Livermore, CA

2003-07-08

An x-ray interferometer for analyzing high density plasmas and optically opaque materials includes a point-like x-ray source for providing a broadband x-ray source. The x-rays are directed through a target material and then are reflected by a high-quality ellipsoidally-bent imaging crystal to a diffraction grating disposed at 1.times. magnification. A spherically-bent imaging crystal is employed when the x-rays that are incident on the crystal surface are normal to that surface. The diffraction grating produces multiple beams which interfere with one another to produce an interference pattern which contains information about the target. A detector is disposed at the position of the image of the target produced by the interfering beams.

Abdominal x-ray

MedlinePlus

... are, or may be, pregnant. Alternative Names Abdominal film; X-ray - abdomen; Flat plate; KUB x-ray ... Guidelines Viewers & Players MedlinePlus Connect for EHRs For Developers U.S. National Library of Medicine 8600 Rockville Pike, ...

X-Ray Toolkit

DOE Office of Scientific and Technical Information (OSTI.GOV)

2015-10-20

Radiographic Image Acquisition & Processing Software for Security Markets. Used in operation of commercial x-ray scanners and manipulation of x-ray images for emergency responders including State, Local, Federal, and US Military bomb technicians and analysts.

Generation of Bright Phase-matched Circularly-polarized Extreme Ultraviolet High Harmonics

DTIC Science & Technology

2014-12-08

circularly-polarized laser pulses field-ionize a gas in a hollow - core waveguide. We use this new light source for magnetic circular dichroism...polarized with opposite helicity in a gas-filled hollow waveguide (see Supplementary Section 6 for details on the important features of this source...mJ/pulse) driving lasers are focused into a 150-µm-diameter, 2-cm-long gas-filled hollow waveguide using lenses with focal lengths of 50 cm and 75 cm

X-ray imaging performance of scintillator-filled silicon pore arrays

DOE Office of Scientific and Technical Information (OSTI.GOV)

Simon, Matthias; Engel, Klaus Juergen; Menser, Bernd

2008-03-15

The need for fine detail visibility in various applications such as dental imaging, mammography, but also neurology and cardiology, is the driver for intensive efforts in the development of new x-ray detectors. The spatial resolution of current scintillator layers is limited by optical diffusion. This limitation can be overcome by a pixelation, which prevents optical photons from crossing the interface between two neighboring pixels. In this work, an array of pores was etched in a silicon wafer with a pixel pitch of 50 {mu}m. A very high aspect ratio was achieved with wall thicknesses of 4-7 {mu}m and pore depthsmore » of about 400 {mu}m. Subsequently, the pores were filled with Tl-doped cesium iodide (CsI:Tl) as a scintillator in a special process, which includes powder melting and solidification of the CsI. From the sample geometry and x-ray absorption measurement the pore fill grade was determined to be 75%. The scintillator-filled samples have a circular active area of 16 mm diameter. They are coupled with an optical sensor binned to the same pixel pitch in order to measure the x-ray imaging performance. The x-ray sensitivity, i.e., the light output per absorbed x-ray dose, is found to be only 2.5%-4.5% of a commercial CsI-layer of similar thickness, thus very low. The efficiency of the pores to transport the generated light to the photodiode is estimated to be in the best case 6.5%. The modulation transfer function is 40% at 4 lp/mm and 10%-20% at 8 lp/mm. It is limited most likely by the optical gap between scintillator and sensor and by K-escape quanta. The detective quantum efficiency (DQE) is determined at different beam qualities and dose settings. The maximum DQE(0) is 0.28, while the x-ray absorption with the given thickness and fill factor is 0.57. High Swank noise is suspected to be the reason, mainly caused by optical scatter inside the CsI-filled pores. The results are compared to Monte Carlo simulations of the photon transport inside the pore

Indus-2 X-ray lithography beamline for X-ray optics and material science applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dhamgaye, V. P., E-mail: vishal@rrcat.gov.in; Lodha, G. S., E-mail: vishal@rrcat.gov.in

2014-04-24

X-ray lithography is an ideal technique by which high aspect ratio and high spatial resolution micro/nano structures are fabricated using X-rays from synchrotron radiation source. The technique has been used for fabricating optics (X-ray, visible and infrared), sensors and actuators, fluidics and photonics. A beamline for X-ray lithography is operational on Indus-2. The beamline offers wide lithographic window from 1-40keV photon energy and wide beam for producing microstructures in polymers upto size ∼100mm × 100mm. X-ray exposures are possible in air, vacuum and He gas environment. The air based exposures enables the X-ray irradiation of resist for lithography and alsomore » irradiation of biological and liquid samples.« less

Compact x-ray source and panel

DOEpatents

Sampayon, Stephen E [Manteca, CA

2008-02-12

A compact, self-contained x-ray source, and a compact x-ray source panel having a plurality of such x-ray sources arranged in a preferably broad-area pixelized array. Each x-ray source includes an electron source for producing an electron beam, an x-ray conversion target, and a multilayer insulator separating the electron source and the x-ray conversion target from each other. The multi-layer insulator preferably has a cylindrical configuration with a plurality of alternating insulator and conductor layers surrounding an acceleration channel leading from the electron source to the x-ray conversion target. A power source is connected to each x-ray source of the array to produce an accelerating gradient between the electron source and x-ray conversion target in any one or more of the x-ray sources independent of other x-ray sources in the array, so as to accelerate an electron beam towards the x-ray conversion target. The multilayer insulator enables relatively short separation distances between the electron source and the x-ray conversion target so that a thin panel is possible for compactness. This is due to the ability of the plurality of alternating insulator and conductor layers of the multilayer insulators to resist surface flashover when sufficiently high acceleration energies necessary for x-ray generation are supplied by the power source to the x-ray sources.

Effects of central metal ions on vibrational circular dichroism spectra of tris-(beta-diketonato)metal(III) complexes.

PubMed

Sato, Hisako; Taniguchi, Tohru; Nakahashi, Atsufumi; Monde, Kenji; Yamagishi, Akihiko

2007-08-06

Vibrational circular dichroism (VCD) spectra of a series of [M(III)(acac)3] (acac = acetylacetonato; M = Cr, Co, Ru, Rh, Ir, and Al) and [M(III)(acac)2(dbm)] (dbm = dibenzoylmethanato; M = Cr, Co, and Ru) have been investigated experimentally and/or theoretically in order to see the effect of the central metal ion on the vibrational dynamics of ligands. The optical antipodes give the mirror-imaged spectra in the region of 1700-1000 cm(-1). The remarkable effect of the central metal ion is observed experimentally on the VCD peaks due to C-O stretches (1500-1300 cm(-1)) for both [M(III)(acac)3] and [M(III)(acac)2(dbm)]. In the case of Delta-[M(III)(acac)3], for example, the order of frequency of two C-O stretches (E and A2 symmetries) is dependent on the kind of a central metal ion as follows: E (-) > A2 (+) for M = Co, Rh, and Ir, while A2 (+) > E (-) for M = Cr and Ru. In the case of Delta-[M(III)(acac)2(dbm)], the order of frequency of three C-O stretches (A, B, and B symmetries) is as follows: A (-) > B (+) > B (+) for Co(III), B (+) > A (-) > B (-) for Cr(III), and A (-) > B (+) > B (-) for Ru(III). These results imply that the energy levels of C-O stretches are delicately affected by the kind of central metal ion. Since such detailed information is not obtained from the IR spectra alone, the VCD spectrum can probe the effect of the central metal ion on interligand cooperative vibration modes.

Symbiotic Stars in X-rays

NASA Technical Reports Server (NTRS)

Luna, G. J. M.; Sokoloski, J. L.; Mukai, K.; Nelson, T.

2014-01-01

Until recently, symbiotic binary systems in which a white dwarf accretes from a red giant were thought to be mainly a soft X-ray population. Here we describe the detection with the X-ray Telescope (XRT) on the Swift satellite of 9 white dwarf symbiotics that were not previously known to be X-ray sources and one that was previously detected as a supersoft X-ray source. The 9 new X-ray detections were the result of a survey of 41 symbiotic stars, and they increase the number of symbiotic stars known to be X-ray sources by approximately 30%. Swift/XRT detected all of the new X-ray sources at energies greater than 2 keV. Their X-ray spectra are consistent with thermal emission and fall naturally into three distinct groups. The first group contains those sources with a single, highly absorbed hard component, which we identify as probably coming from an accretion-disk boundary layer. The second group is composed of those sources with a single, soft X-ray spectral component, which likely arises in a region where low-velocity shocks produce X-ray emission, i.e. a colliding-wind region. The third group consists of those sources with both hard and soft X-ray spectral components. We also find that unlike in the optical, where rapid, stochastic brightness variations from the accretion disk typically are not seen, detectable UV flickering is a common property of symbiotic stars. Supporting our physical interpretation of the two X-ray spectral components, simultaneous Swift UV photometry shows that symbiotic stars with harder X-ray emission tend to have stronger UV flickering, which is usually associated with accretion through a disk. To place these new observations in the context of previous work on X-ray emission from symbiotic stars, we modified and extended the alpha/beta/gamma classification scheme for symbiotic-star X-ray spectra that was introduced by Muerset et al. based upon observations with the ROSAT satellite, to include a new sigma classification for sources with

X-ray laser

DOEpatents

Nilsen, Joseph

1991-01-01

An X-ray laser (10) that lases between the K edges of carbon and oxygen, i.e. between 44 and 23 Angstroms, is provided. The laser comprises a silicon (12) and dysprosium (14) foil combination (16) that is driven by two beams (18, 20) of intense line focused (22, 24) optical laser radiation. Ground state nickel-like dysprosium ions (34) are resonantly photo-pumped to their upper X-ray laser state by line emission from hydrogen-like silicon ions (32). The novel X-ray laser should prove especially useful for the microscopy of biological specimens.

The Maximal C3 Self-Complementary Trinucleotide Circular Code X in Genes of Bacteria, Archaea, Eukaryotes, Plasmids and Viruses

PubMed Central

Michel, Christian J.

2017-01-01

In 1996, a set X of 20 trinucleotides was identified in genes of both prokaryotes and eukaryotes which has on average the highest occurrence in reading frame compared to its two shifted frames. Furthermore, this set X has an interesting mathematical property as X is a maximal C3 self-complementary trinucleotide circular code. In 2015, by quantifying the inspection approach used in 1996, the circular code X was confirmed in the genes of bacteria and eukaryotes and was also identified in the genes of plasmids and viruses. The method was based on the preferential occurrence of trinucleotides among the three frames at the gene population level. We extend here this definition at the gene level. This new statistical approach considers all the genes, i.e., of large and small lengths, with the same weight for searching the circular code X. As a consequence, the concept of circular code, in particular the reading frame retrieval, is directly associated to each gene. At the gene level, the circular code X is strengthened in the genes of bacteria, eukaryotes, plasmids, and viruses, and is now also identified in the genes of archaea. The genes of mitochondria and chloroplasts contain a subset of the circular code X. Finally, by studying viral genes, the circular code X was found in DNA genomes, RNA genomes, double-stranded genomes, and single-stranded genomes. PMID:28420220

Optical and biological properties of plasma-treated Neurospora crassa spores as studied by absorption, circular dichroism, and Raman spectroscopy

NASA Astrophysics Data System (ADS)

Lee, Geon Joon; Park, Gyungsoon; Choi, Eun Ha

2017-11-01

We studied the effect of plasma treatment on the optical, structural and biological properties of Neurospora crassa ( N. crassa) spores. An atmospheric-pressure plasma jet (APPJ) was used to generate reactive oxygen and nitrogen species in aqueous solution. The APPJ treatment of N. crassa spores in water significantly reduced the viability of spores. The reduction in the spore viability can be attributed to the reactive species from the plasma itself and those derived from the reaction of plasma radicals with aqueous solution. These structural modifications were contingent on the medium in which N. crassa spores were suspended; plasma treatment of N. crassa spores in PBS did not significantly affect the viability of spores as compared with N. crassa spores in water. Scanning electron microscopy images and circular dichroism spectra indicated that the spore cell wall was damaged by plasma treatment. The optical absorption spectrum of untreated N. crassa spores exhibited two resonance absorption bands at approximately λ1 ≈ 260 nm and λ2 ≈ 472 nm, originating from deoxyribonucleic acid (DNA) and β-carotene. The Raman spectrum of untreated N. crassa spores exhibited three main peaks at 1519, 1157 and 1006 cm -1, attributed to β-carotene inside the cell wall. The Raman spectra showed that the APPJ treatment of N. crassa spores in water caused degradation of β-carotene, affecting the viability of spores.

Observation of femtosecond X-ray interactions with matter using an X-ray–X-ray pump–probe scheme

PubMed Central

Inoue, Ichiro; Inubushi, Yuichi; Sato, Takahiro; Tono, Kensuke; Katayama, Tetsuo; Kameshima, Takashi; Ogawa, Kanade; Togashi, Tadashi; Owada, Shigeki; Amemiya, Yoshiyuki; Tanaka, Takashi; Hara, Toru

2016-01-01

Resolution in the X-ray structure determination of noncrystalline samples has been limited to several tens of nanometers, because deep X-ray irradiation required for enhanced resolution causes radiation damage to samples. However, theoretical studies predict that the femtosecond (fs) durations of X-ray free-electron laser (XFEL) pulses make it possible to record scattering signals before the initiation of X-ray damage processes; thus, an ultraintense X-ray beam can be used beyond the conventional limit of radiation dose. Here, we verify this scenario by directly observing femtosecond X-ray damage processes in diamond irradiated with extraordinarily intense (∼1019 W/cm2) XFEL pulses. An X-ray pump–probe diffraction scheme was developed in this study; tightly focused double–5-fs XFEL pulses with time separations ranging from sub-fs to 80 fs were used to excite (i.e., pump) the diamond and characterize (i.e., probe) the temporal changes of the crystalline structures through Bragg reflection. It was found that the pump and probe diffraction intensities remain almost constant for shorter time separations of the double pulse, whereas the probe diffraction intensities decreased after 20 fs following pump pulse irradiation due to the X-ray–induced atomic displacement. This result indicates that sub-10-fs XFEL pulses enable conductions of damageless structural determinations and supports the validity of the theoretical predictions of ultraintense X-ray–matter interactions. The X-ray pump–probe scheme demonstrated here would be effective for understanding ultraintense X-ray–matter interactions, which will greatly stimulate advanced XFEL applications, such as atomic structure determination of a single molecule and generation of exotic matters with high energy densities. PMID:26811449

X ray spectra of X Per. [oso-8 observations

NASA Technical Reports Server (NTRS)

Becker, R. H.; Boldt, E. A.; Holt, S. S.; Pravdo, S. H.; Robinson-Saba, J.; Serlemitsos, P. J.; Swank, J. H.

1978-01-01

The cosmic X-ray spectroscopy experiment on OSO-8 observed X Per for twenty days during two observations in Feb. 1976 and Feb. 1977. The spectrum of X Per varies in phase with its 13.9 min period, hardening significantly at X-ray minimum. Unlike other X-ray binary pulsar spectra, X Per's spectra do not exhibit iron line emission or strong absorption features. The data show no evidence for a 22 hour periodicity in the X-ray intensity of X Per. These results indicate that the X-ray emission from X Per may be originating from a neutron star in a low density region far from the optically identified Be star.

Effects of structural distortion induced by Sc substitution in LuFe2O4